A photocatalytic material, a manufacturing method thereof, and an application thereof

Abstract

A kind of photocatalytic material, its manufacturing method and application, the manufacturing method of photocatalytic material includes the following steps: 1) provide photocatalytic material precursor covered by liquid film, 2) to photocatalytic material precursor irradiation wavelength is 200nm below ray, obtain photocatalytic material.The photocatalytic material has the advantages such as simple manufacturing method and the response value of long wavelength light is significantly improved.

Description

Photocatalytic material, manufacturing method and application thereof Technical Field

[0001] The present invention relates to the field of photocatalytic technology, and in particular to a photocatalytic material, a manufacturing method thereof and applications thereof. Background Art

[0002] Among all semiconductor metal oxide catalysts, TiO2 boasts not only high catalytic activity but also low cost, non-toxicity, and high stability, making it the most promising photocatalyst. TiO2 is an n-type semiconductor and exists in three crystal forms: anatase, rutile, and brookite. Rutile is the most thermodynamically stable of the three. Anatase and brookite titanium oxides can be transformed into rutile upon calcination at temperatures between 600 and 800°C. The band gaps of rutile, anatase, and brookite titanium oxides are 3.02 eV, 3.20 eV, and 3.14 eV, respectively, with anatase exhibiting the highest photocatalytic activity.

[0003] However, its large bandgap (3.0-3.2 eV) limits its response to ultraviolet light, which accounts for only 5% of sunlight's energy. Consequently, its practical applications are significantly limited. Furthermore, TiO2's high photogenerated electron-hole recombination rate also restricts its use in photocatalytic technology. Therefore, there is an urgent need to develop TiO2 catalysts with high visible light catalytic activity.

[0004] Among many methods, halogen doping can effectively improve the photocatalytic performance of TiO2, and has the advantages of low cost and simple preparation method. Halogen doping can enhance the visible light absorption ability of TiO2 and promote the separation of photogenerated charges. Halogen-doped TiO2 includes F-doping, Cl-doping, Br-doping and I-doping. Among them, F-doped and I-doped TiO2 have high visible light catalytic performance and are easy to prepare, making them popular research objects. In comparison, there are fewer preparation methods for Cl-doped and Br-doped TiO2, and their visible light catalytic activity is low. Cl-doped and Br-doped TiO2 catalysts with high visible light catalytic activity are difficult to prepare using simple methods.

[0005] F doping of TiO2 will enhance its surface acidity and visible light absorption, although it will not significantly change its band gap. - Can replace O atoms. - and Ti 4+ The charge compensation effect between 3+ The formation of Ti 3+The presence of I can inhibit the recombination of photogenerated electrons and holes in TiO2. In addition, F doping can also increase the annealing temperature of the transformation of anatase phase TiO2 to rutile phase. I doping and F doping have different mechanisms of action. 5+ and Ti 4+ The radii are almost the same, and in terms of atomic radius matching, Ti 4+ Can be easily I 5+ I doping can change the band gap of titanium oxide and inhibit the recombination of photogenerated electrons and holes. Through first-principles calculations, it is speculated that in I-doped TiO2, its light absorption range is extended from the ultraviolet to the visible light region, which is the reason for the I 5p with I 5s The orbital is the same as that of O in titanium oxide 2P and Ti 3d This is caused by orbital hybridization.

[0006] In their paper "Preparation and Photocatalytic Performance of Nitrogen-Halogen Co-doped Nano-TiO2," Zheng Yafang et al. provide a method for preparing halogen- and nitrogen-codoped TiO2 using a sol-gel method. First, use a graduated cylinder to measure 17 mL of butyl titanate and 59.5 mL of anhydrous ethanol to obtain a mixed solution A. After stirring at medium speed on a magnetic stirrer for 10 minutes, pour solution A into a separatory funnel for later use. Use a graduated cylinder to measure 59.5 mL of anhydrous ethanol, 6.8 mL of deionized water, and 6.8 mL of glacial acetic acid into a three-necked flask to obtain a mixed solution B. A certain amount of the doping reagents used are added to solution B: ammonium fluoride, ammonium chloride, ammonium bromide, and ammonium iodide. Set the water temperature to 25°C and mechanically stir solution B in a constant-temperature water bath until uniformly mixed. Adjust the pH of solution B to ≤3 with concentrated nitric acid. Still in a water bath at 25°C with mechanical stirring, solution A in the separatory funnel was added to solution B at a rate of 1 drop / second. Stirring was continued for 1 hour after the addition was complete. The sol was placed in a conical flask, sealed with plastic wrap, and allowed to gel at room temperature. After gelation, the sample was dried in an electric forced-air drying oven at 80°C for 20 hours. The resulting sample was ground into a powder and calcined in a box-type resistance furnace at a constant temperature for 2 hours to produce a co-doped titanium dioxide photocatalyst powder. UV-visible diffuse reflectance spectroscopy analysis showed that the nitrogen-fluorine doped photocatalyst had the strongest response to visible light. Performance tests revealed that the optimal performance was achieved at a doping level of 0.15, with a dark adsorption removal efficiency of 48.3% and a total removal efficiency of 79.4% for methylene blue. The visible light photocatalytic activity of the other doped photocatalysts was very poor, with total methylene blue removal efficiencies consistently less than 20%. Furthermore, the visible light activity of the nitrogen-chlorine-, nitrogen-bromine-, and nitrogen-iodine-doped photocatalysts varied little with the doping level.

[0007] CN1259129C discloses a bromine-doped photocatalytic polycrystalline material exhibiting photocatalytic activity under visible light conditions, belonging to the field of inorganic nanophotocatalytic materials. The material is composed of the following three elements: titanium, oxygen, and bromine, with the weight percentages being: titanium at 54.55%-59.90%, oxygen at 35.45%-40.00%, and bromine at 0.10%-10.00%. Bromine exists in the photocatalytic polycrystalline material in both non-bonded and bonded forms. When bonded, bromine and titanium form Ti-Br chemical bonds within the crystal lattice of the photocatalytic crystal material; when non-bonded, bromine is intercalated within the interstitial spaces of the photocatalytic crystal material. Bromine doping reduces the material's original bandgap to a level that can utilize visible light (400-800nm). Because the material possesses a bandgap wide enough to be excited by visible light irradiation, it achieves full-band absorption of visible light and exhibits high catalytic activity under visible light. Summary of the Invention

[0008] Photocatalytic technology has potential applications in areas such as pollutant degradation (VOCs and wastewater), photocatalytic water splitting to produce hydrogen, carbon dioxide reduction to produce chemicals, reforming to produce synthesis gas, nitrogen fixation, and alkane conversion. However, in the field of VOC treatment, the application of high-volume, low-concentration VOC degradation remains a challenge.

[0009] In actual applications, the light sources commonly used for photocatalytic degradation of VOCs include mercury lamps, UV-LEDs, and sunlight. In ordinary mercury lamps, 254nm ultraviolet light accounts for 70% of the total energy, and another 30% is long-wave light, including long-wave ultraviolet light and visible light. In addition to ultraviolet and visible light, sunlight also contains about 43% infrared light. Therefore, photocatalysts that can simultaneously match the visible light / infrared light response of multiple light sources have high practical value.

[0010] The inventors of the present invention have found that after a photocatalyst precursor is mixed with a salt containing a dopant element in a solution, the doped element can be doped into the photocatalyst precursor lattice under vacuum ultraviolet light irradiation, forming defects and doping (oxygen vacancies, hydroxyl groups, Ti 3+ and metal / non-metal doping, etc.). It can be matched with a variety of light sources (low / medium pressure mercury lamp UV light source, UV-LED light source, sunlight, etc.), and has excellent industrial application prospects.

[0011] For oxygen-containing photocatalysts, the formation of oxygen vacancies will result in the localization of one or two electrons at their location. The localized electrons will have a direct impact on the electronic structure, thereby generating an intermediate energy level below the conduction band. For example, for TiO2, this energy level is located at 0.75-1.18eV below the conduction band. Only a small amount of photon energy is needed to excite the electrons in the valence band from the top of the valence band to the intermediate state. The electrons in the intermediate state will continue to transition to the conduction band under very small energy excitation. The lower energy required for the two transitions can be met by visible light or infrared light, thereby broadening and enhancing the absorption of visible light and infrared light by the photocatalyst. Similarly, -OH and Ti 3+ It can also form similar intermediate energy levels, thereby expanding the visible light / infrared light absorption range.

[0012] When the doping element is a non-metal, such as B, C, N, S, or F, its 2p orbital is close in energy to the oxygen in the original photocatalyst. Hybridization of the two 2p orbitals shifts the valence band upward, narrowing the band gap and thus expanding the light absorption range. Doping with non-metallic elements also prevents the recombination of photogenerated electrons and holes.

[0013] Precious metals (Au, Pt, Ag, Pd, etc.) possess plasmon resonance absorption properties. When doped into nano-photocatalytic materials, they can broaden the photocatalyst's absorption of visible light. Precious metals can also form Schottky barriers at the interface with photocatalysts, such as TiO2, effectively promoting the separation of photogenerated electrons and holes, thereby improving their photocatalytic efficiency.

[0014] After doping with metal elements (Se, Mn, Fe, Co, Ni, Cu, Zn, etc.), a donor energy level can be generated above the valence band of the photocatalyst, or an acceptor energy level can be generated below the valence band. When it is irradiated with light, in addition to the electron excitation from the valence band to the conduction band, the electrons will also jump from the donor energy level to the conduction band, or from the valence band to the acceptor energy level generated by the doping, thereby enabling the semiconductor to absorb visible light. For example, after TiO2 is doped with a transition metal containing a 3d electron orbital, an occupied state of a t2g orbital can be generated in the middle of the forbidden band, and electrons can jump between the t2g energy level and the valence band (conduction band). In addition, metal doping can form a capture center with a valence state higher than that of TiO2. 4+ The metal ions capture electrons and have a valence lower than Ti 4+ The metal ions in the electrolyte capture holes, thereby suppressing the electron-hole recombination.

[0015] Current research shows that when two or more elements are co-doped, a synergistic effect may occur, making the photocatalytic performance significantly higher than that of a single doping.

[0016] Specifically, in response to the above-mentioned various defects and doping, the present invention relates to the following aspects.

[0017] 1. A photocatalytic material comprising titanium dioxide, wherein the surface Ti 3+ Content and surface Ti 4+ The content ratio is 1:19-19:1 (preferably 1:4-4:1), and in its ultraviolet-visible diffuse reflectance spectrum, the absorbance of light with a wavelength of 760nm is 0.20-2.0 (preferably 0.30-1.8), the absorbance of light with a wavelength of 800nm ​​is 0.25-1.8 (preferably 0.35-1.6), and the absorbance of light with a wavelength of 850nm is 0.25-1.7 (preferably 0.35-1.5).

[0018] 2. The photocatalytic material according to any of the preceding or following aspects has a particle size distribution range of 5-150 nm (preferably 10-110 nm) or an average particle size of 20-85 nm (preferably 30-70 nm) as measured by SEM.

[0019] 3. The photocatalytic material according to any of the above or the following aspects, wherein the surface Ti measured by XPS method 3+ The content is 5%-95% (preferably 20%-80%), and the surface Ti measured by XPS method 4+ The content is 5%-95% (preferably 20%-80%), and / or, after fitting the O1s peak of the XPS measurement, the oxygen vacancy O V The content of the peak is 10%-80% (preferably 15%-60%), and / or, the mass loss percentage measured by thermogravimetric analysis at 300°C is 0.2-7wt% (preferably 0.5-5wt%), and / or, the surface hydroxyl content measured by infrared spectroscopy is 0.03-3mmo l / g (preferably 0.05-1.5mmo l / g), and / or, the surface Ti content after 100°C deionized water cycle washing is 3+ The content loss rate is less than 2% (preferably less than 1%).

[0020] 4. The photocatalytic material according to any of the above or the following aspects further comprises an element selected from the periodic table II At least one doping element selected from Group IA elements (preferably at least one of B and Ga), Group IVA elements of the periodic table (preferably at least one of C and Ge), Group VA elements of the periodic table (preferably at least one of N and P), non-oxygen elements of Group VIA of the periodic table (preferably at least one of S and Se), Group VIIA elements of the periodic table (preferably F), non-noble transition metal elements of the periodic table other than Ti (preferably selected from at least one of Mn, Fe, Co, Ni, Cu, and Zn), noble metal elements of the periodic table (preferably selected from at least one of Ag, Au, Pd, and Pt), and rare earth metal elements of the periodic table (preferably selected from at least one of Ce, La, Nd, and Gd), preferably at least one doping element selected from N, Mn, and F, particularly preferably simultaneously containing N, Mn, and F as doping elements, and / or, based on the total weight of the photocatalytic material, the content of the doping elements (calculated as elements) alone or in total is 0.01-15 wt% (preferably 0.01-10 wt% or 0.1-5 wt%).

[0021] 5. The photocatalytic material according to any of the preceding or following aspects, wherein the doping is surface doping, and / or the F doping is alternative oxygen doping or a mixture of interstitial doping and alternative oxygen doping (preferably alternative oxygen doping), and / or the N doping includes lattice doping and interstitial doping, wherein the proportion of the lattice doping in the overall doping is 80-20% (preferably 70-30%), the proportion of the interstitial doping in the overall doping is 20-80% (preferably 30-70%), and the sum of the two is 100%, and / or the doping elements observable by spherical aberration electron microscopy are distributed in a single atom.

[0022] 6. A method for producing a photocatalytic material, comprising the following steps:

[0023] 1) providing a photocatalytic material precursor covered by a liquid film,

[0024] 2) irradiating the photocatalytic material precursor with radiation (preferably vacuum ultraviolet light) having a wavelength of less than 200 nm (preferably 100-200 nm or 120-200 nm) to obtain the photocatalytic material.

[0025] 7. The manufacturing method described in any of the preceding or following aspects, wherein the operating conditions of the irradiation include: an operating temperature of -50-95°C (preferably 10-70°C), an operating pressure of 0-1 MPaG (preferably 0-0.1 MPaG), a lower limit of the duration of 0.1 h (preferably 1 h, 2 h or 3 h), and an upper limit of the duration of 120 h (preferably 60 h, 36 h, 20 h, 15 h or 10 h).

[0026] 8. The manufacturing method described in any of the above or below aspects, wherein the photocatalytic material precursor is selected from at least one of sulfide-type photocatalytic materials and their precursors, metal oxide-type photocatalytic materials and their precursors, carbon nitride-based photocatalytic materials and their precursors, metal oxygenates and their precursors, and composite materials of these photocatalytic materials and their precursors, and is particularly preferably selected from at least one of TiO2, ZrO2, ZnO, BiVO4, WO3, SnO2, and composite materials of these photocatalytic materials and their precursors, and is more preferably selected from at least one of titanium dioxide and its precursors, and / or, based on the total weight of the photocatalytic material precursor, the photocatalytic material precursor contains more than 80wt% (preferably 80-99.9wt% or 85-99.5wt%) of titanium dioxide.

[0027] 9. The manufacturing method described in any of the above or below aspects, wherein the photocatalytic material precursor is in the form of solid particles, and the particle size distribution range of the solid particles measured by SEM method is 5-150nm (preferably 10-110nm) or the average particle size is 20-85nm (preferably 30-70nm).

[0028] 10. The manufacturing method according to any one of the preceding or following aspects, wherein the average thickness of the liquid film is 0.5-200 mm (preferably 1-120 mm or 5-80 mm).

[0029] 11. The production method according to any one of the preceding or following aspects, wherein the irradiation is performed under an inert gas atmosphere, preferably under the condition of aeration with an inert gas flow or a nitrogen flow.

[0030] 12. The manufacturing method according to any one of the preceding or following aspects, wherein the irradiation dose is 0.01-50 W / g (preferably 0.1-20 W / g), and the irradiation power of the rays is 0.1-200 W (preferably 1-50 W).

[0031] 13. The manufacturing method according to any one of the preceding or following aspects, wherein the mass ratio of the liquid to the photocatalytic material precursor is 0.1-10000:1 (preferably 2-5000:1, more preferably 5-1000:1).

[0032] 14. The manufacturing method according to any of the above or the following aspects, wherein the liquid further comprises an element selected from the group consisting of elements of Group IIIA of the Periodic Table (preferably at least one of B and Ga), elements of Group IVA of the Periodic Table (preferably at least one of C and Ge), elements of Group VA of the Periodic Table (preferably at least one of N and P), non-oxygen elements of Group VIA of the Periodic Table (preferably at least one of S and Se), elements of Group VIIA of the Periodic Table (preferably F), non-noble transition metal elements of the Periodic Table other than Ti (preferably selected from the group consisting of Mn, Fe, Co, Ni, Cu, Zn, ), at least one doping element selected from the group consisting of precious metal elements of the periodic table (preferably at least one selected from Ag, Au, Pd and Pt) and rare earth metal elements of the periodic table (preferably at least one selected from Ce, La, Nd, Gd), preferably at least one doping element selected from N, Mn and F, particularly preferably comprising N, Mn and F as doping elements, and based on the total weight of the photocatalytic material precursor, the amount of the doping elements (calculated as elements) used individually or in total is 0.01-1000wt% (preferably 0.1-200wt%).

[0033] 15. The manufacturing method according to any one of the preceding or following aspects further comprises the step of irradiating the photocatalytic material precursor with ultraviolet light having a wavelength of 200-400 nm.

[0034] 16. The manufacturing method according to any one of the preceding or following aspects, wherein the ratio of the ultraviolet light to the radiation is 1:1-30:1 (preferably 3:1-20:1).

[0035] 17. In the production method described in any one of the preceding or following aspects, the photocatalytic material is not subjected to a heat treatment at 300° C. or higher (preferably 200° C. or higher).

[0036] 18. A photocatalytic product (such as photocatalytic particles, photocatalytic plates or photocatalytic films) comprising the photocatalytic material described in any one of the preceding or following aspects or a photocatalytic material manufactured by the manufacturing method described in any one of the preceding or following aspects.

[0037] 19. A photocatalytic conversion method, comprising the step of irradiating a raw material to be converted (such as a VOCs-containing gas or hydrocarbon) with light in the presence of the photocatalytic material described in any of the preceding or following aspects, the photocatalytic material manufactured by the manufacturing method described in any of the preceding or following aspects, or the photocatalytic product described in any of the preceding or following aspects. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] FIG1 is a graph showing the UV-visible diffuse reflectance spectra of the products of Comparative Example 1, Example 8, and Example 36.

[0039] Technical Effects

[0040] Compared with the prior art, the present invention has the following advantages:

[0041] According to the present invention, other non-metallic, metallic or precious metal elements can be successfully doped into the photocatalytic precursor, and a certain number of other valence metal cations, oxygen vacancies and hydroxyl groups can be generated. At the same time, a variety of defects / doping are formed that are beneficial to expanding the light response range and promoting electron-hole separation, so that the material has visible light and infrared light response, and has high practical value.

[0042] For example, the F and N doped titanium oxide of the present invention, F is doped into the titanium oxide lattice structure in the form of replacing oxygen, and N is interstitial doping and lattice doping, and Ti 3+ , oxygen vacancies and -OH; the formation of oxygen vacancies can produce an intermediate state energy level below the conduction band; after N doping, its 2p orbital energy is close to that of O in the original photocatalyst, and after the 2p orbitals of the two are hybridized, the valence band moves up and the band gap is shortened; oxygen vacancies and nitrogen doping can play a role in expanding the light absorption range. F doping can not only promote the separation of photogenerated electrons and holes, but also promote the 3+ and the formation of oxygen vacancies. -OH and Ti 3+ It can also form similar intermediate energy levels, thereby expanding the visible light / infrared light absorption range. DETAILED DESCRIPTION

[0043] The specific embodiments of the present invention are described in detail below. However, it should be noted that the protection scope of the present invention is not limited by these specific embodiments, but is determined by the claims in the appendix.

[0044] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In the event of conflict, the definitions in this specification will prevail.

[0045] When this specification uses the prefix "well known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, the objects introduced by the prefix include those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become generally recognized in the art to be suitable for similar purposes.

[0046] In the context of the present invention, all numerical values ​​for parameters (eg, amounts or conditions) are to be understood as being modified in all instances by the term "about," regardless of whether "about" actually appears before the numerical value.

[0047] In the context of the present invention, unless otherwise specified, the various devices used in the present invention may use structures conventionally selected in the art without particular limitation.

[0048] In the context of the present invention, “substantially” means that deviations that are acceptable or reasonable to those skilled in the art are allowed, such as deviations within ±2%, within ±1.5%, within ±1%, within ±0.5% or within ±0.1%.

[0049] In the context of the present invention, a scanning electron microscope is used to perform statistical analysis on the particle size distribution range or average particle size. The scanning electron microscope (SEM) instrument model is a Hitachi S-4800, and the secondary electron resolution of the device is 1.4nm (1kV), 1.0nm (15kV), the electron gun is a cold field emission electron source, and the magnification is 20-800,000. The catalyst powder to be tested is adhered to a conductive adhesive, compacted, and then sprayed with gold to make a sample for testing to observe the surface structure of the catalyst and measure the particle size. The particle size is measured and statistically analyzed using NanoMeasurer software.

[0050] In the context of the present invention, the surface Ti 3+ and Ti 4+ The content, loss rate, oxygen vacancies and doping type are measured by X-ray photoelectron spectroscopy (XPS).

[0051] XPS is an elemental analysis technique. X-rays of a certain energy are irradiated onto the sample surface and interact with the substance to be tested, causing the sample to emit electrons with characteristic energy. This process can be expressed by the following formula: hγ=E k +E b +E r

[0052] hγ: energy of the X-ray; E k : energy of photoelectrons; E b : binding energy of electrons; E r : The recoil energy of the atom. r Very small, negligible. It can analyze the chemical composition of a sample. X-ray photoelectron spectroscopy uses an incident beam of X-rays, which interact with atoms on the sample surface, exciting and ionizing the electrons in the inner shells of the atoms within the sample. This allows for the analysis of the composition and structure of all elements in the sample, excluding hydrogen and helium.

[0053] According to the measurement method of the present invention, the X-ray photoelectron spectrometer is a Thermo Fisher Multilab 2000, with a Mg / Al double anode as the X-ray source, and the vacuum degree in the analysis chamber is 5×10 -10 mbar, and the vacuum degree is obtained by two turbomolecular pumps; the equipment detector is a single-channel electron multiplier; the electron energy analyzer is a hemispherical sector analyzer; after the sample is gently ground, it is pressed into a tablet, and the resulting flat, uniform, and compact sample is sent into the analysis chamber for testing. XPS is used to analyze the elemental composition, valence state, and doping method of the product. Combined with literature information, the type of element and valence state and other information can be judged based on the position and line shape of the peak. For example, the peak near 530eV usually corresponds to the O1s electronic energy level, and the asymmetric Gaussian line shape indicates that it is composed of a variety of oxygen bonding states superimposed. At this time, the content information of O corresponding to different existence states can be obtained by fitting; for example, after fitting the O1s of a certain titanium oxide, peaks of 532.2, 531.2, and 530.2eV are obtained. Combined with literature information, the three peaks correspond to adsorbed oxygen (O a ), oxygen vacancies (O v ) lattice oxygen (O L ). The same method can also be used to obtain Ti 3+ and Ti 4+ According to the peak area, Ti 3+ and oxygen vacancies (O v ) and other active sites. The peaks near 399eV and 699eV correspond to F1s and N1s, respectively. Separating these peaks reveals the signal peaks for interstitial doping and substitutional oxygen doping, respectively. For F, the interstitial and substitutional oxygen doping peaks are located near 685.3eV and 687.8eV, respectively, while the interstitial and substitutional oxygen doping peaks for N are located near 399.3eV and 396.0eV, respectively.

[0054] In the context of the present invention, the mass loss percentage is measured by thermogravimetric analysis (TGA). TGA analysis of the samples was performed using a Perkin Elliner PE 2400II thermogravimetric analyzer (USA). Experimental conditions included an N2 atmosphere, a test temperature range of 50-400°C, a heating rate of 10°C / min, and a test sample weight of 10 ± 1 mg.

[0055] In the context of the present invention, the surface hydroxyl content is measured using infrared spectroscopy. Infrared light irradiated on an object can cause the covalent bonds within the molecules of the substance to vibrate or rotate. The infrared light absorbed during vibration has a specific wavelength, so infrared spectroscopy can obtain information such as skeleton vibration and surface groups. The samples were tested using an Agilent Cary 630 infrared spectrometer with a wavelength range of 400-4000 cm -1Before testing, the powder sample was mixed with KBr at a ratio of 1:200 and ground evenly. The sample was directly pressed into a uniform and transparent sheet using a tablet press for testing. The step length was set to 2 cm. -1 , background was subtracted with KBr.

[0056] In the context of the present invention, the absorbance of the photocatalyst at different wavelengths of light was measured using solid-state UV-visible diffuse reflectance spectroscopy. UV-visible diffuse reflectance absorption spectroscopy is an important technique for analyzing the electronic structure of semiconductor photocatalysts, which is closely related to their photocatalytic activity. The sample was placed in the integrating sphere of a spectrophotometer (UV-2600, Shimadzu Corporation, Japan), using BaSO₄ as a reference. The excitation wavelength was set to 200-900 nm, and the scanning speed was 1000 nm / min.

[0057] In the context of this invention, the structure of the prepared single-atom dispersed photocatalyst samples was characterized using in situ aberration-corrected transmission electron microscopy (ACTEM) (JEOL JEM-ARM200F, Japan). Before testing, a small amount of sample was dispersed in ethanol and ultrasonically dispersed evenly. A small amount of the suspension was dropped onto a copper grid using a rubber-tipped dropper. After vacuum drying, the sample was placed in a vacuum chamber and tested at an accelerating voltage of 200 kV.

[0058] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight and pressure is gauge pressure.

[0059] In the context of the present invention, any two or more embodiments or aspects of the present invention may be arbitrarily combined, and the technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the scope of protection of the present invention.

[0060] According to one embodiment of the present invention, a photocatalytic material is provided. According to the present invention, the photocatalytic material can exhibit chemical reaction catalytic performance under light irradiation.

[0061] According to one embodiment of the present invention, the photocatalytic material comprises titanium dioxide. Preferably, the photocatalytic material comprises at least 80 wt% (preferably 80-99.9 wt% or 85-99.5 wt%) of titanium dioxide, based on the total weight of the photocatalytic material. The titanium dioxide is anatase, rutile, or a mixture of the two.

[0062] According to one embodiment of the present invention, the surface Ti of the photocatalytic material measured by XPS method is 3+ Content and surface Ti 4+ The content ratio is 1:19-19:1 (preferably 1:4-4:1). More specifically, the surface Ti content of the photocatalytic material measured by XPS is3+ The content is generally 5%-95% (preferably 20%-80%), and the surface Ti measured by XPS method is 4+ The content is generally 5%-95% (preferably 20%-80%).

[0063] According to one embodiment of the present invention, the surface oxygen vacancies O of the photocatalytic material measured by XPS are V The content of the peak is 10%-80% (preferably 15%-60%).

[0064] According to one embodiment of the present invention, the photocatalytic material exhibits an absorbance of 0.20-2.0 (preferably 0.30-1.8) at a wavelength of 760 nm, 0.25-1.8 (preferably 0.35-1.6) at a wavelength of 800 nm, and 0.25-1.7 (preferably 0.35-1.5) at a wavelength of 850 nm in its UV-visible diffuse reflectance spectrum. The photocatalytic material of the present invention has a high utilization rate for visible light and even infrared light, significantly improving its light response compared to original titanium oxide.

[0065] According to one embodiment of the present invention, the photocatalytic material is in any form selected from particles, powders, plates, strips and heteromorphic shapes (preferably particles). Optionally, the photocatalytic material can be a solid or hollow solid.

[0066] According to one embodiment of the present invention, the photocatalytic material exhibits a mass loss of 0.2-7 wt% (preferably 0.5-5 wt%) as measured by thermogravimetric analysis at 300°C. This measurement indicates that the photocatalytic material of the present invention contains a certain degree of thermally volatile components; without being bound by any theory, the inventors believe that these thermally volatile components may be due to hydroxyl groups or bound water on the photocatalytic material. As evidence, the surface hydroxyl content of the photocatalytic material of the present invention, as measured by infrared spectroscopy, is generally 0.03-3 mmol / g (preferably 0.05-1.5 mmol / g).

[0067] According to one embodiment of the present invention, the particle size distribution range of the photocatalytic material measured by SEM method is 5-150 nm (preferably 10-110 nm) or the average particle size is 20-85 nm (preferably 30-70 nm).

[0068] According to one embodiment of the present invention, the surface Ti of the photocatalytic material after being washed 10 times with deionized water at 100°C is 3+ The content loss rate is less than 2% (preferably less than 1%). This measurement shows that on the surface of the photocatalytic material of the present invention, Ti 3+ It is combined in the form of chemical bonds, thus showing strong resistance to cyclic washing.

[0069] According to one embodiment of the present invention, the photocatalytic material may also contain various doping elements or any combination thereof conventionally used in the art in the manufacture of photocatalytic materials, such as at least one doping element selected from the group consisting of elements of Group IIIA of the Periodic Table, elements of Group IVA of the Periodic Table, elements of Group VA of the Periodic Table, non-oxygen elements of Group VIA of the Periodic Table, elements of Group VIIA of the Periodic Table, non-precious transition metal elements other than Ti in the Periodic Table, precious metal elements in the Periodic Table, and rare earth metal elements in the Periodic Table.

[0070] According to one embodiment of the present invention, the Group IIIA element of the Periodic Table is preferably at least one of B and Ga. The Group IVA element of the Periodic Table is preferably at least one of C and Ge. The Group VA element of the Periodic Table is preferably at least one of N and P. The non-oxygen element of Group VIA of the Periodic Table is preferably at least one of S and Se. The Group VIIA element of the Periodic Table is preferably F. The non-noble transition metal element of the Periodic Table other than Ti is preferably selected from at least one of Mn, Fe, Co, Ni, Cu, and Zn, with Mn being more preferred. The noble metal element of the Periodic Table is preferably selected from at least one of Ag, Au, Pd, and Pt. The rare earth metal element of the Periodic Table is preferably selected from at least one of Ce, La, Nd, and Gd. The doping element is preferably at least one selected from N, Mn, and F, with a combination of N and F or a combination of N, Mn, and F being particularly preferred. According to the present invention, the photocatalytic precursor is successfully doped with other elements, generating a certain number of other valence metal cations, oxygen vacancies, heterojunctions, and hydroxyl groups, resulting in the material having visible light and even infrared light response.

[0071] According to one embodiment of the present invention, the amount of the doping element, for example, based on the total weight of the photocatalytic material, the content of the doping element (calculated as element) alone or in total is generally 0.01-15wt% (preferably 0.01-10wt% or 0.1-5wt%).

[0072] According to a preferred embodiment of the present invention, F and N doped titanium oxide, F was doped into the titanium oxide lattice structure in the form of replacing oxygen, and N was interstitial doping and lattice doping, and Ti 3+ and oxygen vacancies; F doping can promote the separation of photogenerated electrons and holes; Ti 3+ The introduction of Ti 3+ / Ti 4+ The redox cycle of ion pairs improves the redox performance of the catalyst.

[0073] According to one embodiment of the present invention, in the photocatalytic material, the doping is surface doping. Surface doping herein means that the doping element is substantially distributed on the surface of the photocatalytic material or within a depth of approximately 3 nm from the surface. Furthermore, preferably, when observed using spherical aberration electron microscopy, the doping element (particularly a metal element) is substantially monoatomic in distribution on the surface of the photocatalytic material.

[0074] According to a preferred embodiment of the present invention, in the photocatalytic material, when F doping is included, the F doping is alternative oxygen doping, or a mixture of interstitial doping and alternative oxygen doping, preferably alternative oxygen doping. Alternatively, when N doping is included, the N doping generally includes lattice doping and interstitial doping. Preferably, the proportion of the lattice doping in the overall doping is 80-20% (preferably 70-30%), the proportion of the interstitial doping in the overall doping is 20-80% (preferably 30-70%), and the sum of the two is 100%.

[0075] According to one embodiment of the present invention, a method for producing a photocatalytic material is provided. According to the present invention, the method can be used to produce the aforementioned photocatalytic material of the present invention, but the present invention is not limited to these photocatalytic materials.

[0076] According to one embodiment of the present invention, the method for manufacturing a photocatalytic material comprises step 1): providing a photocatalytic material precursor covered by a liquid film. Preferably, the photocatalytic material precursor is in solid form, not liquid or dissolved.

[0077] According to one embodiment of the present invention, the photocatalytic material precursor is selected from any one of particles, powders, plates, strips and heteromorphic moldings, preferably in the form of particles. For example, the particle size distribution range of the particles measured by SEM is 5-150nm (preferably 10-110nm) or the average particle size is 20-85nm (preferably 30-70nm). The inventors of the present invention have found that if the particle size is too large, the specific surface area is small, and the loading amount of dopant per unit weight is low, resulting in reduced activity; if the particle size is too small, the volume fraction of atoms located on the surface of the particles becomes higher, the surface energy increases, resulting in poor stability of the generated active sites, thereby affecting its reaction activity; in addition, if the particle size is too small, it will also make it difficult for the catalyst to settle, making it difficult to separate.

[0078] According to one embodiment of the present invention, the photocatalytic material precursor is a material or its precursor that can undergo a photochemical reaction under the action of light, preferably selected from sulfide-type photocatalytic materials and their precursors, metal oxide-type photocatalytic materials and their precursors, carbon nitride-based photocatalytic materials and their precursors, metal oxygen-containing salts and their precursors, and at least one of the composite materials of these photocatalytic materials and their precursors, particularly preferably selected from TiO2, ZrO2, ZnO, BiVO4, WO3, SnO2, and at least one of the composite materials of these photocatalytic materials and their precursors, more preferably selected from at least one of titanium dioxide and its precursors. Preferably, based on the total weight of the photocatalytic material precursor, the photocatalytic material precursor contains more than 80wt% (preferably 80-99.9wt% or 85-99.5wt%) of titanium dioxide. As titanium dioxide, it can be anatase type, rutile type or a mixture of the two.

[0079] According to one embodiment of the present invention, the liquid forming the liquid film is insoluble in the photocatalytic material precursor, and is preferably selected from at least one of water, esters and alcohols, in particular water. The water-solid interface phenomenon is very important in natural systems, and the surface wetting process depends on the type and size of the intermolecular forces at the water-solid interface. When the particulate matter is completely immersed in water, its surface is covered with a bound water layer, in which the water molecules are arranged in an orderly manner. In addition to the water in the adsorbed water layer, there are two kinds of water with different properties between the fully infiltrated stacked solid particles, namely: free water and capillary water. Under the action of capillary force, the water retained between the particles is capillary water; the water with ordinary water properties in the gaps between the stacked particles is free water. In the context of the present invention, the thickness of the liquid film is given by the formula d=5*(V L / S) is determined. Where, d is the thickness of the liquid film (mm); V L : Volume of liquid added per gram of photocatalytic material (mL); S: Area of ​​solid-liquid mixture per gram of catalyst particles in the direction of light irradiation (cm 2 ).

[0080] According to the present invention, the photocatalytic material precursor is covered by the liquid film. In order to achieve the technical effect of the present invention, the liquid forms the liquid film on at least the surface of the photocatalytic material precursor, preferably forming a continuous liquid surface. The inventors of the present invention have found that if the thickness of the liquid is too small, doping will be unsuccessful, and it will not have visible light or even infrared light absorption. This may be due to the small amount of wetting liquid, which cannot form a continuous adsorbed water layer, and is easy to evaporate and dry, making it difficult for dopants such as fluorine to contact the catalytic material, or difficult to present an ionic state, and unable to produce active components involved in doping. For this reason, it is preferred that the average thickness of the liquid film is generally 0.5-200mm (preferably 1-120mm or 5-80mm).

[0081] According to one embodiment of the present invention, the method for manufacturing the photocatalytic material includes step 2): irradiating the photocatalytic material precursor with rays having a wavelength of less than 200nm to obtain the photocatalytic material. Preferably, the wavelength of the rays is 100-200nm or 120-200nm, more preferably vacuum ultraviolet light (VUV) of 150-190nm. The inventors of the present invention have found that if the wavelength is too short, the cost of ultraviolet light will increase significantly and it will not be easy to amplify. If the wavelength is too long, the energy of ultraviolet light will decrease and it will not be able to effectively excite the reactants to generate free radicals. According to one embodiment of the present invention, the operating conditions of the irradiation include: an operating temperature of -50-95°C (preferably 10-70°C) and an operating pressure of 0-1MPaG (preferably 0-0.1MPaG).

[0082] According to one embodiment of the present invention, the lower limit of the duration of the irradiation is generally 0.1h (preferably 1h, 2h or 3h), and the upper limit of the duration of the irradiation is generally 120h (preferably 60h, 36h, 20h, 15h or 10h). The inventors of the present invention have found that if the time is too short, the reaction is incomplete and the doping effect is poor. If the time is too long, as the reaction proceeds, intermediate products or by-products continue to increase, the reaction tends to equilibrium, and no more beneficial effects are produced on the product, resulting in waste.

[0083] According to one embodiment of the present invention, to achieve more uniform irradiation, the irradiation is performed while stirring the photocatalytic material precursor covered by the liquid film. According to the present invention, the stirring can be performed in any manner conventionally known in the art and is not particularly limited. For example, the stirring rate is generally 10-1000 rpm.

[0084] According to one embodiment of the present invention, the irradiation is carried out under an inert gas atmosphere, preferably under an inert gas flow or nitrogen flow aeration (for example, an aeration rate of 0.01-10 L / min / g). The inventors of the present invention have found that aeration is beneficial to the active component Ti 3+ formation.

[0085] According to one embodiment of the present invention, the irradiation dose is generally 0.01-50 W / g (preferably 0.1-20 W / g). In addition, the irradiation power of the radiation is generally 0.1-200 W (preferably 1-50 W).

[0086] According to one embodiment of the present invention, the liquid may also contain various doping elements or any combination thereof conventionally used in the art in the manufacture of photocatalytic materials, such as at least one doping element selected from the group consisting of elements of Group IIIA of the Periodic Table, elements of Group IVA of the Periodic Table, elements of Group VA of the Periodic Table, non-oxygen elements of Group VIA of the Periodic Table, elements of Group VIIA of the Periodic Table, non-precious transition metal elements other than Ti in the Periodic Table, precious metal elements in the Periodic Table, and rare earth metal elements in the Periodic Table.

[0087] According to one embodiment of the present invention, the elements of Group IIIA of the Periodic Table are preferably at least one of B and Ga. The elements of Group IVA of the Periodic Table are preferably at least one of C and Ge. The elements of Group VA of the Periodic Table are preferably at least one of N and P. The non-oxygen elements of Group VIA of the Periodic Table are preferably at least one of S and Se. The elements of Group VIIA of the Periodic Table are preferably F. The non-noble transition metal elements of the Periodic Table other than Ti are preferably selected from at least one of Mn, Fe, Co, Ni, Cu, and Zn, more preferably Mn. The noble metal elements of the Periodic Table are preferably selected from at least one of Ag, Au, Pd, and Pt. The rare earth metal elements of the Periodic Table are preferably selected from at least one of Ce, La, Nd, and Gd. As the doping element, at least one selected from N, Mn, and F is preferred, and a combination of N and F or a combination of N, Mn, and F is particularly preferred as the doping element.

[0088] According to one embodiment of the present invention, as described above, the content of the doping elements (calculated as elements) individually or in total is 0.01-15 wt% (preferably 0.01-10 wt% or 0.1-5 wt%) based on the total weight of the photocatalytic material. Therefore, in order to manufacture the photocatalytic material of the present invention, the amount of the doping elements used is such that the content of the doping elements (calculated as elements) individually or in total reaches the numerical range specified in the present invention. There is no particular limitation, but for example, based on the total weight of the photocatalytic material precursor, the amount of the doping elements (calculated as elements) individually or in total is generally 0.01-1000 wt% (preferably 0.1-200 wt%).

[0089] According to a preferred embodiment of the present invention, the inventors of the present invention have found that F doping is very beneficial to the generation of Ti 3+ For example, the amount of F (calculated as an element) is generally 0.01-1000 wt% (preferably 0.1-200 wt%) based on the total weight of the photocatalytic material precursor.

[0090] According to one embodiment of the present invention, the mass ratio of the liquid to the photocatalytic material precursor is such that the photocatalytic material precursor is covered by the liquid film as a minimum requirement, and is generally 0.1-10000:1 (preferably 2-5000:1, and more preferably 5-1000:1). The inventors of the present invention have found that in order to achieve the technical effect of the present invention, the liquid can at least keep the catalyst in a wetted state, preferably forming a continuous liquid surface or having liquid fluidity. The inventors of the present invention have found that if the amount of the liquid is too low, doping will fail, and it will not absorb visible light or even infrared light. This may be due to the small amount of wetting liquid, which cannot form an adsorption liquid layer on the surface of the catalyst, and is easy to evaporate and dry under light irradiation, making it difficult for dopants such as fluorine to be in an ionic state and unable to produce active components involved in doping.

[0091] According to one embodiment of the present invention, the amount of the doping element (calculated as the element) is generally 0.01-1000 wt% (preferably 0.1-200 wt%) based on the total weight of the photocatalytic material precursor. Of course, this amount can be appropriately varied depending on the doping element, which will be readily apparent to those skilled in the art.

[0092] According to one embodiment of the present invention, one or more doping elements are introduced into the liquid at once or in multiple steps. For example, one or more doping elements can be introduced into the liquid before, simultaneously with, or after irradiating the photocatalytic material precursor with the radiation. More specifically, step 2) can be repeated multiple times (e.g., 2-4 times), preferably between two consecutive steps 2), with one or more doping elements introduced into the liquid.

[0093] According to one embodiment of the present invention, the doping element as described above is generally used in the form of a precursor. Preferably, the precursor of the doping element is soluble in the liquid, preferably soluble or easily soluble in water. As the precursor, any compound used as a precursor of the doping element in the art can be used, specifically, for example, lithium fluoride, sodium fluoride, potassium fluoride, potassium bifluoride, sodium bifluoride, lithium bifluoride, ammonium fluoride, ammonium phosphate, potassium permanganate, NaBH4, boron oxide, NaBO2, Ga(NO3)3, polyacrylamide, ethanol, glucose, pyrrole, GeCl4, Na2GeO3, phosphoric acid, ammonium phosphate, sodium phosphate, CS2, sodium thiosulfate, thiourea, selenium tetrachloride, H2SeO3, Na2 SeO3, MnCl2, Mn(NO3)2, MnSO4, manganese acetate, potassium permanganate, Fe(NO3)3·9H2O, Fe2(SO4)3, FeSO4, [Co(NH3)6]Cl3, cobalt nitrate hexahydrate, Ni(OH)3, oxalic acid, NiCl2, nickel sulfate hexahydrate, Cu(NO3)2, CuCl2, copper acetate, ZnCl2, Zn(Ac)2·2H2O, AgNO3, HAuCl4·4H2O, PdCl2, [PdCl4] 2- 、[Pd(H2O)4] 2+ 、PtCl6 2- 、H2Pt(OH)6、[Pt(NH3)4] 2+ , (NH4)2Ce(NO3)6, cerium nitrate hexahydrate, acylamide, dicyandiamide (C2N4H4), ammonia water, ammonium oxalate, urea, 2,2-bipyridine, hexamethylenetetramine, ammonium carbonate, guanidine (CN3H5), ammonium chloride, at least one of methylethylamine.

[0094] According to one embodiment of the present invention, the manufacturing method further comprises the step of irradiating the photocatalytic material precursor with ultraviolet light having a wavelength of 200-400 nm. For example, the ratio of the ultraviolet light to the radiation is 1:1-30:1 (preferably 3:1-20:1).

[0095] According to one embodiment of the present invention, the UV light irradiation dose is generally 0.01-200 W / g (preferably 0.1-50 W / g). In addition, the UV light irradiation power is generally 0.1-1000 W (preferably 1-200 W). Moreover, the UV light conversion efficiency is generally 0.1-80% (preferably 1-60%).

[0096] According to one embodiment of the present invention, the lower limit of the duration of the ultraviolet light irradiation is 0.1h (preferably 1h, 2h or 3h), and the upper limit of the duration of the ultraviolet light irradiation is 120h (preferably 60h, 36h, 20h, 15h or 10h). In addition, the ultraviolet light irradiation and the radiation irradiation can be performed synchronously, sequentially or alternately, without particular limitation.

[0097] According to one embodiment of the present invention, the manufacturing method further comprises the steps of solid-liquid separation, washing (optional) and drying the photocatalytic material.

[0098] According to one embodiment of the present invention, the solid-liquid separation can be performed in any manner conventionally known in the art, such as centrifugal separation or filtration, and is not particularly limited.

[0099] According to one embodiment of the present invention, the washing is an optional step, and the washing can be performed in any manner conventionally known in the art, such as washing with water once or multiple times, etc., without particular limitation.

[0100] According to one embodiment of the present invention, the drying operating conditions include: a drying temperature of 30-150° C. (preferably 35-120° C., more preferably 40-90° C.), and a drying time of 0.1-80 h (preferably 1-15 h).

[0101] According to one embodiment of the present invention, the photocatalytic material is not subjected to a heat treatment above 300°C (preferably above 200°C). The inventors of the present invention have found that high temperature calcination may remove dopants such as fluorine, or reduce the Ti 3+ Oxidation leads to a decrease in the visible light and infrared photocatalytic activity of the photocatalytic material.

[0102] According to one embodiment of the present invention, the manufacturing method comprises the following steps:

[0103] Under the conditions of aeration and stirring with an inert gas flow, the liquid (preferably water) is mixed with the photocatalytic material precursor (preferably titanium dioxide) to obtain the photocatalytic material precursor covered with the liquid film,

[0104] Under the conditions of aeration and stirring with an inert gas flow, a precursor of a first doping element is added to the photocatalytic material precursor covered by the liquid film to obtain a first raw material mixture,

[0105] Under the conditions of inert gas flow aeration and stirring, irradiating (first irradiation) vacuum ultraviolet light to the first raw material mixture to obtain a first product mixture,

[0106] The first product mixture is separated from the solid and liquid, washed (optionally) and dried to obtain the photocatalytic material.

[0107] According to one embodiment of the present invention, the mass ratio of the photocatalytic material precursor to the liquid is generally 1:1-10,000 (preferably 1:2-5,000, more preferably 1:5-1,000), and the mass ratio of the photocatalytic material precursor to the precursor of the first doping element is generally 1:0.01-10 (preferably 1:0.05-5, more preferably 1:0.1-2). In addition, the duration of the first irradiation is generally 0.1-120 hours (preferably 0.5-60 hours, more preferably 1-36 hours).

[0108] According to one embodiment of the present invention, the manufacturing method further comprises the following steps:

[0109] adding a precursor of a second doping element to the first product mixture to obtain a second raw material mixture,

[0110] Under the conditions of inert gas flow aeration and stirring, irradiating the second raw material mixture with vacuum ultraviolet light (second irradiation) to obtain a second product mixture,

[0111] The second product mixture is subjected to solid-liquid separation, washing (optional) and drying to obtain the photocatalytic material.

[0112] According to the present invention, the second doping element may be the same as or different from the first doping element, preferably different, and may be freely selected from the doping elements described above in this specification without particular limitation. Preferably, the doping elements are used in combination, in particular, nitrogen and fluorine are used in combination, so that the liquid may contain multiple (e.g., two or three) doping elements.

[0113] According to one embodiment of the present invention, the mass ratio of the first product mixture (calculated as the photocatalytic material precursor) to the second doping element precursor is generally 1:0.0001-0.3 (preferably 1:0.0003-0.15). In addition, the duration of the second irradiation is generally 0.3-20 hours (preferably 0.5-15 hours, more preferably 1-10 hours).

[0114] According to one embodiment of the present invention, a photocatalytic product (such as photocatalytic particles, photocatalytic plates or photocatalytic films) is also provided, comprising the photocatalytic material described in any of the preceding or subsequent aspects of this specification.

[0115] According to one embodiment of the present invention, a conversion method is also involved, such as degradation of pollutants (VOCs, wastewater), photolysis of water to produce hydrogen, reduction of carbon dioxide to produce chemicals, reforming to produce synthesis gas, nitrogen fixation and alkane conversion.

[0116] According to one embodiment of the present invention, the VOCs-containing gas may contain formaldehyde. Preferably, the content of formaldehyde in the VOCs-containing gas is 1-10000 ppm (preferably 2-1000 ppm, more preferably 5-500 ppm).

[0117] According to the present invention, the conversion method includes the step of irradiating the raw material to be converted (such as VOCs-containing gas) with light in the presence of the photocatalytic material described in any preceding or subsequent aspect of this specification or the photocatalytic product described in any preceding or subsequent aspect of this specification.

[0118] According to one embodiment of the present invention, the wavelength of the light is 100-3000 nm (preferably 150-2000 nm). In addition, the irradiation dose of the light is 0.0001-10000 kW / m 3 (Preferably 0.005-1000kW / m 3 ).

[0119] According to one embodiment of the present invention, the operating conditions of the irradiation include: an operating temperature of -50-90°C (preferably 10-70°C), an operating pressure of 0-1 MPaG (preferably 0-0.5 MPaG), a duration of 0.1-2000 h (preferably 0.2-200 h), and a volume space velocity of 0.01-1,000,000 h -1 (Preferably 0.1-200,000h -1 ).

[0120] Example

[0121] The present invention is further described in detail below using examples and comparative examples, but the present invention is not limited to these examples.

[0122] Example 1

[0123] At room temperature, a cylindrical quartz glass reaction vessel with a square bottom (side length 80 mm), a height of 90 mm, and a total volume of about 0.6 L was placed on a magnetic stirrer, a stirring bar was added, 0.4 L of pure water was poured into the vessel (the liquid level was about 62 mm), and stirring was continued at 200 rpm. At the same time, nitrogen was introduced to the bottom of the vessel at a rate of 50 ml / min; then 1.0 g of anatase titanium dioxide with a particle size ranging from 20 to 70 nm and an average particle size of 40.2 nm was added to the vessel, and stirring and ventilation were continued until oxygen Titanium oxide and water are mixed evenly to obtain a first raw material mixture; the first raw material mixture is irradiated from top to bottom using an MLI-1000ArF laser from the German MLase company. The laser can output 193nm vacuum ultraviolet light (maximum power 6W, power adjustable), and the spot size and shape are adjusted through a beam expander to match the inner surface of the reaction vessel. The output spot power is tested and adjusted using a beam analyzer (PM10X laser power meter from Coherent, USA), and the spot power acting on the solution surface is adjusted to 2W. At this point, titanium oxide and water are evenly mixed, the particles are randomly dispersed in the water, the average thickness of the liquid film is 31mm, and the irradiation dose is 2W / g. The irradiation reaction is carried out for 24 hours to obtain the first product mixture. Subsequently, the light source is turned off, and stirring and ventilation are stopped; after natural sedimentation for a period of time, the supernatant is removed, filtered, and the sample is washed several times with distilled water, and dried at 60°C for 6 hours to obtain the product.

[0124] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.64, the absorbance at 800nm ​​was 0.66, and the absorbance at 850nm was 0.69.

[0125] The XPS peaks of oxygen and titanium in the product were analyzed, and peak fitting was performed for O1s and Ti 2p according to the peak shapes and references. After fitting O 1s, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, O 总 =O a +O v +O L , calculated as O v / O 总 =35.3%, before reaction O v / O 总 =2.1%; Ti 2p fitting gives Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 38.2%, Ti 4+ (Ti 4+ / Ti total) content is 61.8%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.618, and the unreacted Ti 3+ The content is 0. The mass loss percentage measured by thermogravimetric analysis at 300 ° C is 0.95%, the surface hydroxyl content measured by infrared spectroscopy is 0.43mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.8nm respectively, and the surface Ti after 100 ° C deionized water cycle washing is 10 times. 3+ The content loss rate is 0.4%.

[0126] Weigh four embedding agents, 812 resin (1.5g), DDSA (0.72g), MNA (1.32g), and DP-30 (0.10g), and mix them in order. Then embed the catalyst in the embedding tube and cure at 60°C for 48h. After the sample is trimmed, it is ultrathinly sliced ​​(ultrathin microtome, UC-6, Leica, Germany) with a slice thickness of 10nm. The obtained slices are tested by TEM-EELS (JEOL JEM-ARM200F, Japan). The test results show that Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ti is found inside the particles. 3+ existence.

[0127] This material is suitable for VOCs treatment. The following takes the degradation of formaldehyde as an example to illustrate how to use this material.

[0128] To 16 ml of ethanol, add 0.4 g of the catalyst from Example 1 and stir to disperse the sample in the ethanol to obtain a catalyst suspension. Four glass slides (10 cm × 4 cm) were then evenly dripped with the suspension onto the slides. The samples were then dried in an oven at 60°C to form a uniform catalyst film on the slides. For activity evaluation experiments, the slides were placed in a 0.8 L (20 cm × 10 cm × 4 cm) organic glass reactor and a gas containing 100 ppm formaldehyde was introduced. After the formaldehyde gas and the catalyst reached adsorption-desorption equilibrium, the light source was turned on. This was a PL-X300DF high-performance simulated daylight xenon lamp (150 W) from Bofeilai Company, emitting wavelengths from 300 to 2500 nm. The company's CUT600 nm filter was used to filter out light below 600 nm, leaving only visible and infrared light above 600 nm. The formaldehyde concentration in the reactor was continuously monitored using an infrared photoacoustic spectrometer. The formaldehyde concentration at adsorption equilibrium before turning on the light is recorded as C0, and the real-time formaldehyde concentration in the reactor after turning on the light is recorded as C. C / C0 is the rate of change of formaldehyde concentration with time. The removal rate after 90 minutes is 85.2%.

[0129] Example 2

[0130] The spot power acting on the solution was adjusted to 3 W, and the other conditions were the same as in Example 1. The irradiation dose was 3 W / g. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0131] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.67, the absorbance at 800nm ​​was 0.69, and the absorbance at 850nm was 0.72.

[0132] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =41.3%; after fitting, Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 42.6%, Ti 4+ (Ti 4+ / Ti total ) content is 57.4%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.742, the mass loss percentage measured by thermogravimetric analysis at 300 ° C is 1.13%, the surface hydroxyl content measured by infrared spectroscopy is 0.47 mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70 nm and 40.3 nm respectively, and the surface Ti after 100 ° C deionized water cycle washing is 3+ The content loss rate is 0.53%.

[0133] TEM-EELS test results show that Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ti is found inside the particles. 3+ existence.

[0134] The formaldehyde concentration test showed that the removal rate was 87.4% after 90 minutes.

[0135] Example 3

[0136] 0.3 g of sodium fluoride was added to the first raw material mixture of Example 1 to obtain the first raw material mixture of this example. Other conditions were the same. Sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0137] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.68, the absorbance at 800nm ​​was 0.69, and the absorbance at 850nm was 0.71.

[0138] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =44.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 46.1%, Ti 4+ (Ti 4+ / Ti total ) content is 53.9%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.855; the fluorine element is 1.20%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.52%, the surface hydroxyl content measured by infrared spectroscopy is 0.33mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.4nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 100%. 3+ The content loss rate is 0.46%.

[0139] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0140] The formaldehyde concentration test showed that the removal rate was 92.2% after 90 minutes.

[0141] Example 4

[0142] After adding titanium oxide in Example 1, 0.7 g of sodium fluoride was added to form the first raw material mixture of this example, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0143] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.76, the absorbance at 800nm ​​was 0.77, and the absorbance at 850nm was 0.79.

[0144] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =49.6%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 57.1%, Ti 4+ (Ti 4+ / Ti total ) content is 42.9%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 1.331; the fluorine element is 1.39%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.71%, the surface hydroxyl content measured by infrared spectroscopy is 0.41mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.1nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.57%.

[0145] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0146] The formaldehyde concentration test showed that the removal rate was 95.3% after 90 minutes.

[0147] Example 5

[0148] The sodium fluoride in Example 4 was replaced with ammonium fluoride as the first raw material mixture in this example, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0149] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.77, the absorbance at 800nm ​​was 0.80, and the absorbance at 850nm was 0.82.

[0150] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总=47.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 48.2%, Ti 4+ (Ti 4+ / Ti total ) content is 51.8%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.93; the fluorine element is 0.53%, and it is a substitution for oxygen doping; the nitrogen element content is 0.62%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 49.6% and 50.4%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.48%, the surface hydroxyl content measured by infrared spectroscopy is 0.34mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.7nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 0.02%.

[0151] TEM-EELS test results show that fluorine, nitrogen and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine, nitrogen and Ti are found inside the particles. 3+ existence.

[0152] Formaldehyde concentration test showed that the removal rate was 98.4% after 90 minutes.

[0153] Example 6

[0154] After adding titanium oxide in Example 2, 0.7 g of ammonium fluoride was added to form the first raw material mixture of this example, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0155] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.83, the absorbance at 800nm ​​was 0.85, and the absorbance at 850nm was 0.86.

[0156] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =51.8%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti3+ / Ti total ) content is 52.1%, Ti 4+ (Ti 4+ / Ti total ) content is 47.9%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 1.09; the fluorine element is 0.64%, and it is a substitution for oxygen doping; the nitrogen element content is 0.81%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 54.2% and 45.8%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.69%, the surface hydroxyl content measured by infrared spectroscopy is 0.41mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.5nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100℃ is 0. 3+ The content loss rate is 0.09%.

[0157] TEM-EELS test results show that fluorine, nitrogen and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine, nitrogen and Ti are found inside the particles. 3+ existence.

[0158] Formaldehyde concentration test showed that the removal rate was 99.1% after 90 minutes.

[0159] Example 7

[0160] The irradiation time of the first raw material mixture in Example 3 was changed to 0.5 hours, and the other conditions remained unchanged. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0161] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.54, the absorbance at 800nm ​​was 0.56, and the absorbance at 850nm was 0.59.

[0162] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =24.1%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 30.8%, Ti 4+ (Ti4+ / Ti total ) content is 69.2%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.445; the fluorine element is 0.22%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.48%, the surface hydroxyl content measured by infrared spectroscopy is 0.31mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.1nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.32%.

[0163] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0164] The formaldehyde concentration test showed that the removal rate was 76.3% after 90 minutes.

[0165] Example 8

[0166] The irradiation time of the first raw material mixture in Example 3 was changed to 120 hours, while the other conditions remained unchanged. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0167] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.52, the absorbance at 800nm ​​was 0.53, and the absorbance at 850nm was 0.55.

[0168] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =22.9%; after fitting, Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 33.4%, Ti 4+ (Ti 4+ / Ti total ) content is 66.6%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.502; the fluorine element is 0.33%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.71%, the surface hydroxyl content measured by infrared spectroscopy is 0.36mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.7nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.56%.

[0169] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0170] The formaldehyde concentration test showed that the removal rate was 80.6% after 90 minutes.

[0171] Example 9

[0172] The nano-titanium oxide in Example 3 was replaced with particles having a particle size range of 10-40 nm and an average particle size of 20.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0173] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.58, the absorbance at 800nm ​​was 0.61, and the absorbance at 850nm was 0.63.

[0174] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 = = 26.4%, before reaction O v / O 总 =2.4%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 47.8%, Ti 4+ (Ti 4+ / Ti total ) content is 52.2%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.916, and the unreacted Ti 3+The content is 0; the fluorine element is 1.17%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.36%, the surface hydroxyl content measured by infrared spectroscopy is 0.34mmol / g, the particle size distribution range and average particle size measured by SEM are 10-40nm and 20.4nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.91%.

[0175] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0176] The formaldehyde concentration test showed that the removal rate was 77.6% after 90 minutes.

[0177] Example 10

[0178] The nano-titanium oxide in Example 3 was replaced with particles having a particle size range of 60-100 nm and an average particle size of 81.4 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0179] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.56, the absorbance at 800nm ​​was 0.58, and the absorbance at 850nm was 0.59.

[0180] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =30.2%, before reaction O v / O 总 =2.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 46.9%; Ti 4+ (Ti 4+ / Ti total ) content is 53.1%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.883; the fluorine element is 1.22%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.29%, the surface hydroxyl content measured by infrared spectroscopy is 0.31mmol / g, and the particle size distribution range and average particle size measured by SEM are 60-100nm and 81.1nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.88%.

[0181] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0182] The formaldehyde concentration test showed that the removal rate was 79.8% after 90 minutes.

[0183] Example 11

[0184] The nano-titanium oxide in Example 3 was replaced with tetragonal ZrO2 with a particle size in the range of 20-45 nm and an average particle size of 34.6 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0185] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.43, the absorbance at 800nm ​​was 0.44, and the absorbance at 850nm was 0.45.

[0186] Combined with the literature information, XPS was used to analyze the elemental composition and valence of the product. The product is composed of Zr, O, and F. The position and linear symmetry analysis of the Zr 3d peak show that the zirconium element exists 3+ and Zr 4+ Two valence states, after fitting, Zr 3+ and Zr 4+ Peak, Zr 3+ / Zr total 48.9%, Zr before reaction 3+ / Zr total The XPS spectrum of the O 1s electron energy level is an asymmetric Gaussian line shape, indicating that it is composed of a variety of oxygen bonding states superimposed; after fitting the O1s, the corresponding adsorbed oxygen (O a ), oxygen vacancies (O V ) lattice oxygen (O L ) peak, O V / O 总 The value is 40.2%, and the O v / O 总The value is 8.2%. The fluorine content is 0.72%. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.88%. The particle size distribution range and average particle size measured by SEM are 20-45nm and 33.8nm respectively.

[0187] TEM-EELS test results show that Zr 3+ The fluorine elements are mainly distributed within about 3 nm from the surface of the ZrO2 particles, and no fluorine is found inside the particles.

[0188] The formaldehyde concentration test showed that the removal rate was 82.4% after 90 minutes.

[0189] Example 12

[0190] The nano-titanium oxide in Example 3 was replaced with hexagonal wurtzite ZnO with a particle size ranging from 25 to 65 nm and an average particle size of 32.5 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0191] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.52, the absorbance at 800nm ​​was 0.54, and the absorbance at 850nm was 0.56.

[0192] Combined with the literature information, XPS was used to analyze the elemental composition and valence of the product. The product is composed of Zn, O, and F. The position and linear symmetry analysis of the Zn 2p peak show that Zn is a single component. 2+ The XPS spectrum of O 1s electron energy level is an asymmetric Gaussian line, indicating that it is composed of multiple oxygen bonding states. After fitting O1s, the corresponding adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O V / O 总 The value is 18.2%, and the O v / O 总 The value is 4.2%. The fluorine content is 0.68%. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.79%. The particle size distribution range and average particle size measured by SEM are 25-65nm and 32.8nm respectively.

[0193] The TEM-EELS test results show that the fluorine element is mainly distributed within about 3 nm from the surface of the ZnO particles, and no fluorine is found inside the particles.

[0194] The formaldehyde concentration test showed that the removal rate was 79.6% after 90 minutes.

[0195] Example 13

[0196] The nano-titanium oxide in Example 3 was replaced with monoclinic BiVO4 with a particle size ranging from 20 to 70 nm and an average particle size of 31.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0197] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.51, the absorbance at 800nm ​​was 0.52, and the absorbance at 850nm was 0.54.

[0198] XPS was used to analyze the elemental composition and valence state of the product. The product is composed of Bi, V, O, and F. The double peak position of Bi 4f indicates that the chemical state of bismuth is Bi 3+ According to the peak shape, the peaks of O1s, V 2p and F1s were fitted in combination with the literature. After fitting O 1s, the peaks corresponding to adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =28.3%, O before BiVO4 reaction v / O 总 =5.1%; after fitting, V 4+ and V 5+ Peak, V 4+ The content of BiVO4 is 30.3%, which is 2.4% higher than that before the reaction. 4+ The presence of fluorine can improve light absorption to a certain extent. The fluorine content is 0.80%. The mass loss measured by thermogravimetric analysis at 300°C is 0.81%. The particle size distribution range and average particle size measured by SEM are 20-70nm and 31.5nm, respectively.

[0199] TEM-EELS test results show that fluorine and V 4+ It is mainly distributed within about 3nm from the surface of BiVO4 particles, and no fluorine and V are found inside the particles. 4+ existence.

[0200] The formaldehyde concentration test showed that the removal rate was 83.5% after 90 minutes.

[0201] Example 14

[0202] The nano-titanium oxide in Example 3 was replaced with monoclinic WO3 with a particle size in the range of 20-80 nm and an average particle size of 51.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0203] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.42, the absorbance at 800nm ​​was 0.44, and the absorbance at 850nm was 0.46.

[0204] Analyze the XPS peaks of nitrogen and tungsten elements in the product. According to the peak shape, the peaks corresponding to adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =25.8%, O before WO3 reaction v / O L =5.6%; after fitting, we get W 5+ and W 6+ Peak, W before and after the reaction 5+ The contents of the fluorine element are 4.1% and 49.6% respectively; the fluorine content is 0.69%. The mass loss measured by thermogravimetric analysis at 300°C is 0.79%. The particle size distribution range and average particle size measured by SEM are 20-80nm and 50.5nm respectively.

[0205] TEM-EELS test results show that W 5+ The fluorine elements are mainly distributed within about 3nm from the surface of the tungsten oxide particles, and no fluorine and W are found inside the particles. 5+ existence.

[0206] The formaldehyde concentration test showed that the removal rate was 76.5% after 90 minutes.

[0207] Example 15

[0208] The nano-titanium oxide in Example 3 was replaced with rutile SnO2 with a particle size ranging from 20 to 50 nm and an average particle size of 31.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0209] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.47, the absorbance at 800nm ​​was 0.49, and the absorbance at 850nm was 0.51.

[0210] XPS was used to analyze the elemental composition and valence state of the product. The product is composed of Sn, O, and F elements. The double peak position of Sn 3d (487.5, 495.6 eV) indicates that the chemical state of tin is Sn 4+ According to the peak shape, the peaks of O1s and F1s were fitted in combination with the literature. After fitting O 1s, the peaks corresponding to adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =23.6%, O before SnO2 reaction v / O 总 =3.1%; fluorine element is 0.91%, and is used to replace oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.74%, and the particle size distribution range and average particle size measured by SEM are 20-50nm and 31.5nm, respectively.

[0211] The TEM-EELS test results show that the fluorine element is mainly distributed within about 3 nm from the surface of the SnO2 particles, and no fluorine is found inside the particles.

[0212] The formaldehyde concentration test showed that the removal rate was 84.3% after 90 minutes.

[0213] Example 16

[0214] The aeration condition in Example 3 was eliminated, and the other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0215] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.30, the absorbance at 800nm ​​was 0.32, and the absorbance at 850nm was 0.34.

[0216] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =13.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 26.4%, Ti 4+ (Ti 4+ / Titotal ) content is 73.6%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.359; the fluorine element is 0.69%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.76%, the surface hydroxyl content measured by infrared spectroscopy is 0.25mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.7nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.75%.

[0217] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0218] The formaldehyde concentration test showed that the removal rate was 71.8% after 90 minutes.

[0219] Example 17

[0220] The dried product of Example 3 was calcined at 250° C. for 1 hour, with the remaining conditions being the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0221] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.27, the absorbance at 800nm ​​was 0.28, and the absorbance at 850nm was 0.31.

[0222] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =10.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) value is 22.4%, Ti 4+ (Ti 4+ / Ti total ) content is 77.6%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.289; the fluorine element is 0.16%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.22%, the surface hydroxyl content measured by infrared spectroscopy is 0.16mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.4nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.88%.

[0223] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0224] The formaldehyde concentration test showed that the removal rate was 69.2% after 90 minutes.

[0225] Example 18

[0226] The first raw material mixture in Example 3 was irradiated with 248nm ordinary ultraviolet light (power of 2W) and 193nm vacuum ultraviolet light at the same time, and the other conditions were the same. The light source and irradiation method used for the 193nm vacuum ultraviolet light were the same as those in Example 3. The 248nm ultraviolet light used a CL7750 light source from OptoSystems, which acted on the first raw material mixture from the side of the reactor through quartz glass. The photogenerated medium of CL7750 was KrF. The output ultraviolet light was adjusted to the spot size and shape through a beam expander to match the side of the reaction vessel. The output spot power was tested and adjusted using a beam analyzer (PM10X laser power meter from Coherent, USA). The spot power acting on the solution was adjusted to 2W, and the irradiation doses of 248nm and 193nm were both 2W / g.

[0227] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.59, the absorbance at 800nm ​​was 0.62, and the absorbance at 850nm was 0.64.

[0228] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =27.4%; after fitting, Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 45.6%, Ti4+ (Ti 4+ / Ti total ) content is 54.4%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.838; the fluorine element is 0.75%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.13%, the surface hydroxyl content measured by infrared spectroscopy is 0.23mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.8nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.71%.

[0229] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0230] The formaldehyde concentration test showed that the removal rate was 84.4% after 90 minutes.

[0231] Example 19

[0232] The first raw material mixture in Example 3 was irradiated simultaneously with 248 nm conventional ultraviolet light (total power of 40 W) and 193 nm vacuum ultraviolet light, with all other conditions being the same. The light source and irradiation method used for the 193 nm vacuum ultraviolet light were the same as those in Example 3, with all other conditions being the same as those in Example 3. The 248 nm ultraviolet light was applied using two OptoSystems CL7750 light sources, each of which was supplied by OptoSystems, through quartz glass and directed at the first raw material mixture from either side of the reactor. The photogenerating medium of the CL7750 was KrF. The output ultraviolet light was adjusted in size and shape via a beam expander to match the side of the reaction vessel. The output spot power was tested and adjusted using a beam profiler (PM10X laser power meter from Coherent, USA). The power of each spot acting on the solution was adjusted to 20 W, for a total power of 40 W. The 248 nm and 193 nm irradiation doses were 40 W / g and 2 W / g, respectively.

[0233] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.51, the absorbance at 800nm ​​was 0.53, and the absorbance at 850nm was 0.54.

[0234] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a) peak, calculated to be O V / O 总 =22.1%; after fitting, Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 43.2%, Ti 4+ (Ti 4+ / Ti total ) content is 56.8%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.761; the fluorine element is 0.58%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.97%, the surface hydroxyl content measured by infrared spectroscopy is 0.19mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.4nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.64%.

[0235] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0236] The formaldehyde concentration test showed that the removal rate was 81.6% after 90 minutes.

[0237] Example 20

[0238] The power of the 248nm ordinary ultraviolet light of the two CL7750 light sources in Example 3 is adjusted to 35W, so that the total power is 70W. Other conditions remain the same, and the irradiation doses at 248nm and 193nm are 70W / g and 2W / g respectively.

[0239] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.46, the absorbance at 800nm ​​was 0.47, and the absorbance at 850nm was 0.49.

[0240] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =19.4%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Titotal ) is 39.7%, Ti 4+ (Ti 4+ / Ti total ) content is 60.3%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.658; the fluorine element is 0.52%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.75%, the surface hydroxyl content measured by infrared spectroscopy is 0.16mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.7nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.60%.

[0241] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0242] The formaldehyde concentration test showed that the removal rate was 77.5% after 90 minutes.

[0243] Example 21

[0244] The mass of sodium fluoride in Example 9 was changed to 2.0 g, and the irradiation time was extended to 64 hours. The other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0245] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.24, the absorbance at 800nm ​​was 0.26, and the absorbance at 850nm was 0.27.

[0246] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =12.6%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 6.5%, Ti 4+ (Ti 4+ / Ti total ) content is 93.5%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.070; the fluorine element is 19.8%. Fluorine doping includes lattice doping and interstitial doping. The proportions of lattice doping and interstitial doping in the total doping are 85.3% and 14.7%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.61%. The surface hydroxyl content measured by infrared spectroscopy is 0.24 mmol / g. The particle size distribution range and average particle size measured by SEM are 10-40 nm and 19.1 nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0.61%. 3+ The content loss rate is 0.62%.

[0247] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0248] The formaldehyde concentration test showed that the removal rate was 68.9% after 90 minutes.

[0249] Example 22

[0250] The mass of sodium fluoride in Example 3 was changed to 0.03 g, and the irradiation time was changed to 8 minutes, with the remaining conditions remaining the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0251] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.23, the absorbance at 800nm ​​was 0.25, and the absorbance at 850nm was 0.26.

[0252] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =13.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 5.5%, Ti 4+ (Ti 4+ / Ti total ) content is 94.5%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.058; the fluorine element is 0.005%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.32%, the surface hydroxyl content measured by infrared spectroscopy is 0.05mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.1nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.45%.

[0253] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0254] The formaldehyde concentration test showed that the removal rate was 65.4% after 90 minutes.

[0255] Example 23

[0256] The irradiation time in Example 22 was changed to 1 hour, and the other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0257] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.49, the absorbance at 800nm ​​was 0.51, and the absorbance at 850nm was 0.53.

[0258] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =22.3%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 25.3%, Ti 4+ (Ti 4+ / Ti total ) content is 74.7%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.339; the fluorine element is 0.05%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.25%, the surface hydroxyl content measured by infrared spectroscopy is 0.22mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.9nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 1.25%.

[0259] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0260] The formaldehyde concentration test showed that the removal rate was 79.5% after 90 minutes.

[0261] Example 24

[0262] The irradiation time in Example 21 was changed to 42 hours, and the other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0263] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.52, the absorbance at 800nm ​​was 0.54, and the absorbance at 850nm was 0.55.

[0264] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =20.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 24.5%, Ti 4+ (Ti 4+ / Ti total ) content is 75.5%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.325; the fluorine element is 11.7%. Fluorine doping includes lattice doping and interstitial doping. The proportions of lattice doping and interstitial doping in the total doping are 90.4% and 9.6%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.45%. The surface hydroxyl content measured by infrared spectroscopy is 0.38mmol / g. The particle size distribution range and average particle size measured by SEM are 10-40nm and 18.8nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 10. 3+ The content loss rate is 0.21%.

[0265] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0266] The formaldehyde concentration test showed that the removal rate was 80.2% after 90 minutes.

[0267] Example 25

[0268] The irradiation time in Example 21 was changed to 36 hours, and the other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0269] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.67, the absorbance at 800nm ​​was 0.69, and the absorbance at 850nm was 0.71.

[0270] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =24.6%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 29.6%, Ti 4+ (Ti 4+ / Ti total ) content is 70.4%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.42; the fluorine element is 8.1%. Fluorine doping includes lattice doping and interstitial doping. The proportions of lattice doping and interstitial doping in the total doping are 94.6% and 5.4%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.12%. The surface hydroxyl content measured by infrared spectroscopy is 0.34mmol / g. The particle size distribution range and average particle size measured by SEM are 10-40nm and 20.4nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 20.4nm. 3+ The content loss rate is 0.33%.

[0271] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0272] The formaldehyde concentration test showed that the removal rate was 81.4% after 90 minutes.

[0273] Example 26

[0274] The irradiation time in Example 22 was changed to 5 hours, and the other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0275] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.61, the absorbance at 800nm ​​was 0.62, and the absorbance at 850nm was 0.64.

[0276] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =37.1%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 41.2%, Ti 4+ (Ti 4+ / Ti total ) content is 58.8%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.701; the fluorine element is 0.22%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.08%, the surface hydroxyl content measured by infrared spectroscopy is 0.39mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.9nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.52%.

[0277] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0278] The formaldehyde concentration test showed that the removal rate was 85.8% after 90 minutes.

[0279] Example 27

[0280] The irradiation time in Example 4 was changed to 36 hours, and the other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0281] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.78, the absorbance at 800nm ​​was 0.80, and the absorbance at 850nm was 0.83.

[0282] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =54.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 52.6%, Ti 4+ (Ti 4+ / Ti total ) content is 47.4%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 1.11; the fluorine element is 2.1%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.39%, the surface hydroxyl content measured by infrared spectroscopy is 0.43mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.8nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.46%.

[0283] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0284] The formaldehyde concentration test showed that the removal rate was 96.2% after 90 minutes.

[0285] Example 28

[0286] The irradiation time in Example 21 was changed to 15 hours, and the other conditions remained the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0287] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.74, the absorbance at 800nm ​​was 0.75, and the absorbance at 850nm was 0.77.

[0288] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =42.9%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 44.8%, Ti 4+ (Ti 4+ / Ti total ) content is 55.2%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.812; the fluorine element is 4.5%. Fluorine doping includes lattice doping and interstitial doping. The proportions of lattice doping and interstitial doping in the total doping are 97.4% and 2.6%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.84%. The surface hydroxyl content measured by infrared spectroscopy is 0.36mmol / g. The particle size distribution range and average particle size measured by SEM are 10-40nm and 21.1nm, respectively. The surface Ti after 100°C deionized water cycle washing is 100nm. 3+ The content loss rate is 0.26%.

[0289] TEM-EELS test results show that fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0290] The formaldehyde concentration test showed that the removal rate was 93.2% after 90 minutes.

[0291] Example 29

[0292] 40 mg of potassium permanganate was added to the first product mixture in Example 5, and the reaction was continued under light for 3 hours, with other conditions remaining unchanged, to obtain a second product mixture. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0293] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.95, the absorbance at 800nm ​​was 0.97, and the absorbance at 850nm was 0.99.

[0294] The ICP test shows that the manganese content is 1.15%. The Mn observed by spherical aberration electron microscopy is distributed in a single atom. The XPS peaks of oxygen and titanium in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =53.4%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 54.3%, Ti 4+ (Ti 4+ / Ti total ) content is 45.7%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 1.19; the fluorine element is 0.58%, and it is a substitution for oxygen doping; the nitrogen element content is 0.69%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 61.2% and 38.8% respectively. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.59%, the surface hydroxyl content measured by infrared spectroscopy is 0.42mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.7nm respectively. The surface Ti after 10 cycles of deionized water washing at 100℃ is 0. 3+ The content loss rate is 0.04%.

[0295] TEM-EELS test results show that the elements manganese, fluorine, nitrogen and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no manganese, fluorine, nitrogen and Ti are found inside the particles. 3+ existence.

[0296] Formaldehyde concentration test showed that the removal rate was 99.8% after 90 minutes.

[0297] Example 30

[0298] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 29 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0299] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.79, the absorbance at 800nm ​​was 0.81, and the absorbance at 850nm was 0.83.

[0300] The ICP test shows that the manganese content is 0.96%. The manganese can be observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium elements in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =42.4%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 31.2%, Ti 4+ (Ti 4+ / Ti total ) content is 68.8%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.453. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.52%, the surface hydroxyl content measured by infrared spectroscopy is 0.22mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.4nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate was 1.1%.

[0301] TEM-EELS test results show that the elements manganese and Ti 3+ Mainly distributed within about 3nm from the surface of titanium oxide particles, no Mn and Ti were found inside the particles. 3+ existence.

[0302] The formaldehyde concentration test showed that the removal rate was 92.6% after 90 minutes.

[0303] Example 31

[0304] The potassium permanganate in Example 29 was replaced with NaBO2, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0305] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.80, the absorbance at 800nm ​​was 0.81, and the absorbance at 850nm was 0.82.

[0306] ICP test shows that the B element content is 0.47%. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the corresponding peaks are obtained after fitting. L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =37.4%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 35.6%, Ti 4+ (Ti 4+ / Ti total ) content is 64.4%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.553; the fluorine element is 0.66%, which is lattice doping. The nitrogen content is 0.59%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 48.7% and 51.3%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.44%, the surface hydroxyl content measured by infrared spectroscopy is 0.55mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.4nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate was 2.1%.

[0307] TEM-EELS test results show that fluorine, nitrogen, boron and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine, nitrogen, boron and Ti are found inside the particles. 3+ existence.

[0308] The formaldehyde concentration test showed that the removal rate was 90.6% after 90 minutes.

[0309] Example 32

[0310] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 31 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0311] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.44, the absorbance at 800nm ​​was 0.46, and the absorbance at 850nm was 0.47.

[0312] ICP test shows that the B element content is 0.53%. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the corresponding peaks are obtained after fitting. L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =16.8%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 24.9%, Ti 4+ (Ti 4+ / Ti total ) content is 75.1%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.332; the boron content is 0.53%. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.32%, the surface hydroxyl content measured by infrared spectroscopy is 0.36mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.5nm respectively. The surface Ti after 100℃ deionized water washing cycle is 10 times. 3+ The content loss rate is 0.57%.

[0313] TEM-EELS test results show that boron and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no boron and Ti are found inside the particles. 3+ existence.

[0314] The formaldehyde concentration test showed that the removal rate was 81.7% after 90 minutes.

[0315] Example 33

[0316] The potassium permanganate in Example 29 was replaced by Ga(NO 3 ) 3 , and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0317] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.83, the absorbance at 800nm ​​was 0.84, and the absorbance at 850nm was 0.86.

[0318] The Ga content in the ICP test is 0.78%. The Ga can be observed in a single atomic distribution by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =38.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 36.4%, Ti 4+ (Ti 4+ / Ti total ) content is 63.6%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.572; the fluorine element is 0.62%, and fluorine is lattice doping. The nitrogen content is 0.66%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 54.3% and 45.7%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.22%, the surface hydroxyl content measured by infrared spectroscopy is 0.48mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 37.7nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 1.26%.

[0319] TEM-EELS test results show that fluorine, nitrogen, Ga and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine, nitrogen, Ga and Ti elements are found inside the particles. 3+ existence.

[0320] The formaldehyde concentration test showed that the removal rate was 92.4% after 90 minutes.

[0321] Example 34

[0322] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 33 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0323] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.42, the absorbance at 800nm ​​was 0.44, and the absorbance at 850nm was 0.45.

[0324] ICP test shows that the Ga content is 0.85%; the Ga can be observed in a single atomic distribution by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =19.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 24.3%, Ti 4+ (Ti 4+ / Ti total ) content is 75.7%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.321; the mass loss percentage measured by thermogravimetric analysis at 300 ° C is 0.88%, the surface hydroxyl content measured by infrared spectroscopy is 0.26 mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70 nm and 40.7 nm respectively, and the surface Ti after 100 ° C deionized water cycle washing is 10 times. 3+ The content loss rate is 0.89%.

[0325] TEM-EELS test results show that Ga and Ti 3+ Mainly distributed within about 3nm from the surface of titanium oxide particles, no Ga and Ti were found inside the particles. 3+ existence.

[0326] The formaldehyde concentration test showed that the removal rate was 82.1% after 90 minutes.

[0327] Example 35

[0328] The ammonium fluoride in Example 5 was replaced by ethanol, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0329] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.71, the absorbance at 800nm ​​was 0.72, and the absorbance at 850nm was 0.74.

[0330] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =36.9%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 37.6%, Ti 4+ (Ti 4+ / Ti total ) content is 63.4%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.593; the carbon content is 0.86%. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.22%, the surface hydroxyl content measured by infrared spectroscopy is 0.29mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.3nm respectively. The surface Ti after 10 cycles of deionized water washing at 100℃ is 0.1%. 3+The content loss rate was 1.1%.

[0331] TEM-EELS test results show that carbon and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no carbon and Ti are found inside the particles. 3+ existence.

[0332] The formaldehyde concentration test showed that the removal rate was 89.9% after 90 minutes.

[0333] Example 36

[0334] The ammonium fluoride in Example 29 was replaced with ethanol, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0335] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.86, the absorbance at 800nm ​​was 0.87, and the absorbance at 850nm was 0.88.

[0336] The Mn content of the product was 0.98% as determined by ICP. The Ge was observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product were analyzed. The peak shapes were fitted to obtain the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =44.1%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 49.6%, Ti 4+ (Ti 4+ / Ti total ) content is 50.4%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.984; the carbon content is 0.89%. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.33%, the surface hydroxyl content measured by infrared spectroscopy is 0.47mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.1nm respectively. The surface Ti after 100℃ deionized water washing cycle is 10 times. 3+ The content loss rate is 0.78%.

[0337] TEM-EELS test results show that the elements carbon, manganese and Ti 3+It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no carbon, manganese and Ti are found inside the particles. 3+ existence.

[0338] The formaldehyde concentration test showed that the removal rate was 94.2% after 90 minutes.

[0339] Example 37

[0340] The potassium permanganate in Example 29 was replaced with Na2GeO3, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0341] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.82, the absorbance at 800nm ​​was 0.83, and the absorbance at 850nm was 0.85.

[0342] The ICP test shows that the Ge content is 1.43%. The Ge is observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =37.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 37.1%, Ti 4+ (Ti 4+ / Ti total ) content is 62.9%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.59; the fluorine element is 0.69%, and the fluorine doping is lattice doping. The nitrogen content is 0.49%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 45.9% and 54.1%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.58%, the surface hydroxyl content measured by infrared spectroscopy is 0.44mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.7nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 0.69%.

[0343] TEM-EELS test results show that fluorine, nitrogen, germanium and Ti 3+It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine, nitrogen, germanium and Ti are found inside the particles. 3+ existence.

[0344] The formaldehyde concentration test showed that the removal rate was 93.4% after 90 minutes.

[0345] Example 38

[0346] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 37 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0347] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.41, the absorbance at 800nm ​​was 0.42, and the absorbance at 850nm was 0.44.

[0348] The ICP test shows that the Ge content is 1.32%. The Ge is observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =33.1%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 20.7%, Ti 4+ (Ti 4+ / Ti total ) content is 79.3%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.261. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.92%, the surface hydroxyl content measured by infrared spectroscopy is 0.23mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.3nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.53%.

[0349] TEM-EELS test results show that Ge and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no germanium and Ti are found inside the particles. 3+ existence.

[0350] The formaldehyde concentration test showed that the removal rate was 79.6% after 90 minutes.

[0351] Example 39

[0352] The ammonium fluoride in Example 5 was replaced with sodium phosphate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0353] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.67, the absorbance at 800nm ​​was 0.68, and the absorbance at 850nm was 0.70.

[0354] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =26.4%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 40.2%, Ti 4+ (Ti 4+ / Ti total ) content is 59.8%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.672; phosphorus is 0.88%, and fluorine is lattice doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.66%, the surface hydroxyl content measured by infrared spectroscopy is 0.41mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.5nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.99%.

[0355] TEM-EELS test results show that phosphorus and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no phosphorus and Ti are found inside the particles. 3+ existence.

[0356] The formaldehyde concentration test showed that the removal rate was 88.5% after 90 minutes.

[0357] Example 40

[0358] The ammonium fluoride in Example 29 was replaced with sodium phosphate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0359] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.81, the absorbance at 800nm ​​was 0.83, and the absorbance at 850nm was 0.86.

[0360] The ICP test shows that the Mn content is 0.97%. The doping elements observed by spherical aberration electron microscopy are distributed in single atoms. The XPS peaks of oxygen and titanium elements in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =46.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 46.7%, Ti 4+ (Ti 4+ / Ti total ) content is 53.3%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.876; the phosphorus content is 0.92%. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.72%, the surface hydroxyl content measured by infrared spectroscopy is 0.49mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.7nm respectively. The surface Ti after 10 cycles of deionized water washing at 100℃ is 0.49mmol / g. 3+ The content loss rate is 0.92%.

[0361] TEM-EELS test results show that the elements phosphorus, manganese and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no phosphorus, manganese and Ti are found inside the particles. 3+ existence.

[0362] Formaldehyde concentration test shows that the removal rate is 91.3% after 90 minutes

[0363] Example 41

[0364] The ammonium fluoride in Example 5 was replaced with sodium thiosulfate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0365] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.68, the absorbance at 800nm ​​was 0.69, and the absorbance at 850nm was 0.71.

[0366] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =32.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 43.1%, Ti 4+ (Ti 4+ / Ti total ) content is 56.9%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.757; the S element is 1.4%. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.35%, the surface hydroxyl content measured by infrared spectroscopy is 0.35mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.9nm respectively. The surface Ti after 10 cycles of deionized water washing at 100℃ is 0.1%. 3+ The content loss rate is 0.88%.

[0367] TEM-EELS test results show that sulfur and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no sulfur and Ti are found inside the particles. 3+ existence.

[0368] Formaldehyde concentration test showed that the removal rate was 86.4% after 90 minutes.

[0369] Example 42

[0370] The ammonium fluoride in Example 29 was replaced with sodium thiosulfate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0371] ICP testing revealed a Mn content of 1.09%, with spherical aberration electron microscopy revealing a monoatomic distribution of the doped element. UV-visible diffuse reflectance absorption spectroscopy revealed absorbance values ​​of 0.82 at 760nm, 0.85 at 800nm, and 0.88 at 850nm.

[0372] Analyze the XPS peaks of oxygen and titanium in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =47.1%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 47.4%, Ti 4+ (Ti 4+ / Ti total ) content is 52.6%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.901; the sulfur content is 1.32%. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.24%, the surface hydroxyl content measured by infrared spectroscopy is 0.50mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.5nm respectively. The surface Ti after 100℃ deionized water cycle washing is 100%. 3+ The content loss rate was 1.4%.

[0373] TEM-EELS test results show that manganese, sulfur and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no manganese, sulfur and Ti are found inside the particles. 3+ existence.

[0374] Formaldehyde concentration test shows that the removal rate is 90.7% after 90 minutes

[0375] Example 43

[0376] The potassium permanganate in Example 29 was replaced with Na2SeO3, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0377] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.80, the absorbance at 800nm ​​was 0.81, and the absorbance at 850nm was 0.83.

[0378] The Se content of the product was 1.34% as determined by ICP. The spherical aberration electron microscopy method showed that the Se element was distributed in a single atom. The XPS peaks of oxygen and titanium in the product were analyzed. The peak shapes were fitted to obtain the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =36.3%; after fitting, we get Ti 4+ and Ti3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 39.6%, Ti 4+ (Ti 4+ / Ti total ) content is 60.4%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.656; the fluorine element is 0.79%, and the fluorine element is lattice doping. The nitrogen content is 0.53%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 55.6% and 44.4%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.33%, the surface hydroxyl content measured by infrared spectroscopy is 0.49mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.2nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 1.45%.

[0379] TEM-EELS test results show that the elements F, N, Se and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Se and Ti are found inside the particles. 3+ existence.

[0380] The formaldehyde concentration test showed that the removal rate was 91.9% after 90 minutes.

[0381] Example 44

[0382] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 43 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0383] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.42, the absorbance at 800nm ​​was 0.45, and the absorbance at 850nm was 0.47.

[0384] The Se content of the product was 1.45% as determined by ICP. The doped Se was observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product were analyzed. The peak shapes were fitted to obtain the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =33.4%; after fitting, we get Ti 4+ and Ti3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 21.6%, Ti 4+ (Ti 4+ / Ti total ) content is 78.4%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.276. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.11%, the surface hydroxyl content measured by infrared spectroscopy is 0.18mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.5nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 1.55%.

[0385] TEM-EELS test results show that Se and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Se and Ti are found inside the particles. 3+ existence.

[0386] The formaldehyde concentration test showed that the removal rate was 78.9% after 90 minutes.

[0387] Example 45

[0388] The potassium permanganate in Example 29 was replaced by Fe(NO3)39H2O, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0389] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.84, the absorbance at 800nm ​​was 0.86, and the absorbance at 850nm was 0.88.

[0390] The ICP test shows that the Fe content is 0.43%. The doped Fe element is observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium elements in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =44.1%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 40.2%, Ti 4+ (Ti4+ / Ti total ) content is 59.8%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.672; the fluorine element is 0.63%, and the fluorine element is lattice doping. The nitrogen content is 0.65%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 62.1% and 37.9% respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.05%, the surface hydroxyl content measured by infrared spectroscopy is 0.44mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.1nm respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 20-70nm and 38.1nm. 3+ The content loss rate is 1.32%.

[0391] TEM-EELS test results show that the elements F, N, Fe and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Fe and Ti are found inside the particles. 3+ existence.

[0392] Formaldehyde concentration test shows that the removal rate is 98.5% after 90 minutes

[0393] Example 46

[0394] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 45 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0395] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.50, the absorbance at 800nm ​​was 0.51, and the absorbance at 850nm was 0.52.

[0396] The ICP test shows that the Fe content is 0.45%. The doping element Fe can be observed as a single atom distribution by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium elements in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =25.6%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 27.9%, Ti 4+ (Ti4+ / Ti total ) content is 72.1%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.387. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.86%, the surface hydroxyl content measured by infrared spectroscopy is 0.23mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.6nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.96%.

[0397] TEM-EELS test results show that Fe and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Fe and Ti are found inside the particles. 3+ existence.

[0398] Formaldehyde concentration test showed that the removal rate was 82.9% after 90 minutes.

[0399] Example 47

[0400] The potassium permanganate in Example 29 was replaced with cobalt nitrate hexahydrate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0401] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.86, the absorbance at 800nm ​​was 0.87, and the absorbance at 850nm was 0.88.

[0402] The ICP test shows that the Co content is 0.52%. The spherical aberration electron microscopy method can observe that Co is distributed in a single atom. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =44.9%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 41.2%, Ti 4+ (Ti 4+ / Ti total ) content is 58.8%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.701; the fluorine element is 0.58%, and the fluorine element is lattice doping. The nitrogen content is 0.66%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 58.4% and 41.6%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.22%, the surface hydroxyl content measured by infrared spectroscopy is 0.42mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.1nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 0.82%.

[0403] TEM-EELS test results show that fluorine, nitrogen, cobalt and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine, nitrogen, cobalt and Ti are found inside the particles. 3+ existence.

[0404] Formaldehyde concentration test shows that the removal rate is 98.5% after 90 minutes

[0405] Example 48

[0406] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 47 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0407] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.51, the absorbance at 800nm ​​was 0.53, and the absorbance at 850nm was 0.55.

[0408] The ICP test shows that the Co content is 0.49%. The Co observed by spherical aberration electron microscopy is distributed in a single atom. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the corresponding peaks are obtained after fitting. L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =27.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 26.9%, Ti 4+ (Ti 4+ / Ti total ) content is 73.1%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.382. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.76%, the surface hydroxyl content measured by infrared spectroscopy is 0.17mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.4nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.79%.

[0409] TEM-EELS test results show that Co and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Co and Ti are found inside the particles. 3+ existence.

[0410] Formaldehyde concentration test showed that the removal rate was 83.5% after 90 minutes.

[0411] Example 49

[0412] The potassium permanganate of Example 29 was replaced by nickel sulfate hexahydrate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0413] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.85, the absorbance at 800nm ​​was 0.86, and the absorbance at 850nm was 0.89.

[0414] The ICP test shows that the Ni content is 0.61%. The doping elements observed by spherical aberration electron microscopy are distributed in single atoms. The XPS peaks of oxygen and titanium elements in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =43.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 43.4%, Ti 4+ (Ti 4+ / Ti total ) content is 56.6%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.767; the fluorine element is 0.49%, and the fluorine element is lattice doping. The nitrogen content is 0.72%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 57.3% and 42.7% respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.17%, the surface hydroxyl content measured by infrared spectroscopy is 0.39mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.5nm respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 0.86%.

[0415] TEM-EELS test results show that Ni, F, N and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ni, F, N and Ti are found inside the particles. 3+ existence.

[0416] Formaldehyde concentration test shows that the removal rate is 98.7% after 90 minutes

[0417] Example 50

[0418] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 49 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0419] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.55, the absorbance at 800nm ​​was 0.56, and the absorbance at 850nm was 0.58.

[0420] The Ni content of the product was 0.64% as determined by ICP. The Ni element was observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product were analyzed. The peak shapes were fitted to obtain the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =31.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 29.3%, Ti 4+ (Ti 4+ / Ti total ) content is 70.7%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.414. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.92%, the surface hydroxyl content measured by infrared spectroscopy is 0.25mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.6nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.96%.

[0421] TEM-EELS test results show that the elements Ni and Ti 3+ Mainly distributed within about 3nm from the surface of titanium oxide particles, no Ni and Ti were found inside the particles. 3+ existence.

[0422] Formaldehyde concentration test showed that the removal rate was 83.1% after 90 minutes.

[0423] Example 51

[0424] The potassium permanganate in Example 29 was replaced by Cu(NO 3 ) 2 , and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0425] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.85, the absorbance at 800nm ​​was 0.87, and the absorbance at 850nm was 0.88.

[0426] The Mn content of the ICP test is 0.98%, and the doping elements observed by spherical aberration electron microscopy are distributed in single atoms. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =42.1%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 44.6%, Ti 4+ (Ti 4+ / Ti total ) content is 55.4%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.805; the fluorine element is 0.71%, and the fluorine element is lattice doping. The nitrogen content is 0.55%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 56.9% and 43.1% respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.73%, the surface hydroxyl content measured by infrared spectroscopy is 0.42mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.8nm respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0.73%. 3+ The content loss rate is 0.73%.

[0427] TEM-EELS test results show that the elements F, N, Cu and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Cu and Ti are found inside the particles. 3+ existence.

[0428] Formaldehyde concentration test shows that the removal rate is 98.8% after 90 minutes

[0429] Example 52

[0430] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 51 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0431] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.54, the absorbance at 800nm ​​was 0.55, and the absorbance at 850nm was 0.57.

[0432] The ICP test shows that the Cu content is 0.96%. The spherical aberration electron microscopy method can observe that the Cu element is distributed in a single atom. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =33.6%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 28.1%, Ti 4+ (Ti 4+ / Ti total ) content is 71.9%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.391. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.84%, the surface hydroxyl content measured by infrared spectroscopy is 0.23mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.2nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.84%.

[0433] TEM-EELS test results show that Cu and Ti 3+ Mainly distributed within about 3nm from the surface of titanium oxide particles, no Cu and Ti were found inside the particles. 3+ existence.

[0434] Formaldehyde concentration test showed that the removal rate was 82.6% after 90 minutes.

[0435] Example 53

[0436] The potassium permanganate in Example 29 was replaced by ZnCl2, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0437] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.84, the absorbance at 800nm ​​was 0.85, and the absorbance at 850nm was 0.86.

[0438] The ICP test shows that the Zn content is 1.32%. The doping element Zn is observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the corresponding peaks are obtained after fitting. L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =40.2%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 42.9%, Ti 4+ (Ti 4+ / Ti total ) content is 57.1%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.751; the fluorine element is 0.64%, and the fluorine element is lattice doping. The nitrogen content is 0.61%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 48.7% and 51.3%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.24%, the surface hydroxyl content measured by infrared spectroscopy is 0.47mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.4nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 1.45%.

[0439] TEM-EELS test results show that the elements fluorine, nitrogen, zinc and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine, nitrogen, zinc and Ti are found inside the particles. 3+ existence.

[0440] Formaldehyde concentration test shows that the removal rate is 98.6% after 90 minutes

[0441] Example 54

[0442] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 53 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0443] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.56, the absorbance at 800nm ​​was 0.57, and the absorbance at 850nm was 0.59.

[0444] The ICP test shows that the Zn content is 1.36%. The doping element Zn is observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the corresponding peaks are obtained after fitting. L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =24.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 27.3%, Ti 4+ (Ti 4+ / Ti total ) content is 72.7%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.376. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.75%, the surface hydroxyl content measured by infrared spectroscopy is 0.22mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.1nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 1.33%.

[0445] TEM-EELS test results show that Zn and Ti 3+ Mainly distributed within about 3nm from the surface of titanium oxide particles, no Zn and Ti were found inside the particles. 3+ existence.

[0446] Formaldehyde concentration test showed that the removal rate was 82.1% after 90 minutes.

[0447] Example 55

[0448] The potassium permanganate of Example 29 was replaced by AgNO 3 , and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as those of Example 1.

[0449] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.92, the absorbance at 800nm ​​was 0.94, and the absorbance at 850nm was 0.95.

[0450] The Ag content in the ICP test is 1.47%, and the doped Ag is observed to be distributed in a single atom by spherical aberration electron microscopy. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =47.9%; after fitting, Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 49.1%, Ti 4+ (Ti 4+ / Ti total ) content is 50.9%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.965; the fluorine element is 0.67%, and the fluorine element is lattice doping. The nitrogen content is 0.53%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 47.9% and 52.1% respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.33%, the surface hydroxyl content measured by infrared spectroscopy is 0.52mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.6nm respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 1.27%.

[0451] TEM-EELS test results show that F, N, Ag and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Ag and Ti are found inside the particles. 3+ existence.

[0452] Formaldehyde concentration test shows that the removal rate is 99.4% after 90 minutes

[0453] Example 56

[0454] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 55 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0455] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.65, the absorbance at 800nm ​​was 0.68, and the absorbance at 850nm was 0.69.

[0456] The Ag content in the ICP test was 1.58%, and the spherical aberration electron microscopy method showed that the Ag element was distributed in a single atom. The XPS peaks of oxygen and titanium in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =35.8%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 34.2%, Ti 4+ (Ti 4+ / Ti total ) content is 65.8%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.52. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.52%, the surface hydroxyl content measured by infrared spectroscopy is 0.24mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.0nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 1.34%.

[0457] TEM-EELS test results show that the elements Ag and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no elements Ag and Ti are found inside the particles. 3+ existence.

[0458] Formaldehyde concentration test showed that the removal rate was 87.3% after 90 minutes.

[0459] Example 57

[0460] The potassium permanganate in Example 29 was replaced with HAuCl4·4H2O, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0461] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.91, the absorbance at 800nm ​​was 0.92, and the absorbance at 850nm was 0.93.

[0462] The Au content of the ICP test is 1.41%, and the doped Au element can be observed by spherical aberration electron microscopy to be distributed in a single atom. The XPS peaks of oxygen and titanium in the product were analyzed. According to the peak shape, the corresponding peaks of lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =47.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 48.5%, Ti 4+ (Ti 4+ / Ti total ) content is 51.5%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.942; the fluorine element is 0.58%, and the fluorine element is lattice doping. The nitrogen content is 0.63%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 54.4% and 45.6%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.26%, the surface hydroxyl content measured by infrared spectroscopy is 0.37mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 38.7nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 0.69%.

[0463] TEM-EELS test results show that F, N, Au and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Au and Ti are found inside the particles. 3+ existence.

[0464] Formaldehyde concentration test shows that the removal rate is 99.3% after 90 minutes

[0465] Example 58

[0466] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 57 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0467] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.66, the absorbance at 800nm ​​was 0.68, and the absorbance at 850nm was 0.70.

[0468] The ICP test shows that the Au content is 1.38%. The spherical aberration electron microscopy method can observe that the doped element Au is distributed in a single atom. The XPS peaks of oxygen and titanium in the product are analyzed. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =37.6%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 33.7%, Ti 4+ (Ti 4+ / Ti total ) content is 66.3%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.508. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.62%, the surface hydroxyl content measured by infrared spectroscopy is 0.24mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.3nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.84%.

[0469] TEM-EELS test results show that the elements Au and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Au and Ti elements are found inside the particles. 3+ existence.

[0470] Formaldehyde concentration test showed that the removal rate was 89.6% after 90 minutes.

[0471] Example 59

[0472] The potassium permanganate in Example 29 was replaced by PdCl2(H2O)2. The sample analysis and formaldehyde degradation test methods were the same as those in Example 1.

[0473] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.90, the absorbance at 800nm ​​was 0.92, and the absorbance at 850nm was 0.95.

[0474] The Pd content of the ICP test is 1.51%. The Pd doping element can be observed by spherical aberration electron microscopy to be distributed in a single atom. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =46.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 49.6%, Ti 4+ (Ti 4+ / Ti total ) content is 50.4%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.984; the fluorine element is 0.55%, which is lattice doping. The nitrogen content is 0.66%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 51.3% and 48.7% respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.42%, the surface hydroxyl content measured by infrared spectroscopy is 0.56mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.7nm respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 0.91%.

[0475] TEM-EELS test results show that the elements F, N, Pd and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Pd and Ti are found inside the particles. 3+ existence.

[0476] Formaldehyde concentration test shows that the removal rate is 99.2% after 90 minutes

[0477] Example 60

[0478] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 59 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0479] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.66, the absorbance at 800nm ​​was 0.67, and the absorbance at 850nm was 0.69.

[0480] The Pd content of the ICP test is 1.49%. The Pd doping element can be observed by spherical aberration electron microscopy to be distributed in a single atom. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =38.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 34.6%, Ti 4+ (Ti 4+ / Ti total ) content is 65.4%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.529. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.83%, the surface hydroxyl content measured by infrared spectroscopy is 0.17mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.4nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 1.24%.

[0481] TEM-EELS test results show that the elements Pd and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Pd and Ti are found inside the particles. 3+ existence.

[0482] Formaldehyde concentration test showed that the removal rate was 88.4% after 90 minutes.

[0483] Example 61

[0484] The potassium permanganate in Example 29 was replaced by potassium hexachloroplatinate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0485] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.89, the absorbance at 800nm ​​was 0.91, and the absorbance at 850nm was 0.92.

[0486] The Pt content of the ICP test is 1.25%. The Pt doping element can be observed by spherical aberration electron microscopy to be distributed in a single atom. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =46.7%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 46.8%, Ti 4+ (Ti 4+ / Ti total ) content is 53.2%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.880; the fluorine element is 0.61%, and the fluorine element is lattice doping. The nitrogen content is 0.58%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 52.6% and 47.4%, respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.32%, the surface hydroxyl content measured by infrared spectroscopy is 0.59mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.3nm, respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 1.02%.

[0487] TEM-EELS test results show that the elements F, N, Pt and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Pt and Ti are found inside the particles. 3+ existence.

[0488] Formaldehyde concentration test showed that the removal rate was 99.1% after 90 minutes.

[0489] Example 62

[0490] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 61 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0491] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.64, the absorbance at 800nm ​​was 0.66, and the absorbance at 850nm was 0.67.

[0492] The Pt content of the ICP test is 1.33%. The Pt doping element can be observed by spherical aberration electron microscopy to be distributed in a single atom. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =39.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 32.3%, Ti 4+ (Ti 4+ / Ti total ) content is 67.7%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.477. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.39%, the surface hydroxyl content measured by infrared spectroscopy is 0.26mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.6nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 1.09%.

[0493] TEM-EELS test results show that the elements Pt and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Pt and Ti are found inside the particles. 3+ existence.

[0494] Formaldehyde concentration test showed that the removal rate was 86.5% after 90 minutes.

[0495] Example 63

[0496] The potassium permanganate in Example 29 was replaced with cerium nitrate hexahydrate, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0497] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.88, the absorbance at 800nm ​​was 0.89, and the absorbance at 850nm was 0.90.

[0498] The ICP test shows that the Ce content is 0.99%. The spherical aberration electron microscopy method can observe that the doped Ce element is distributed in a single atom. The XPS peaks of oxygen and titanium elements in the product are analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =45.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 45.4%, Ti 4+ (Ti 4+ / Ti total ) content is 54.6%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.832; the fluorine element is 0.63%, and the fluorine element is lattice doping. The nitrogen content is 0.61%, and N doping includes lattice doping and interstitial doping. The proportion of lattice doping and interstitial doping in the total doping is 57.4% and 42.6% respectively. The mass loss percentage measured by thermogravimetric analysis at 300°C is 1.42%, the surface hydroxyl content measured by infrared spectroscopy is 0.52mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.6nm respectively. The surface Ti after 10 cycles of deionized water washing at 100°C is 0. 3+ The content loss rate is 0.96%.

[0499] TEM-EELS test results show that the elements F, N, Ce and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no F, N, Ce and Ti are found inside the particles. 3+ existence.

[0500] Formaldehyde concentration test shows that the removal rate is 99.0% after 90 minutes

[0501] Example 64

[0502] The steps of adding ammonium fluoride and irradiating for 24 hours in Example 63 were omitted, and the remaining conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0503] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.61, the absorbance at 800nm ​​was 0.62, and the absorbance at 850nm was 0.64.

[0504] The Ce content of the ICP test is 0.98%, and the Ce doping element observed by spherical aberration electron microscopy is distributed in a single atom. The XPS peaks of oxygen and titanium elements in the product were analyzed. According to the peak shape, the corresponding peaks to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =32.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, Ti 3+ (Ti 3+ / Ti total ) content is 31.4%, Ti 4+ (Ti 4+ / Ti total ) content is 68.6%, and the surface Ti 3+ Content and surface Ti 4+The content ratio is 0.458. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 1.54%, the surface hydroxyl content measured by infrared spectroscopy is 0.19mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.2nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.91%.

[0505] TEM-EELS test results show that the elements Ce and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ce and Ti are found inside the particles. 3+ existence.

[0506] The formaldehyde concentration test showed that the removal rate was 85.6% after 90 minutes.

[0507] Example 65

[0508] The nano-titanium oxide in Example 5 was replaced with tetragonal ZrO2 with a particle size in the range of 20-45 nm and an average particle size of 34.6 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0509] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.45, the absorbance at 800nm ​​was 0.46, and the absorbance at 850nm was 0.48.

[0510] Combined with the literature information, XPS was used to analyze the elemental composition and valence of the product. The product is composed of Zr, O, F and N. The position and linear symmetry analysis of the Zr 3d peak show that the zirconium element exists 3+ and Zr 4+ Two valence states, after fitting, Zr 3+ and Zr 4+ Peak, Zr 3+ / Zr total 51.3%, Zr before reaction 3+ / Zr total The XPS spectrum of the O 1s electron energy level is an asymmetric Gaussian line shape, indicating that it is composed of a variety of oxygen bonding states superimposed; after fitting the O1s, the corresponding adsorbed oxygen (O a ), oxygen vacancies (O V ) lattice oxygen (O L ) peak, O V / O 总 The value is 41.4%, and the O v / O 总The value is 8.2%. The fluorine content is 0.41%, and the nitrogen content is 0.36%. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.62%. The particle size distribution range and average particle size measured by SEM are 20-45nm and 34.2nm respectively.

[0511] TEM-EELS test results show that Zr 3+ , fluorine and nitrogen elements are mainly distributed within about 3nm from the surface of ZrO2 particles, and no Zr is found inside the particles. 3+ , fluorine and nitrogen elements.

[0512] The formaldehyde concentration test showed that the removal rate was 85.7% after 90 minutes.

[0513] Example 66

[0514] The nano-titanium oxide in Example 5 was replaced with hexagonal wurtzite ZnO with a particle size ranging from 25 to 65 nm and an average particle size of 32.5 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0515] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.55, the absorbance at 800nm ​​was 0.56, and the absorbance at 850nm was 0.58.

[0516] Combined with the literature information, XPS was used to analyze the elemental composition and valence of the product. The product is composed of Zn, O, F, and N. The position and linear symmetry analysis of the Zn 2p peak showed that Zn is a single component. 2+ The XPS spectrum of O 1s electron energy level is an asymmetric Gaussian line, indicating that it is composed of multiple oxygen bonding states. After fitting O1s, the corresponding adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O V / O 总 The value is 16.9%, before ZnO reaction O v / O 总 The value is 4.2%. The fluorine content is 0.32%, and the nitrogen content is 0.29%. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.64%. The particle size distribution range and average particle size measured by SEM are 25-65nm and 32.5nm respectively.

[0517] The TEM-EELS test results show that fluorine and nitrogen elements are mainly distributed within about 3 nm from the surface of ZnO particles, and no fluorine and nitrogen are found inside the particles.

[0518] The formaldehyde concentration test showed that the removal rate was 83.6% after 90 minutes.

[0519] Example 67

[0520] The nano-titanium oxide in Example 5 was replaced with monoclinic BiVO4 with a particle size ranging from 20 to 70 nm and an average particle size of 31.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0521] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.54, the absorbance at 800nm ​​was 0.56, and the absorbance at 850nm was 0.58.

[0522] XPS was used to analyze the elemental composition and valence state of the product. The product is composed of Bi, V, O, F, and N. The double peak position of Bi 4f indicates that the chemical state of bismuth is Bi 3+ According to the peak shape, the peaks of O1s, V 2p and F1s were fitted in combination with the literature. After fitting O 1s, the peaks corresponding to adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =25.8%, O before BiVO4 reaction v / O 总 =5.1%; after fitting, V 4+ and V 5+ Peak, V 4+ The content is 24.3%, which is higher than that of BiVO4 before reaction. 4+ The content is 2.4%. For BiVO4, oxygen vacancies and V 4+ The presence of fluorine can improve light absorption to a certain extent. The fluorine content is 0.44%, and the nitrogen content is 0.31%. The mass loss measured by thermogravimetric analysis at 300°C is 0.68%. The particle size distribution range and average particle size measured by SEM are 20-70nm and 31.2nm, respectively.

[0523] TEM-EELS test results show that fluorine and nitrogen elements as well as V 4+ It is mainly distributed within about 3nm from the surface of BiVO4 particles, and no fluorine, nitrogen and V are found inside the particles. 4+ existence.

[0524] The formaldehyde concentration test showed that the removal rate was 88.7% after 90 minutes.

[0525] Example 68

[0526] The nano-titanium oxide in Example 5 was replaced with monoclinic WO3 with a particle size in the range of 20-80 nm and an average particle size of 51.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0527] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.44, the absorbance at 800nm ​​was 0.46, and the absorbance at 850nm was 0.49.

[0528] Analyze the XPS peaks of W, O, F and N elements in the product. According to the shape of the O1s spectrum peak, the peaks corresponding to the adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =23.4%, O before WO3 reaction v / O L =5.6%; after fitting, we get W 5+ and W 6+ Peak, W before and after the reaction 5+ The contents of fluorine and nitrogen are 4.1% and 41.4%, respectively; the fluorine content is 0.69% and the nitrogen content is 0.27%. The mass loss measured by thermogravimetric analysis at 300°C is 0.59%. The particle size distribution range and average particle size measured by SEM are 20-80nm and 50.8nm, respectively.

[0529] TEM-EELS test results show that W 5+ , fluorine and nitrogen are mainly distributed within about 3nm from the surface of tungsten oxide particles, and no nitrogen, fluorine and W are found inside the particles. 5+ existence.

[0530] The formaldehyde concentration test showed that the removal rate was 81.3% after 90 minutes.

[0531] Example 69

[0532] The nano-titanium oxide in Example 5 was replaced with rutile SnO2 with a particle size ranging from 20 to 50 nm and an average particle size of 31.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0533] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.49, the absorbance at 800nm ​​was 0.52, and the absorbance at 850nm was 0.53.

[0534] XPS was used to analyze the elemental composition and valence state of the product. The product is composed of Sn, O, F, and N. The double peak position of Sn 3d (487.5, 495.6 eV) indicates that the chemical state of tin is Sn 4+ According to the peak shape, the peaks of O1s, F 1s and N1s were fitted in combination with the literature. After fitting O 1s, the peaks corresponding to adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =20.3%, O before SnO2 reaction v / O 总 =3.1%; fluorine content is 0.58%, replacing oxygen doping; nitrogen content is 0.44%. The mass loss measured by thermogravimetric analysis at 300°C is 0.58%, and the particle size distribution range and average particle size measured by SEM are 20-50nm and 31.1nm, respectively.

[0535] The TEM-EELS test results show that fluorine and nitrogen elements are mainly distributed within about 3 nm from the surface of SnO2 particles, and no fluorine and nitrogen are found inside the particles.

[0536] The formaldehyde concentration test showed that the removal rate was 88.2% after 90 minutes.

[0537] Example 70

[0538] The nano-titanium oxide in Example 29 was replaced with tetragonal ZrO2 with a particle size in the range of 20-45 nm and an average particle size of 34.6 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0539] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.63, the absorbance at 800nm ​​was 0.64, and the absorbance at 850nm was 0.66.

[0540] ICP test shows that the manganese content is 0.96%; the Mn observed by spherical aberration electron microscopy is distributed in a single atom. Combined with literature information, XPS was used to analyze the elemental composition and valence of Zr, O, F and N in the product. The position and linear symmetry analysis of the Zr 3d peak showed that the zirconium element Zr 3+ and Zr 4+ Two valence states, after fitting, Zr 3+ and Zr 4+ Peak, Zr 3+ / Zr total 53.4%, Zr before reaction 3+ / Zr total The XPS spectrum of the O 1s electron energy level is an asymmetric Gaussian line shape, indicating that it is composed of a variety of oxygen bonding states superimposed; after fitting the O1s, the corresponding adsorbed oxygen (O a ), oxygen vacancies (O V ) lattice oxygen (O L ) peak, O V / O 总 The value is 46.3%, and the O v / O 总 The value is 8.2%. The fluorine content is 0.47%, and the nitrogen content is 0.39%. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.71%. The particle size distribution range and average particle size measured by SEM are 20-45nm and 34.9nm respectively.

[0541] TEM-EELS test results show that Zr 3+ , fluorine, nitrogen and manganese are mainly distributed within about 3nm from the surface of ZrO2 particles, and no Zr is found inside the particles. 3+ , fluorine, nitrogen and manganese.

[0542] The formaldehyde concentration test showed that the removal rate was 89.2% after 90 minutes.

[0543] Example 71

[0544] The nano-titanium oxide in Example 29 was replaced with hexagonal wurtzite ZnO with a particle size of 25-65 nm and an average particle size of 32.5 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0545] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.75, the absorbance at 800nm ​​was 0.77, and the absorbance at 850nm was 0.79.

[0546] The ICP test showed that the manganese content was 0.89%; the Mn observed by spherical aberration electron microscopy was distributed in a single atom. Combined with the literature information, XPS was used to analyze the elemental composition and valence of Zn, O, F and N in the product. The position and linear symmetry analysis of the Zn 2p peak showed that the zinc element was a single component Zn. 2+ The XPS spectrum of O 1s electron energy level is an asymmetric Gaussian line, indicating that it is composed of multiple oxygen bonding states superimposed; after fitting O1s, the corresponding adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O V / O 总 The value is 12.4%, and the O v / O 总 The value is 4.2%. The fluorine content is 0.39%, and the nitrogen content is 0.33%. The mass loss percentage measured by thermogravimetric analysis at 300°C is 0.69%. The particle size distribution range and average particle size measured by SEM are 25-65nm and 32.5nm respectively.

[0547] The TEM-EELS test results show that fluorine, nitrogen and manganese elements are mainly distributed within about 3 nm from the surface of ZnO particles, and no fluorine, nitrogen and manganese are found inside the particles.

[0548] The formaldehyde concentration test showed that the removal rate was 88.2% after 90 minutes.

[0549] Example 72

[0550] The nano-titanium oxide in Example 29 was replaced with monoclinic BiVO4 with a particle size ranging from 20 to 70 nm and an average particle size of 31.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0551] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.72, the absorbance at 800nm ​​was 0.75, and the absorbance at 850nm was 0.78.

[0552] ICP test shows that the manganese content is 0.92%; the Mn observed by spherical aberration electron microscopy is distributed in a single atom. XPS is used to analyze the elemental composition and valence of Bi, V, O, F and N in the product. The double peak position of Bi 4f indicates that the chemical state of bismuth is Bi 3+ . O 1s fitting results correspond to the adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a+O v +O L , O V / O 总 =29.7%, O before BiVO4 reaction v / O 总 =5.1%; after fitting, V 4+ and V 5+ Peak, V 4+ The content of BiVO4 is 27.6%, which is higher than the 2.4% before the reaction. 4+ The presence of fluorine can improve light absorption to a certain extent. The fluorine content is 0.80%, and the nitrogen content is 0.36%. The mass loss measured by thermogravimetric analysis at 300°C is 0.75%. The particle size distribution range and average particle size measured by SEM are 20-70nm and 31.7nm, respectively.

[0553] TEM-EELS test results show that fluorine, nitrogen, manganese and V 4+ It is mainly distributed within about 3nm from the surface of BiVO4 particles, and no fluorine, nitrogen, manganese and V are found inside the particles. 4+ existence.

[0554] The formaldehyde concentration test showed that the removal rate was 90.5% after 90 minutes.

[0555] Example 73

[0556] The nano-titanium oxide in Example 29 was replaced with monoclinic WO 3 having a particle size range of 20-80 nm and an average particle size of 51.2 nm, and the other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0557] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.71, the absorbance at 800nm ​​was 0.74, and the absorbance at 850nm was 0.76.

[0558] The ICP test shows that the manganese content is 1.02%. The Mn observed by spherical aberration electron microscopy is distributed in a single atom. The XPS peaks of W, O, F and N in the product were analyzed. According to the shape of the O1s spectrum peak, the corresponding peaks to the adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =28.3%, O before WO3 reactionv / O L =5.6%; after fitting, we get W 5+ and W 6+ Peak, W before and after the reaction 5+ The contents of fluorine and nitrogen are 4.1% and 45.7%, respectively; the fluorine content is 0.38%, and the nitrogen content is 0.32%. The mass loss measured by thermogravimetric analysis at 300°C is 0.65%. The particle size distribution range and average particle size measured by SEM are 20-80nm and 51.5nm, respectively.

[0559] TEM-EELS test results show that W 5+ , fluorine, nitrogen and manganese are mainly distributed within about 3nm from the surface of tungsten oxide particles, and no W is found inside the particles. 5+ , the presence of fluorine, nitrogen and manganese.

[0560] The formaldehyde concentration test showed that the removal rate was 84.6% after 90 minutes.

[0561] Example 74

[0562] The nano-titanium oxide in Example 29 was replaced with rutile SnO2 with a particle size ranging from 20 to 50 nm and an average particle size of 31.2 nm. Other conditions were the same. The sample analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0563] The test results of UV-visible diffuse reflectance absorption spectrum showed that the absorbance at a wavelength of 760nm was 0.66, the absorbance at 800nm ​​was 0.68, and the absorbance at 850nm was 0.69.

[0564] ICP test shows that the manganese content is 1.06%; the Mn observed by spherical aberration electron microscopy is distributed in a single atom. XPS is used to analyze the elemental composition and valence of Sn, O, F and N in the product. The double peak position of Sn 3d (487.5, 495.6eV) indicates that the chemical state of tin is Sn 4+ According to the peak shape, the peaks of O 1s, F 1s and N 1s were fitted in combination with the literature. After fitting O 1s, the peaks corresponding to adsorbed oxygen (O a ), oxygen vacancies (O V ) and lattice oxygen (O L ) peak, O 总 =O a +O v +O L , O V / O 总 =26.4%, O before SnO2 reaction v / O 总=3.1%; fluorine content is 0.56%, replacing oxygen doping; nitrogen content is 0.48%. The mass loss measured by thermogravimetric analysis at 300°C is 0.62%. The particle size distribution range and average particle size measured by SEM are 20-50nm and 31.6nm, respectively.

[0565] The TEM-EELS test results show that fluorine, nitrogen and manganese elements are mainly distributed within about 3 nm from the surface of SnO2 particles, and no fluorine, nitrogen and manganese elements are found inside the particles.

[0566] The formaldehyde concentration test showed that the removal rate was 91.5% after 90 minutes.

[0567] Example 75

[0568] The height of the cylindrical quartz glass container in Example 1 was increased to 300 mm, and the volume of pure water added was changed to 1.54 L (the liquid level was about 240 mm). At this time, the average thickness of the liquid film was 120 mm, and the other conditions were the same.

[0569] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.49, the absorbance at 800nm ​​was 0.52, and the absorbance at 850nm was 0.53.

[0570] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =23.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 34.1%, Ti 4+ (Ti 4+ / Ti total ) content is 73.5%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.517, the mass loss percentage measured by thermogravimetric analysis at 300 ° C is 0.63%, the surface hydroxyl content measured by infrared spectroscopy is 0.35 mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70 nm and 40.7 nm respectively, and the surface Ti after 100 ° C deionized water cycle washing is 3+ The content loss rate is 0.43%.

[0571] TEM-EELS test results show that Ti3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ti is found inside the particles. 3+ existence.

[0572] The formaldehyde concentration test showed that the removal rate was 82.3% after 90 minutes.

[0573] Example 76

[0574] The height of the cylindrical quartz glass container in Example 1 was increased to 450 mm, and the volume of pure water added was changed to 2.56 L (the liquid level was about 400 mm). At this time, the average thickness of the liquid film was 200 mm, and the other conditions were the same.

[0575] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.26, the absorbance at 800nm ​​was 0.29, and the absorbance at 850nm was 0.31.

[0576] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =14.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 26.5%, Ti 4+ (Ti 4+ / Ti total ) content is 73.5%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.361, the mass loss percentage measured by thermogravimetric analysis at 300 ° C is 0.54%, the surface hydroxyl content measured by infrared spectroscopy is 0.18 mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70 nm and 40.1 nm respectively, and the surface Ti after 100 ° C deionized water cycle washing is 3+ The content loss rate is 0.54%.

[0577] TEM-EELS test results show that Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ti is found inside the particles. 3+ existence.

[0578] The formaldehyde concentration test showed that the removal rate was 75.3% after 90 minutes.

[0579] Example 77

[0580] The height of the cylindrical quartz glass container in Example 1 was changed to 30 mm, and the volume of pure water added was changed to 6.4 ml. At this time, the average thickness of the liquid film was 0.5 mm, and the other conditions remained the same.

[0581] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.31, the absorbance at 800nm ​​was 0.33, and the absorbance at 850nm was 0.36.

[0582] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =12.6%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 29.1%, Ti 4+ (Ti 4+ / Ti total ) content is 70.9%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.41, the mass loss percentage measured by thermogravimetric analysis at 300 ° C is 0.51%, the surface hydroxyl content measured by infrared spectroscopy is 0.16 mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70 nm and 40.5 nm respectively, and the surface Ti after 100 ° C deionized water cycle washing is 3+ The content loss rate is 0.52%.

[0583] TEM-EELS test results show that Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ti is found inside the particles. 3+ existence.

[0584] The formaldehyde concentration test showed that the removal rate was 75.6% after 90 minutes.

[0585] Example 78

[0586] The height of the cylindrical quartz glass container in Example 1 was changed to 30 mm, and the volume of pure water added was changed to 12.8 ml. At this time, the average thickness of the liquid film was 1 mm, and the other conditions remained the same.

[0587] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.51, the absorbance at 800nm ​​was 0.53, and the absorbance at 850nm was 0.55.

[0588] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =22.7%; after fitting, Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) content is 32.5%, Ti 4+ (Ti 4+ / Ti total ) content is 67.5%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.481, the mass loss percentage measured by thermogravimetric analysis at 300 ° C is 0.59%, the surface hydroxyl content measured by infrared spectroscopy is 0.32 mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70 nm and 40.6 nm respectively, and the surface Ti after 100 ° C deionized water cycle washing 10 times is 0. 3+ The content loss rate is 0.41%.

[0589] TEM-EELS test results show that Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ti is found inside the particles. 3+ existence.

[0590] The formaldehyde concentration test showed that the removal rate was 86.6% after 90 minutes.

[0591] Comparative Example 1

[0592] The first raw material mixture in Example 3 was taken, and stirring and ventilation were stopped. After natural sedimentation, the supernatant was removed and filtered to obtain wet titanium oxide. The mixture was centrifuged and weighed. The catalyst weight gain was 80 mg. The ArF excimer light source system in Example 3 was used and placed 2 cm above the catalyst. The light source spot was adjusted so that the output power was 2 W and the irradiation area was 40 cm. 2 The water film thickness was calculated to be 0.01 mm, and the irradiation dose was 2 W / g. The irradiation time was 24 hours, during which the catalyst was constantly turned to ensure uniform light exposure. Finally, the sample was washed several times with distilled water and dried at 60°C for 6 hours to obtain the product.

[0593] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.07, the absorbance at 800nm ​​was 0.08, and the absorbance at 850nm was 0.09.

[0594] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =6.1%; after fitting, Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 7.8%, Ti 4+ (Ti 4+ / Ti total ) content is 92.2%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.085; the fluorine content is 0.04%. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.07%, the surface hydroxyl content measured by infrared spectroscopy is 0.07mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.3nm respectively. The surface Ti after 10 cycles of deionized water washing at 100℃ is 0.07mmol / g. 3+ The content loss rate is 0.12%.

[0595] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0596] The formaldehyde concentration test showed that the removal rate was 4.1% after 90 minutes.

[0597] Comparative Example 2

[0598] The wet titanium oxide in Comparative Example 1 was dried at 60° C. and then irradiated with ultraviolet light under the same irradiation conditions as in Comparative Example 1. Finally, the sample was washed several times with distilled water and dried to obtain the product.

[0599] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.05, the absorbance at 800nm ​​was 0.06, and the absorbance at 850nm was 0.08.

[0600] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (OL ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =3.2%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 3.5%, Ti 4+ (Ti 4+ / Ti total ) content is 96.5%, the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.036; the fluorine element is 0.02%, and it is an alternative to oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.05%, the surface hydroxyl content measured by infrared spectroscopy is 0.05mmol / g, and the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.8nm respectively. The surface Ti after 100℃ deionized water cycle washing is 3+ The content loss rate is 0.16%.

[0601] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0602] The formaldehyde concentration test showed that the removal rate was 3.5% after 90 minutes.

[0603] Comparative Example 3

[0604] The titanium oxide from Comparative Example 1 was irradiated under vacuum ultraviolet light, using the same irradiation conditions and wetting conditions as in Comparative Example 1. During this process, distilled water was continuously sprayed onto the catalyst, and the catalyst was stirred to maintain a water film thickness of 0.01 mm and uniform exposure to light. Finally, the sample was washed several times with distilled water and dried at 60°C for 6 hours to obtain the product.

[0605] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.18, the absorbance at 800nm ​​was 0.17, and the absorbance at 850nm was 0.15.

[0606] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O总 =8.7%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 8.9%, Ti 4+ (Ti 4+ / Ti total ) content is 91.1%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.098; the fluorine element is 0.09%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.21%, the surface hydroxyl content measured by infrared spectroscopy is 0.11mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 39.4nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.19%.

[0607] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0608] The formaldehyde concentration test showed that the removal rate was 4.2% after 90 minutes.

[0609] Comparative Example 4

[0610] A PL-ZW222L light source system from Beijing Princess Company was used, and the light source can output 222nm ultraviolet light with an output power of about 2W. The light source system is equipped with a reaction bottle with a capacity of 500ml, a cylindrical light source is placed in the center of the volumetric flask, and a water bath is used to control the reaction temperature. 0.4L of pure water was poured into the reaction bottle, and stirring was continued at 200rpm. At the same time, nitrogen was introduced to the bottom of the container at a rate of 50ml / min; then 1.0g of titanium dioxide in particle size embodiment 1 was added to the reaction bottle, and stirring and ventilation were continued until the titanium oxide and water were evenly mixed to obtain a first raw material mixture. Then the light source was turned on, the irradiation dose was 2W / g, the particles were randomly dispersed in the water, the average thickness of the liquid film was 3.5mm, and the reaction was irradiated for 24 hours to obtain a first product mixture. The first product mixture was processed in the same way as in Example 1 to obtain a product, and the product analysis and formaldehyde degradation test methods were also the same as in Example 1.

[0611] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.12, the absorbance at 800nm ​​was 0.14, and the absorbance at 850nm was 0.15.

[0612] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O V / O 总 =2.3%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 9.8%, Ti 4+ (Ti 4+ / Ti total ) content is 90.2%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.109; the fluorine element is 0.18%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.29%, the surface hydroxyl content measured by infrared spectroscopy is 0.14mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.3nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.21%.

[0613] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0614] The formaldehyde concentration test showed that the removal rate was 4.5% after 90 minutes.

[0615] Comparative Example 5

[0616] The ArF excimer laser light source in Example 3 was replaced with a 4W ordinary light source, which only contained 254nm ultraviolet light (photoelectric conversion efficiency was 50%). The light source was cylindrical and waterproof, and was vertically inserted into the center of the reaction vessel and completely immersed in water. The irradiation dose was 2W / g, and the particles were randomly dispersed in the water. The other conditions were the same as in Example 3.

[0617] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.1, the absorbance at 800nm ​​was 0.12, and the absorbance at 850nm was 0.14.

[0618] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (Oa ) peak, calculated to be O V / O 总 =2.5%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total ) is 9.2%, Ti 4+ (Ti 4+ / Ti total ) content is 90.2%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.102; the fluorine element is 0.11%, and it is an alternative oxygen doping. The mass loss percentage measured by thermogravimetric analysis at 300℃ is 0.24%, the surface hydroxyl content measured by infrared spectroscopy is 0.12mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70nm and 40.1nm respectively, and the surface Ti after 100℃ deionized water cycle washing is 10 times. 3+ The content loss rate is 0.23%.

[0619] TEM-EELS test results show that elemental fluorine and Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no fluorine and Ti are found inside the particles. 3+ existence.

[0620] The formaldehyde concentration test showed that the removal rate was 4.2% after 90 minutes.

[0621] Comparative Example 6

[0622] The height of the cylindrical quartz glass container in Example 1 was changed to 30 mm. No water was added. Only nitrogen gas with a relative humidity of 70% was used to continuously purge the powdered catalyst. The catalyst was constantly turned over to ensure uniform light exposure. Other conditions remained the same.

[0623] The UV-visible diffuse reflectance absorption spectrum test results showed that the absorbance at a wavelength of 760nm was 0.09, the absorbance at 800nm ​​was 0.11, and the absorbance at 850nm was 0.13.

[0624] Analyze the XPS peaks of oxygen and titanium elements in the product. According to the peak shape, the peaks corresponding to lattice oxygen (O L ), oxygen vacancies (O V ) and adsorbed oxygen (O a ) peak, calculated to be O v / O 总 =3.4%; after fitting, we get Ti 4+ and Ti 3+ Peak, (Ti 3+ / Ti total) content is 8.2%, Ti 4+ (Ti 4+ / Ti total ) content is 91.8%, and the surface Ti 3+ Content and surface Ti 4+ The content ratio is 0.089, the mass loss percentage measured by thermogravimetric analysis at 300 ° C is 0.15%, the surface hydroxyl content measured by infrared spectroscopy is 0.06 mmol / g, the particle size distribution range and average particle size measured by SEM are 20-70 nm and 40.3 nm respectively, and the surface Ti after 100 ° C deionized water cycle washing is 3+ The content loss rate is 0.25%.

[0625] TEM-EELS test results show that Ti 3+ It is mainly distributed within about 3nm from the surface of titanium oxide particles, and no Ti is found inside the particles. 3+ existence.

[0626] The formaldehyde concentration test showed that the removal rate was 5.2% after 90 minutes.

Claims

1. A method for manufacturing a photocatalytic material, comprising the following steps: 1) Providing a photocatalytic material precursor covered with a liquid film, 2) Irradiating the photocatalytic material precursor with rays having a wavelength of less than 200 nm (preferably 100 - 200 nm or 120 - 200 nm) (preferably vacuum ultraviolet light) to obtain the photocatalytic material.

2. The manufacturing method according to claim 1, wherein the operating conditions of the irradiation include: The operating temperature is -50 - 95 °C (preferably 10 - 70 °C), the operating pressure is 0 - 1 MPaG (preferably 0 - 0.1 MPaG), the lower limit of the duration is 0.1 h (preferably 1 h, 2 h or 3 h), and the upper limit of the duration is 120 h (preferably 60 h, 36 h, 20 h, 15 h or 10 h).

3. The manufacturing method according to claim 1, wherein the photocatalytic material precursor is selected from at least one of sulfide - type photocatalytic materials and their precursors, metal - oxide - type photocatalytic materials and their precursors, carbon nitride - based photocatalytic materials and their precursors, metal oxysalts and their precursors, and composites of these photocatalytic materials and their precursors, particularly preferably selected from at least one of TiO2, ZrO2, ZnO, BiVO4, WO3, SnO2, and composites of these photocatalytic materials and their precursors, more preferably selected from at least one of titanium dioxide and its precursors, and / or, based on the total weight of the photocatalytic material precursor, the photocatalytic material precursor contains 80 wt% or more (preferably 80 - 99.9 wt% or 85 - 99.5 wt%) of titanium dioxide.

4. The manufacturing method according to claim 1, wherein the photocatalytic material precursor is in the form of solid particles, and the particle size distribution range measured by the SEM method of the solid particles is 5 - 150 nm (preferably 10 - 110 nm) or the average particle size is 20 - 85 nm (preferably 30 - 70 nm).

5. The manufacturing method according to claim 1, wherein the average thickness of the liquid film is 0.5 - 200 mm (preferably 1 - 120 mm or 5 - 80 mm).

6. The manufacturing method according to claim 1, wherein the irradiation is carried out in an inert gas atmosphere, preferably under the condition of inert gas flow or nitrogen gas flow aeration.

7. The manufacturing method according to claim 1, wherein the irradiation dose of the irradiation is 0.01 - 50 W / g (preferably 0.1 - 20 W / g), and the irradiation power of the rays is 0.1 - 200 W (preferably 1 - 50 W).

8. The manufacturing method according to claim 1, wherein the mass ratio of the liquid to the photocatalytic material precursor is 0.1 - 10000:1 (preferably 2 - 5000:1, more preferably 5 - 1000:1).

9. The manufacturing method according to claim 1, wherein the liquid further contains at least one doping element selected from Group IIIA elements of the periodic table (preferably at least one of B and Ga), Group IVA elements of the periodic table (preferably at least one of C and Ge), Group VA elements of the periodic table (preferably at least one of N and P), non-oxygen Group VIA elements of the periodic table (preferably at least one of S and Se), Group VIIA elements of the periodic table (preferably F), non-noble transition metal elements of the periodic table other than Ti (preferably at least one selected from Mn, Fe, Co, Ni, Cu, Zn), noble metal elements of the periodic table (preferably at least one selected from Ag, Au, Pd, and Pt), and rare earth metal elements of the periodic table (preferably at least one selected from Ce, La, Nd, Gd), preferably at least one doping element selected from N, Mn, and F, particularly preferably containing N, Mn, and F simultaneously as doping elements, and based on the total weight of the photocatalytic material precursor, the dosage of the doping element(s) (in elemental form) alone or in total is 0.01 - 1000 wt% (preferably 0.1 - 200 wt%).

10. The manufacturing method according to claim 1, without subjecting the photocatalytic material to heat treatment at a temperature above 300 °C (preferably above 200 °C).

11. A photocatalytic material comprising titanium dioxide, wherein the ratio of the surface Ti content measured by XPS method to the surface Ti content is 1:19 - 19:1 (preferably 1:4 - 4:1), and in its ultraviolet-visible diffuse reflection spectrum, the absorbance at a wavelength of 760 nm is 0.20 - 2.0 (preferably 0.30 - 1.8), the absorbance at a wavelength of 800 nm is 0.25 - 1.8 (preferably 0.35 - 1.6), and the absorbance at a wavelength of 850 nm is 0.25 - 1.7 (preferably 0.35 - 1.5). 3+ content to the surface Ti 4+ content is 1:19 - 19:1 (preferably 1:4 - 4:1), and in its ultraviolet-visible diffuse reflection spectrum, the absorbance at a wavelength of 760 nm is 0.20 - 2.0 (preferably 0.30 - 1.8), the absorbance at a wavelength of 800 nm is 0.25 - 1.8 (preferably 0.35 - 1.6), and the absorbance at a wavelength of 850 nm is 0.25 - 1.7 (preferably 0.35 - 1.5).

12. The photocatalytic material according to claim 11, wherein the particle size distribution range measured by the SEM method is 5 - 150 nm (preferably 10 - 110 nm) or the average particle size is 20 - 85 nm (preferably 30 - 70 nm).

13. The photocatalytic material according to claim 11, wherein the surface Ti measured by XPS 3+ content is 5%-95% (preferably 20%-80%), and the surface Ti measured by XPS 4+ content is 5%-95% (preferably 20%-80%), and / or, after the O1s peak of its XPS measurement is fitted, the content of the oxygen vacancy O V peak is 10%-80% (preferably 15%-60%), and / or, the mass loss percentage measured by its thermogravimetric analysis at 300 °C is 0.2-7 wt% (preferably 0.5-5 wt%), and / or, the surface hydroxyl content measured by its infrared spectroscopy is 0.03-3 mmol / g (preferably 0.05-1.5 mmol / g), and / or, the surface Ti 3+ content loss rate after washing 10 times with deionized water at 100 °C is less than 2% (preferably less than 1%).

14. The photocatalytic material according to claim 11, further containing at least one doping element selected from Group IIIA elements of the periodic table (preferably at least one of B and Ga), Group IVA elements of the periodic table (preferably at least one of C and Ge), Group VA elements of the periodic table (preferably at least one of N and P), non-oxygen Group VIA elements of the periodic table (preferably at least one of S and Se), Group VIIA elements of the periodic table (preferably F), non-noble transition metal elements of the periodic table other than Ti (preferably at least one selected from Mn, Fe, Co, Ni, Cu, Zn), noble metal elements of the periodic table (preferably at least one selected from Ag, Au, Pd, and Pt), and rare earth metal elements of the periodic table (preferably at least one selected from Ce, La, Nd, Gd), preferably at least one doping element selected from N, Mn, and F, particularly preferably containing N, Mn, and F simultaneously as doping elements, and / or, based on the total weight of the photocatalytic material, the content of the doping element(s) (in elemental form) alone or in total is 0.01 - 15 wt% (preferably 0.01 - 10 wt% or 0.1 - 5 wt%).

15. The photocatalytic material according to claim 14, wherein the doping is surface doping, and / or, the F doping is substitutional oxygen doping or a mixture of interstitial doping and substitutional oxygen doping (preferably substitutional oxygen doping), and / or, the N doping includes lattice doping and interstitial doping, wherein the proportion of the lattice doping in the total doping is 80-20% (preferably 70-30%), the proportion of the interstitial doping in the total doping is 20-80% (preferably 30-70%), and the sum of the two is 100%.

16. A photocatalytic article (such as photocatalytic particles, a photocatalytic plate or a photocatalytic film), comprising the photocatalytic material according to claim 11 or the photocatalytic material manufactured by the manufacturing method according to claim 1.

17. A photocatalytic conversion method, comprising the step of irradiating a raw material to be converted (such as a gas containing VOCs or hydrocarbons) with light in the presence of the photocatalytic material according to claim 11, the photocatalytic material manufactured by the manufacturing method according to claim 1 or the photocatalytic article according to claim 16.

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