A basic magnesium sulfate-based photocatalytic material and a preparation method thereof

Abstract

The application discloses a kind of basic magnesium sulfate-based photocatalytic materials and preparation method thereof.The basic magnesium sulfate-based photocatalytic material includes: basic magnesium sulfate and transition metal element, the basic magnesium sulfate is 5Mg (OH) 2·MgSO4·7H2O Irregular cement, and the transition metal element includes Ti, Zn, Cu, Fe, Mn, Co, Ni, Ce and the like.The preparation method includes: organic weak acid, magnesium sulfate, transition metal sulfate and water are uniformly mixed to form mixed solution;Active magnesium oxide and nucleating agent are uniformly mixed to form mixed powder;The mixed powder, pore-forming agent and mixed solution are uniformly mixed, and then reaction molding is carried out to obtain the basic magnesium sulfate-based photocatalytic material.The basic magnesium sulfate-based photocatalytic material provided by the application is convenient to form, has good mechanical strength, has good photocatalytic activity, and is a new type of photocatalytic material easy to recycle.

Description

TECHNICAL FIELD

[0001] The application relates to a catalytic material, in particular to a basic magnesium sulfate-based photocatalytic material and a preparation method thereof, and belongs to the technical field of photocatalytic materials. BACKGROUND

[0002] Photocatalytic oxidation is to use a certain wavelength of excitation light source to irradiate a photocatalyst made of a semiconductor material with special electronic structure, and the electrons in the material absorb photons to be excited from the valence band to the conduction band, and holes are formed on the valence band, and then strong oxidizing free radicals are generated, which will have an oxidation-reduction reaction with organic pollutants, and finally the pollutants are oxidized into carbon dioxide, water and the like, so that the green removal of the organic pollutants is realized. The photocatalytic oxidation technology has the advantages of mild reaction conditions, simple operation, low energy consumption, no secondary pollution and mineralization of organic matter, and cannot be compared with other treatment technologies, and thus shows great application potential in organic pollution treatment. Common photocatalysts are some transition metal oxides and sulfides, but these photocatalytic materials are mostly powders, and there is a problem of difficult recycling in the application of removing pollutants in the environment, and the scale application is limited.

[0003] The basic magnesium sulfate is an environmentally friendly air hardening gel material, has good water resistance and salt resistance, stable physical and chemical properties, and is easy to be formed. In the 5Mg(OH)2·MgSO4·7H2O crystal of the basic magnesium sulfate, the MgO6 octahedron is arranged along the b axis, the MgO6 chain is composed of 6 edges and 6 vertices, that is, 12 edges, each octahedron contains Mg atoms, shares with 4 surrounding octahedrons, the infinite heavy chain of the MgO6 octahedron constitutes the main part of the crystal packing, and the hydroxyl anions and / or water molecules and the rotationally disordered sulfate tetrahedron are also embedded therein. At present, the development of the basic magnesium sulfate-based photocatalytic material has not been reported. SUMMARY

[0004] The main purpose of the application is to provide a basic magnesium sulfate-based photocatalytic material and a preparation method thereof, so as to overcome the shortcomings of the prior art.

[0005] In order to achieve the above application purposes, the following technical scheme is adopted in the application.

[0006] The application provides a basic magnesium sulfate-based photocatalytic material, which comprises: basic magnesium sulfate and a transition metal element, the basic magnesium sulfate is an irregular cement body of 5Mg(OH)2·MgSO4·7H2O, and the transition metal element comprises any one or a combination of two or more of Ti, Zn, Cu, Fe, Mn, Co, Ni and Ce.

[0007] In some preferred embodiments, the basic magnesium sulfate-based photocatalytic material comprises the following components in parts by mass: 90-99 parts of basic magnesium sulfate, 1-10 parts of a transition metal element.

[0008] The embodiment of the present application also provides a preparation method of the basic magnesium sulfate-based photocatalytic material, which comprises the following steps:

[0009] The organic weak acid, magnesium sulfate, transition metal sulfate and water are uniformly mixed to form a mixed solution;

[0010] The active magnesium oxide and the nucleating agent are uniformly mixed to prepare a mixed powder;

[0011] The mixed powder, the pore-forming agent and the mixed solution are uniformly mixed, and then reaction molding is performed to prepare the basic magnesium sulfate-based photocatalytic material.

[0012] Compared with the prior art, the present application has at least the following beneficial effects:

[0013] The basic magnesium sulfate-based photocatalytic material provided by the present application is convenient to form, has good mechanical strength, has good photocatalytic activity, and is a new type of photocatalytic material that is easy to recycle. DETAILED DESCRIPTION

[0014] In view of the deficiencies in the prior art, the present inventors have long-term researched and practiced, and have finally proposed the technical solution of the present application, which mainly provides a new type of photocatalytic material that is convenient to form, has good mechanical strength, has good photocatalytic activity, and is easy to recycle. The technical solution, the implementation process and the principles thereof will be further explained as follows.

[0015] One aspect of the embodiment of the present application provides a basic magnesium sulfate-based photocatalytic material, which comprises: basic magnesium sulfate and a transition metal element, wherein the basic magnesium sulfate is an irregular agglomerate of 5Mg(OH)2·MgSO4·7H2O, and the transition metal element comprises any one or a combination of two or more of Ti, Zn, Cu, Fe, Mn, Co, Ni and Ce.

[0016] The present inventors have innovatively doped transition metal ions with an ionic radius smaller than or close to that of magnesium ions into the 5·1·7 phase lattice of basic magnesium sulfate, to replace part of the magnesium ions in the lattice or to be doped into the lattice to form a 5·1·7 phase-like phase, so that the crystal structure is changed and the band gap of the 5·1·7 phase is reduced (the band gap of the 5·1·7 phase of basic magnesium sulfate is about 4.33 eV), which significantly improves the photoeffect ability of the material, increases the light response range, and endows the material with photocatalytic activity.

[0017] As a preferred embodiment, the basic magnesium sulfate-based photocatalytic material comprises the following components in parts by mass: 90-99 parts of basic magnesium sulfate, 1-10 parts of transition metal element.

[0018] Further, the mechanical strength of the basic magnesium sulfate-based photocatalytic material is 0.5-0.8 MPa.

[0019] As another aspect of the present application, a preparation method of a basic magnesium sulfate-based photocatalytic material is provided, which comprises:

[0020] uniformly mixing an organic weak acid, magnesium sulfate, transition metal sulfate and water to form a mixed solution;

[0021] uniformly mixing active magnesium oxide and nucleating agent to form a mixed powder;

[0022] uniformly mixing the mixed powder, pore-forming agent and mixed solution, and then reaction molding to obtain the basic magnesium sulfate-based photocatalytic material.

[0023] In some preferred embodiments, the preparation method specifically comprises the following steps:

[0024] (1) mixing an organic weak acid, magnesium sulfate, transition metal sulfate and water to form a uniform mixed solution;

[0025] (2) mixing active magnesium oxide and nucleating agent to form a uniform mixed powder;

[0026] (3) adding the mixed powder and pore-forming agent into the mixed solution, fully stirring and rapidly mixing, and then reaction molding in a mold to obtain the basic magnesium sulfate-based photocatalytic material.

[0027] The preparation principle of the present application can be as follows: (1) the transition metal sulfate is fully dispersed in the magnesium sulfate solution under the action of the organic weak acid; (2) the nucleating agent is fully mixed with the active magnesium oxide, so that the nucleation reaction occurs fully and the mass transfer is rapid; (3) the magnesium oxide reacts with water to form hydroxyl, and the magnesium sulfate reacts with the hydroxyl to form 5·1·7 phase under the induction of the nucleating agent, while the transition metal ions enter the 5·1·7 phase lattice to replace part of the magnesium ions or inlay in the lattice gap, forming a 5·1·7 phase-like, the crystal structure is changed to reduce the band gap of the 5·1·7 phase, significantly improve its light effect ability, increase the light response range, endow the material with photocatalytic activity, and solidify and form under the action of the pore-forming agent.

[0028] In the preparation conditions of the present application, the transition metal ions do not form metal oxides. The metal ions, due to the ion radius being less than or close to the magnesium ion in the 5·1·7 phase, enter the crystal lattice during the formation of the 5·1·7 crystal, replace part of the magnesium ions in the crystal lattice or are doped into the crystal lattice to form a 5·1·7 phase-like phase, the crystal structure is changed to reduce the band gap of the 5·1·7 phase, significantly improve the light effect ability, and endow the material with photocatalytic activity.

[0029] In some preferred embodiments, in step (1), the transition metal sulfate includes any one or a combination of two or more of titanium sulfate, zinc sulfate, copper sulfate, iron sulfate, ferrous sulfate, manganese sulfate, cobalt sulfate, nickel sulfate, cerium sulfate, etc.

[0030] In some preferred embodiments, in step (1), the organic weak acid includes any one or a combination of two of carboxylic acid R(COOH) n , hydroxyl carboxylic acid HOR(COOH) n , wherein R is a hydrocarbon group, n is an integer greater than or equal to 1, and the mass fraction is 0.5-5 parts. The addition of the organic weak acid has two aspects: one is to provide a certain amount of hydrogen ions to prevent the premature formation of hydroxide by hydrolysis of the metal ions, so that the transition metal ions are fully dispersed in the solution, and are replaced by magnesium ions or inlaid in the 5·1·7 crystal lattice gap when the 5·1·7 crystal is formed. The second is that the organic acid radical is adsorbed on the surface of magnesium oxide to inhibit the production of magnesium hydroxide and promote the growth of the 5·1·7 phase.

[0031] Further, the organic weak acid can be any one or a combination of two or more of gluconic acid, lignin sulfonic acid, itaconic acid, tartaric acid, acetic acid, succinic acid, citric acid, lactic acid, maleic acid, tannic acid, etc., but is not limited thereto.

[0032] In some preferred embodiments, the mass ratio of the organic weak acid, magnesium sulfate, transition metal sulfate, and water is (0.5-5):(5-25):(5-25):(45-89.5). In other words, the mass fraction of the organic weak acid is 0.5-5 parts, the mass fraction of the magnesium sulfate is 5-25 parts, the mass fraction of the transition metal sulfate is 5-25 parts, and the mass fraction of the water is 45-89.5 parts.

[0033] In some preferred embodiments, in step (2), the nucleating agent includes powdered basic magnesium sulfate, and the basic magnesium sulfate is 5·1·7 whisker (5Mg(OH)2·MgSO4·7H2O).

[0034] In some preferred embodiments, in step (2), the mass ratio of the nucleating agent to the active magnesium oxide is 5-15:85-95, namely, the mass fraction of the nucleating agent is 5-15 parts, and the mass fraction of the active magnesium oxide is 85-95 parts.

[0035] In some preferred embodiments, in step (3), the pore-forming agent includes any one or a combination of two or more of hydrogen peroxide, a surfactant, a protein solution (such as a chicken egg protein solution), and the like, but is not limited thereto.

[0036] Further, the surfactant can be any one or a combination of two or more of sodium dodecyl benzene sulfonate, sodium lauryl sulfate, sodium lignosulfonate, sodium dioctyl succinate sulfonate, cetyltrimethylammonium bromide, lauroyl glutamic acid, myristyl trimethyl ammonium bromide, and the like, but is not limited thereto.

[0037] In some preferred embodiments, in step (3), the mass ratio of the mixed powder, the pore-forming agent, and the mixed solution is (20-50):(0.5-5):(45-79.5), namely, the mass fraction of the pore-forming agent is 0.5-5 parts, the mass fraction of the mixed powder is 20-50 parts, and the mass fraction of the mixed solution is 45-79.5 parts.

[0038] In some preferred embodiments, the temperature of the reaction molding is room temperature, the time is kept at more than 24 hours, and the aging time is more than 2 days, and then the product can be used.

[0039] Correspondingly, another aspect of the embodiment of the present application also provides the basic magnesium sulfate-based photocatalytic material prepared by the aforementioned preparation method.

[0040] Further, another aspect of the embodiment of the present application also provides the application of the aforementioned composite photocatalytic material in the field of photocatalytic degradation. For example, the composite photocatalytic material can be used for catalytic degradation of tetracycline hydrochloride, methyl orange, and the like, but is not limited thereto.

[0041] In order to make the objectives, technical solutions, and advantages of the present application clearer, the technical solutions of the present application are further described in detail below in combination with several preferred embodiments. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application. In the following embodiments, the test methods are carried out according to the conventional conditions. In addition, the technical features involved in each embodiment of the present application can be combined with each other as long as they do not conflict with each other.

[0042] The reagents used in the following examples are all of analytical purity.

[0043] Example 1

[0044] The preparation process of the Ti@ basic magnesium sulfate photocatalytic material is as follows:

[0045] (1) 0.5 parts of gluconic acid, 5 parts of magnesium sulfate, 5 parts of titanium sulfate, and 89.5 parts of water are mixed and stirred thoroughly to form a uniform mixture;

[0046] (2) 85 parts of active magnesium oxide and 15 parts of powdered basic magnesium sulfate 5·1·7 phase (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred thoroughly to form a uniform powder mixture;

[0047] (3) 20 parts of the powder mixture, 0.5 parts of 30% hydrogen peroxide, and 79.5 parts of the mixture are added and stirred thoroughly to form a uniform mixture, which is then poured into a 4cm×4cm×4cm mold for reaction molding. After grinding and sieving through a 5-60 mesh sieve, Ti@ basic magnesium sulfate particles are obtained.

[0048] The compressive strength of the Ti@ basic magnesium sulfate particles obtained in this example is 0.6MPa. Under specific conditions of irradiation for 2h under a light source of 280-380nm, 30.1% of tetracycline hydrochloride (100mg / L) and 52.3% of methyl orange (100mg / L) can be degraded.

[0049] Example 2

[0050] The preparation process of the Zn@ basic magnesium sulfate photocatalytic material is as follows:

[0051] (1) 5 parts of lignin sulfonic acid, 10 parts of magnesium sulfate, 20 parts of zinc sulfate, and 70 parts of water are mixed and stirred thoroughly to form a uniform mixture;

[0052] (2) 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium sulfate 5·1·7 phase (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred thoroughly to form a uniform powder mixture;

[0053] (3) 50 parts of the powder mixture, 5 parts of sodium dodecylbenzenesulfonate, and 45 parts of the mixture are added and stirred thoroughly to form a uniform mixture, which is then poured into a 4cm 2 ×0.5cm mold for reaction molding to obtain Zn@ basic magnesium sulfate tablets.

[0054] The compressive strength of the Zn@ basic magnesium sulfate tablets obtained in this example is 0.5MPa. Under specific conditions of irradiation for 2h under a light source of 280-380um, 42.5% of tetracycline hydrochloride (100mg / L) and 48.0% of methyl orange (100mg / L) can be degraded.

[0055] Example 3

[0056] The preparation process of Cu@basic magnesium sulfate photocatalytic material is as follows:

[0057] (1) 5 parts of itaconic acid, 15 parts of magnesium sulfate, 15 parts of copper sulfate and 65 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0058] (2) 90 parts of active magnesium oxide and 10 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0059] (3) 40 parts of the mixed powder, 1 part of sodium lauryl sulfate are added to 57 parts of the mixed solution, and the mixture is stirred and mixed uniformly, then the mixture is poured into 2cm 2 ×0.5cm molds for reaction molding to obtain Cu@basic magnesium sulfate tablets.

[0060] The compressive strength of the Cu@basic magnesium sulfate tablets obtained in this example is 0.7MPa, and under the specific conditions of irradiation for 2h under a light source of 280-600nm, 37.5% of tetracycline hydrochloride (100mg / L) and 56.8% of methyl orange (100mg / L) can be degraded.

[0061] Example 4

[0062] The preparation process of Fe / Ti@basic magnesium sulfate photocatalytic material is as follows:

[0063] (1) 1 part of tartaric acid, 15 parts of magnesium sulfate, 5 parts of iron sulfate, 5 parts of titanium sulfate and 74 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0064] (2) 90 parts of active magnesium oxide and 10 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0065] (3) 40 parts of the mixed powder, 2 parts of egg protein solution are added to 58 parts of the mixed solution, and the mixture is stirred and mixed uniformly, then the mixture is poured into 4cm×4cm×4cm molds for reaction molding, grinding and sieving through a 5-60 mesh sieve to obtain Fe / Ti@basic magnesium sulfate particles.

[0066] The compressive strength of the Fe / Ti@basic magnesium sulfate particles obtained in this example is 0.5MPa, and under the specific conditions of irradiation for 2h under a light source of 280-600nm, 42.7% of tetracycline hydrochloride (100mg / L) and 70.3% of methyl orange (100mg / L) can be degraded.

[0067] Example 5

[0068] The preparation process of the Cu / Fe@basic magnesium sulfate photocatalytic material is as follows:

[0069] (1) 2 parts of acetic acid, 20 parts of magnesium sulfate, 3 parts of copper sulfate, 5 parts of ferrous sulfate, and 71 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0070] (2) 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0071] (3) 40 parts of the mixed powder and 5 parts of sodium lignosulfonate are added to 55 parts of the mixed solution, and the mixture is stirred and mixed uniformly, and then is divided and packed in 4 cm 2 ×0.5 cm molds for reaction molding, grinding, and sieving through a 5-60 mesh sieve to obtain Cu / Fe@basic magnesium sulfate particles.

[0072] The compressive strength of the Cu / Fe@basic magnesium sulfate particles obtained in this example is 0.5 MPa, and under the specific conditions of irradiation for 2 h under a simulated sunlight source, 36.6% of tetracycline hydrochloride (100 mg / L) and 49.1% of methyl orange (100 mg / L) can be degraded.

[0073] Example 6

[0074] The preparation process of the Ni@basic magnesium sulfate photocatalytic material is as follows:

[0075] (1) 2 parts of succinic acid, 23 parts of magnesium sulfate, 5 parts of nickel sulfate, and 70 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0076] (2) 90 parts of active magnesium oxide and 10 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0077] (3) 30 parts of the mixed powder and 2 parts of 30% hydrogen peroxide are added to 68 parts of the mixed solution, and the mixture is stirred and mixed uniformly, and then is divided and packed in 2 cm 2 ×0.5 cm molds for reaction molding to obtain Ni@basic magnesium sulfate tablets.

[0078] The compressive strength of the Ni@basic magnesium sulfate tablets obtained in this example is 0.8 MPa, and under the specific conditions of irradiation for 2 h under a light source of 280-600 nm, 35.6% of tetracycline hydrochloride (100 mg / L) and 40.2% of methyl orange (100 mg / L) can be degraded.

[0079] Example 7

[0080] The preparation process of the Ce / Ni@basic magnesium sulfate photocatalytic material is as follows:

[0081] (1) 5 parts of citric acid, 15 parts of magnesium sulfate, 5 parts of cerium sulfate, 3 parts of nickel sulfate, and 77 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0082] (2) 95 parts of active magnesium oxide and 5 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0083] (3) 40 parts of the mixed powder and 2 parts of dioctyl sodium sulfosuccinate are added to 58 parts of the mixed solution, which is stirred and mixed rapidly and uniformly, and then is divided and filled into 4 cm 2 ×0.5 cm molds for reaction molding, grinding, and sieving through a 5-60 mesh sieve to obtain Ce / Ni@basic magnesium sulfate particles.

[0084] The compressive strength of the Ce / Ni@basic magnesium sulfate particles obtained in this example is 0.7 MPa, and under the specific conditions of irradiation for 2 h under a light source of 280-380 nm, 39.3% of tetracycline hydrochloride (100 mg / L) and 51.5% of methyl orange (100 mg / L) can be degraded.

[0085] Example 8

[0086] The preparation process of the Mn@basic magnesium sulfate photocatalytic material is as follows:

[0087] (1) 5 parts of lactic acid, 20 parts of magnesium sulfate, 3 parts of manganese sulfate, and 72 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0088] (2) 92 parts of active magnesium oxide and 7 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0089] (3) 42 parts of the mixed powder and 3 parts of cetyltrimethylammonium bromide are added to 55 parts of the mixed solution, which is stirred and mixed rapidly and uniformly, and then is divided and filled into 2 cm 2 ×0.5 cm molds for reaction molding to obtain Mn@basic magnesium sulfate tablets.

[0090] The compressive strength of the Mn@basic magnesium sulfate tablets obtained in this example is 0.8 MPa, and under the specific conditions of irradiation for 2 h under a light source of 280-380 nm, 28.7% of tetracycline hydrochloride (100 mg / L) and 37.4% of methyl orange (100 mg / L) can be degraded.

[0091] Example 9

[0092] The preparation process of the Co@basic magnesium sulfate photocatalytic material is as follows:

[0093] (1) 5 parts of maleic acid, 15 parts of magnesium sulfate, 5 parts of cobalt sulfate and 80 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0094] (2) 85 parts of active magnesium oxide and 15 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0095] (3) 25 parts of the mixed powder and 3 parts of lauroyl glutamic acid are added to 72 parts of the mixed solution, and the mixture is stirred and mixed rapidly and uniformly, and then is poured into a 2 cm×2 cm×2 cm mold for reaction and molding, and is ground and sieved through a 5-60 mesh sieve to obtain Co@basic magnesium sulfate particles.

[0096] The compressive strength of the Co@basic magnesium sulfate particles obtained in this example is 0.7 MPa, and under the specific conditions of irradiation for 2 h under a light source of 280-600 nm, 35.0% of tetracycline hydrochloride (100 mg / L) and 41.5% of methyl orange (100 mg / L) can be degraded.

[0097] Example 10

[0098] The preparation process of the Co / Mn@basic magnesium sulfate photocatalytic material is as follows:

[0099] (1) 4 parts of tannic acid, 21 parts of magnesium sulfate, 3 parts of cobalt sulfate, 3 parts of cobalt sulfate and 69 parts of water are mixed and stirred to prepare a uniform mixed solution;

[0100] (2) 90 parts of active magnesium oxide and 10 parts of powdered basic magnesium sulfate 5·1·7 (5Mg(OH)2·MgSO4·7H2O) are mixed and stirred to prepare a uniform mixed powder;

[0101] (3) 35 parts of the mixed powder and 2 parts of tetradecyl trimethyl ammonium bromide are added to 73 parts of the mixed solution, and the mixture is stirred and mixed rapidly and uniformly, and then is poured into a 2 cm×2 cm×2 cm mold for reaction and molding, and is ground and sieved through a 5-60 mesh sieve to obtain Co / Mn@basic magnesium sulfate particles.

[0102] The compressive strength of the Co / Mn@basic magnesium sulfate particles obtained in this example is 0.5 MPa, and under the specific conditions of irradiation for 2 h under a light source of 280-600 nm, 36.5% of tetracycline hydrochloride (100 mg / L) and 43.2% of methyl orange (100 mg / L) can be degraded.

[0103] Comparative Example 1

[0104] This comparative example is substantially identical to Example 1, except that no glucose acid was added in step (1). However, the material was difficult to shape and crumbled in water.

[0105] Comparative Example 2

[0106] This comparative example is substantially identical to Example 1, except that no powdered basic magnesium sulfate was added in step (2).

[0107] The material obtained in this example was tested and had a compressive strength of 0.2 MPa, and under specific conditions of irradiation for 2 h under a light source of 280-600 nm, it degraded 42.0% of tetracycline hydrochloride (100 mg / L) and 45.1% of methyl orange (100 mg / L).

[0108] Comparative Example 3

[0109] This comparative example is substantially identical to Example 1, except that no active magnesium oxide was added in step (2). However, the material could not be shaped.

[0110] Comparative Example 4

[0111] This comparative example is substantially identical to Example 1, except that no hydrogen peroxide was added in step (3).

[0112] The material obtained in this example was tested and had a compressive strength of 2 MPa, and under specific conditions of irradiation for 2 h under a light source of 280-600 nm, it degraded 12.8% of tetracycline hydrochloride (100 mg / L) and 22.4% of methyl orange (100 mg / L).

[0113] In addition, the inventors of the present case also made tests with other raw materials, process operations, process conditions described in the specification with reference to the foregoing examples, and all obtained relatively ideal results.

[0114] Although the present application has been described with reference to the illustrative embodiments, it will be understood by those skilled in the art that various other changes in form and details can be made therein without departing from the spirit and scope of the application. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the application without departing from the scope thereof. Therefore, it is intended that the present application not be limited to the particular disclosed embodiments described herein, but will include all embodiments falling within the scope of the appended claims.

Claims

1. A basic magnesium sulfate-based photocatalytic material, characterized in that, The material comprises the following components by mass: 90-99 parts basic magnesium sulfate, 1-10 parts transition metal elements, wherein the basic magnesium sulfate is an irregular cementitious body of 5Mg(OH)2·MgSO4·7H2O, and the transition metal elements include any one or a combination of two or more of Ti, Zn, Cu, Fe, Mn, Co, Ni, and Ce. The basic magnesium sulfate-based photocatalyst material is prepared by the following method: The organic weak acid, magnesium sulfate, transition metal sulfate and water are mixed evenly to form a mixture; Active magnesium oxide and a nucleating agent are uniformly mixed to form a mixed powder. The nucleating agent includes basic magnesium sulfate, which is an irregular cementitious body of 5Mg(OH)2·MgSO4·7H2O. The mixed powder, pore-forming agent, and mixed liquid are mixed evenly, and then reacted and shaped to obtain the basic magnesium sulfate-based photocatalytic material. The pore-forming agent includes any one or a combination of two or more of hydrogen peroxide, surfactant, and protein solution. The surfactant includes any one or a combination of two or more of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium lignosulfonate, sodium dioctyl succinate sulfonate, hexadecyltrimethylammonium bromide, lauroyl glutamate, and tetradecyltrimethylammonium bromide.

2. The basic magnesium sulfate-based photocatalytic material according to claim 1, characterized in that: The mechanical strength of the basic magnesium sulfate-based photocatalytic material is 0.5~0.8 MPa.

3. A method for preparing a basic magnesium sulfate-based photocatalytic material as described in claim 1 or 2, characterized in that, include: The organic weak acid, magnesium sulfate, transition metal sulfate and water are mixed evenly to form a mixture; Active magnesium oxide and a nucleating agent are uniformly mixed to form a mixed powder. The nucleating agent includes basic magnesium sulfate, which is an irregular cementitious body of 5Mg(OH)2·MgSO4·7H2O. The mixed powder, pore-forming agent, and mixed liquid are mixed evenly, and then reacted and shaped to obtain the basic magnesium sulfate-based photocatalytic material. The pore-forming agent includes any one or a combination of two or more of hydrogen peroxide, surfactant, and protein solution.

4. The preparation method according to claim 3, characterized in that: The organic weak acid includes R(COOH). n HOR(COOH) n Any combination of one or two of the following, where R is a hydrocarbon group and n is an integer greater than or equal to 1.

5. The preparation method according to claim 4, characterized in that: The organic weak acid includes any one or a combination of two or more of gluconic acid, lignin sulfonic acid, itaconic acid, tartaric acid, acetic acid, succinic acid, citric acid, lactic acid, maleic acid, and tannic acid.

6. The preparation method according to claim 3, characterized in that: The transition metal sulfates include any one or a combination of two or more of titanium sulfate, zinc sulfate, copper sulfate, ferric sulfate, ferrous sulfate, manganese sulfate, cobalt sulfate, nickel sulfate, and cerium sulfate.

7. The preparation method according to claim 3, characterized in that: The mass ratio of the organic weak acid, magnesium sulfate, transition metal sulfate and water is (0.5~5):(5~25):(5~25):(45~89.5).

8. The preparation method according to claim 3, characterized in that: The mass ratio of the nucleating agent to active magnesium oxide is 5~15:85~95.

9. The preparation method according to claim 3, characterized in that: The mass ratio of the mixed powder, pore-forming agent and mixed liquid is (20~50):(0.5~5):(45~79.5).

10. The preparation method according to claim 3, characterized in that: The reaction is carried out at room temperature for more than 24 hours and aged for more than 2 days.