Ni and Co bimetallic derivative catalytic material, preparation method and application

Abstract

The invention belongs to the technical field of water pollution control, and discloses a Ni and Co bimetallic derivative catalytic material which is a novel Prussian blue bimetallic derivative catalyst. The prepared catalyst provides a feasible preparation thought for synthesizing a bimetallic Prussian blue derivative catalytic material, under the condition that the pH is neutral, the performance of activating peroxymonosulfate by the synthesized nickel-cobalt oxide catalyst is optimal, 100% degradation of sulfachloropyridazine (SCP) can be achieved within 5 min under the set experiment condition, the kinetic constant k1 is 0.76 min <-1 >, and the catalyst can be widely applied to the field of biodegradation of sulfachloropyridazine (SCP) in the field of biodegradation of sulfachloropyridazine (SCP) in the field of biodegradation of sulfachloropyridazine (SCP). Under set experimental conditions, 100% of bisphenol B (BPB) can be degraded within 2 min, and the dynamic constant k1 is 3.6 min <-1 >. The excellent catalytic performance of the material provides reference for preparation of other MOFs materials and degradation of sulfonamides and bisphenol pollutants by a peroxymonosulfate system.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of water pollution control, and discloses a Ni and Co double-metal derivative catalytic material, a preparation method and application, and particularly relates to a method for preparing a new Prussian blue double-metal oxide catalyst and application of the new Prussian blue double-metal oxide catalyst in a sulfate radical advanced oxidation process for degrading sulfonamide and bisphenol pollutants in water. BACKGROUND

[0002] Advanced oxidation processes have been widely used in the treatment of organic pollutants, especially in the degradation of antibiotics. The sulfate radical-based advanced oxidation technology (SR-AOPs) has high oxidation capacity, high selectivity, wide pH adaptability and long half-life. AOPs rely on active radicals with strong oxidation capacity to destroy chemical bonds or use electron transfer, addition and substitution mechanisms to convert difficult-to-degrade macromolecular substances into low-toxic or non-toxic substances, or even directly mineralize into CO2 and H2O, which has a significant effect on the removal of antibiotics.

[0003] Compared with other catalytic methods such as ultraviolet, ultrasound and electrocatalysis, the catalyst has the advantages of low raw material cost, no need for external energy and significant catalytic effect. In the current research, the activators developed for activating persulfate mainly include metal-based catalysts, non-metal-based catalysts and metal-non-metal composite materials. Among them, heterogeneous catalysis has become a research hotspot due to its simple preparation, low energy consumption, high activation efficiency and easy separation. Homogeneous metal ions and their metal oxide catalysts are generally poor in stability, and the mass transfer in the aqueous solution of the homogeneous system is limited, so the catalyst can effectively react with persulfate, but there is a problem of subsequent metal ion leaching. The heterogeneous system can significantly reduce the leaching of metal ions, and is more conducive to controlling the reaction conditions, becoming a research hotspot. Although traditional cobalt-based functional materials have high performance in activating persulfate to degrade pollutants, they also have some problems, such as large amount of metal ion leaching leading to secondary pollution and catalyst deactivation, which restricts their practical application. Carbon materials have the disadvantages of low catalytic activity and easy deactivation of active sites, and the remaining catalytic activation systems or materials also have their own shortcomings.

[0004] Metal-organic frameworks (MOFs) have attracted extensive attention due to their high porosity, adjustable active centers and easy functional modification (PMS can be activated by MOFs to degrade pollutants in water). As an important member of MOFs, Prussian blue analogs are composed of octahedral [M1(CN)6] n- anionic groups and M 2n+Compared with other MOFs materials, Prussian blue analogues (PBAs) are promising catalysts in advanced oxidation processes due to their unique bimetallic nature providing multiple active sites, excellent electron transfer properties, and variable elemental structure and ease of preparation. PBAs are converted into nitrogen-doped carbon materials with high specific surface area, high porosity and high nitrogen content by high-temperature calcination or inert gas carbonization, which is of great significance to improve the catalytic performance of the catalyst. The morphology of the precursor can be preserved and the catalytic performance can be greatly improved after heat treatment by using PBAs to prepare porous nanostructured oxides, but the deep mechanism of PBAs for the degradation of sulfonamides and bisphenol drugs has not been revealed. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a method for preparing a new Prussian blue bimetallic derivative catalyst and its application in the degradation of sulfonamide and bisphenol pollutants in water by sulfate radical advanced oxidation process, so as to solve the technical problem of low activity of existing metal catalysts in degrading antibiotic pollutants by using advanced oxidation technology.

[0006] It should be noted that the present application combines environmental nanomaterials with advanced oxidation technology to synthesize a new Prussian blue simulated cube composed of pyramid-shaped walls at room temperature by a simple anisotropic chemical etching route, synthesize a bimetallic oxide catalyst, and use Ni-Co PBA oxide porous cubes to remove SCP in a persulfate system.

[0007] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0008] The first technical purpose of the present application is to provide a preparation method of a new Prussian blue bimetallic derivative catalyst, comprising the following steps:

[0009] Dissolve nickel salt and 0.9 mmol C6H5O7Na3 in deionized water to form solution A, and dissolve cobalt salt in deionized water to form solution B;

[0010] Mix solution A and solution B under magnetic stirring at room temperature, and the obtained mixed solution is aged at room temperature. The precipitate is separated, dried, and the dried product is collected and ground into fine powder to obtain blue Ni-Co PBA, and then calcined at high temperature to obtain oxide cube Co3O4 / NiO, which is the new Prussian blue bimetallic derivative catalyst.

[0011] Alternatively, the nickel salt is one or a combination of nickel nitrate, nickel sulfate and nickel chloride, and the cobalt salt is potassium hexacyanocobaltate; the molar ratio of sodium citrate, nickel salt and cobalt salt is 9:6:4.

[0012] Optionally, the high-temperature calcination operation is: heating to 300 DEG C, the heating rate is 4 DEG C / min -1 , the holding time is 2h.

[0013] Optionally, the specific operation of the separation and drying is: centrifuging the reactants at 8000-10000 rpm for 3-5 min, then washing at least once (2-3 times) with pure water, washing at least 3 times (3-4 times) with ethanol, then placing the product in a drying oven at 60-80 DEG C for 6-8h, preferably 60 DEG C.

[0014] The second technical purpose of the present application is to provide a new Prussian blue bimetallic derivative catalyst prepared by the above method, which is an oxide cube Co3O4 / NiO.

[0015] The third technical purpose of the present application is to provide the application of the new Prussian blue bimetallic derivative catalyst prepared by the above method in the field of water pollution control.

[0016] Specifically, the application of the catalyst in the degradation of sulfonamide and bisphenol pollutants in water by sulfate radical advanced oxidation process.

[0017] Compared with the prior art, the present application has the following beneficial effects:

[0018] (1) The synthesis process of the present application is simple and easy to operate, the process is green and environmentally friendly, and the prepared product is an environmentally friendly material;

[0019] (2) The present application prepares a metal-organic framework material with stable structure, which can efficiently load metal nickel and cobalt;

[0020] (3) The present application prepares a new Prussian blue bimetallic oxide catalyst, which utilizes sulfate radical advanced oxidation process to degrade sulfonamide and bisphenol pollutants in water, and utilizes coprecipitation-high temperature calcination method to synthesize oxide cube Co3O4 / NiO by using nickel nitrate hexahydrate as nickel source and potassium hexacyanocobaltate as cobalt source, which can efficiently remove sulfonamidochloropyridazine (SCP) and bisphenol B (BPB) and other antibiotic drugs under the condition of pH=7, and the removal rate can reach 100%. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor on the basis of the provided drawings.

[0022] Figure 1(a) SEM and (b) TEM images of Ni-Co PBA cubes.

[0023] Figure 2 (a) XRD pattern of Ni-Co PBA cubes, (b) XRD pattern of Ni-Co PBA nanocages.

[0024] Figure 3 (a) SEM image of Ni-Co PBA nanocages, (b) SEM image of Ni-Co PBA half-etching-like nanocages.

[0025] Figure 4 (a-b) SEM, (c) TEM and (d) XRD images of calcined oxide cubes Co3O4 / NiO.

[0026] Figure 5 (a) SEM and (b) XRD images of NiO cubes.

[0027] Figure 6 (a) TEM and (b) XRD images of Co3O4.

[0028] Figure 7 (a) Performance of different catalysts on pollutant degradation, (b) pollutant degradation under different pH.

[0029] Figure 8 (a) Performance of different salt ions coexisting system on pollutant degradation, (b) performance of different water quality parameters on pollutant degradation in heterogeneous catalytic system.

[0030] Figure 9 (a) Degradation of different sulfonamide pollutants in heterogeneous system, (b) first-order kinetic constant of degradation of different sulfonamide pollutants, (c) degradation of different bisphenol pollutants, (d) performance of degradation of different bisphenol pollutants. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than 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 scope of protection of the present application.

[0032] Herein the term "embodiment" as "illustrative" of any embodiment described does not necessarily mean that the embodiment is preferred or advantageous over other embodiments. In the embodiments of the present application, the performance index test is carried out by using the conventional test method in the art, unless otherwise specified. It should be understood that the terms described in the present application are only for describing the specific embodiments, and are not used to limit the disclosure of the present application.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; methods and techniques similar to other experimental procedures and techniques described herein are available to one of ordinary skill in the art.

[0034] For a better understanding of the present application, numerous specific details are given in the following embodiments. It will be understood by those skilled in the art that the present application can be implemented without some of the specific details, and the present application is not limited to the specific details described in the embodiments. In the embodiments, some methods, means, instruments, devices, etc. that are well known to those skilled in the art are not described in detail in order to highlight the principles of the present application.

[0035] The technical features disclosed in the embodiments of the present application can be combined in any way without conflict, and the resulting technical solutions belong to the disclosure of the embodiments of the present application.

[0036] The application discloses a method for preparing a new Prussian blue bimetallic oxide catalyst and application of the new Prussian blue bimetallic oxide catalyst in a sulfate radical advanced oxidation process for degrading sulfonamide and bisphenol pollutants in water.

[0037] In order to better understand the present application, the following embodiments are further described in detail, but it should not be understood as limiting the present application. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the application are also regarded as falling within the protection scope of the present application.

[0038] In the present application, if not specifically stated, the devices, instruments, equipment, materials, processes, methods, steps, preparation conditions, etc. used are conventionally used in the art or can be easily obtained by those skilled in the art according to the conventionally used technology in the art.

[0039] Example 1

[0040] 0.6mmol Ni(NO3)2·6H2O and 0.9mmol C6H5O7Na3 were dissolved in 20mL deionized water to form solution A, and 0.4mmol K3Co(CN)6(III) was dissolved in 20mL deionized water to form solution B; then solution A and solution B were mixed by magnetic stirring at room temperature for 15min, and the obtained mixed solution was aged at room temperature for 7 days; the precipitate was collected by centrifugation at 8000rpm for 3min, and further washed with ultrapure water for three times, washed with anhydrous ethanol for three times, and dried at 70℃ overnight; the collected product was ground into fine powder to obtain blue Ni-Co PBA cubes.

[0041] Figure 1a, 1b gives SEM and TEM pictures of Ni-Co PBA, the corresponding XRD is as follows Figure 2 a.

[0042] Example 2

[0043] This example is basically the same as Example 1, except that after synthesizing the Ni-Co PBA cubes, 20 mL of water containing 2.5 mL of NH3·H2O is added to 10 mL of anhydrous ethanol containing 20 mg of Ni-Co PBA cubes, the mixture is magnetically stirred at room temperature for 1 h, and the resulting mixed solution is aged at room temperature for 1 day; the precipitate is collected by centrifugation at 8000 rpm for 3 min, and further washed with ultrapure water three times and with anhydrous ethanol three times, dried at 70°C overnight, the dried product is collected, and the collected product is ground into fine powder to obtain blue Ni-Co PBA nanocages.

[0044] Figure 3 a gives SEM pictures of Ni-Co PBA nanocages, and the corresponding XRD is as follows Figure 2 b.

[0045] Example 3

[0046] This example is basically the same as Example 2, except that after synthesizing the Ni-Co PBA cubes, 20 mL of water containing 2.5 mL of NH3·H2O is added to 10 mL of anhydrous ethanol containing 20 mg of Ni-Co PBA cubes, the mixture is magnetically stirred at room temperature for 1 h, and the resulting mixed solution is aged at room temperature for 6 h as a comparison, and after the same operation of centrifugation, washing and drying, blue Ni-Co PBA semi-etching nanocages are obtained.

[0047] Figure 3 b gives SEM pictures of Ni-Co PBA semi-etching nanocages.

[0048] Example 4

[0049] This example is basically the same as Example 1, except that after synthesizing the Ni-Co PBA cubes, 200 mg of Ni-Co PBA cubes are heated in a muffle furnace at 300°C for 4°C min -1 Calcination for 2 h obtains Ni-Co PBA oxide cubes Co3O4 / NiO.

[0050] Figure 4 a, 4b, 4c give SEM and TEM pictures of oxide cubes Co3O4 / NiO, and the corresponding XRD is as follows Figure 4 d.

[0051] Example 5

[0052] This example is substantially the same as Example 2, except that after the synthesis of the Ni-Co PBA nanocage, the prepared Ni-Co PBA nanocage was heated in air at a rate of 2°C / min to 350°C in a muffle furnace for 2h -1 The Ni-Co oxide cage was obtained by calcination for 2h.

[0053] Example 6

[0054] 1.5g of polyvinylpyrrolidone (PVP) was weighed into 40mL of deionized water, and after stirring and dissolving, 30mL of ethylene glycol (EG) was added, and magnetic stirring was performed for 30min. 1.746g of Ni(NO3)2·6H2O and 1.8g of urea CO(NH2)2 were added to the above mixed solution, and magnetic stirring was continued for 30min to fully dissolve. The obtained solution was transferred into a 100mL polytetrafluoroethylene-lined hydrothermal reactor, and reacted at 160°C for 12h. The obtained product was washed with deionized water and anhydrous ethanol for 3 times each, and placed in a 60°C oven for drying for 15h. Finally, the dried powder was placed in a muffle furnace and heated at a rate of 4°C / min to 400°C -1 The NiO cube was obtained by calcination for 2h.

[0055] Figure 5 a gives the SEM image of the NiO cube, and the corresponding XRD is Figure 5 b.

[0056] Example 7

[0057] Cobalt hydroxide was prepared by adding 2mL of ammonia water to 0.5g of cobalt nitrate hexahydrate using the precipitation method, and then heated to 300°C at a rate of 4°C / min in a muffle furnace, and then kept at this temperature for 120min to obtain Co3O4. -1

[0058] Figure 6 a gives the TEM image of Co3O4, and the corresponding XRD is Figure 6 b.

[0059] Experimental Example 8

[0060] This experimental example studies the effect of different reaction conditions on the degradation of sulfonamide and bisphenol pollutants by the oxide cube Co3O4 / NiO (Example 4) in the PMS system:

[0061] 1. Effect of different catalysts

[0062] ​Using different materials to catalyze the degradation of SCP, only per-sulfate (PMS) and sulfachloropyridazine (SCP) pollutants exist, and the concentration of SCP is almost unchanged. For the synthetic catalyst material oxide cube Co3O4 / NiO, the adsorption effect on pollutants is investigated without PMS, and SCP is almost not adsorbed, Figure 7 It can be found that the synthetic Prussian blue derivative catalyst can completely degrade SCP in 5 min. The catalytic activation of PMS by Ni-Co PBA cube to degrade SCP is very limited, and less than 40% is degraded in 5 min. Co3O4 and NiO also have certain ability to activate PMS to degrade SCP. Under the same conditions, the removal rate of Co3O4 in 5 min can reach about 54%, and the removal rate of NiO in 5 min is about 68%.

[0063] 2, Influence of different pH

[0064] Using different pH to catalyze the degradation of SCP, Figure 7 It can be found that under the condition of pH 7, SCP can be completely degraded in 5 min. Under the same conditions, under the condition of pH 3, SCP is degraded by about 20% in 5 min; under the condition of pH 5, SCP is degraded by about 80% in 5 min; under the condition of pH 9, SCP is degraded by about 82% in 5 min; under the condition of pH 11, SCP is degraded by about 32% in 5 min. When pH=3, 5, 7, 9 and 11, the final degradation efficiency in 15 min is 30%, 100%, 100%, 100% and 47%, respectively.

[0065] 3, Influence of different salt ion catalytic system

[0066] Using different salt ion catalytic system to catalyze the degradation of SCP, Figure 8 It can be found that under the condition of adding different anion and cation salt ions, under the same conditions, compared with the normal catalytic system without adding salt ions, in the system containing humic acid (HA), SCP is degraded by about 96.28% in 7 min; in the Cl￣ system, SCP is degraded by about 95.38% in 7 min; in the NO3￣ system, SCP is degraded by about 100% in 7 min; in the SO4 2 ￣ system, SCP is degraded by about 88.77% in 7 min; in the CO3 2 ￣ system, SCP is degraded by about 84.90% in 7 min; in the K + system, SCP is degraded by about 91.13% in 7 min; in the Na + system, SCP is degraded by about 95.38% in 7 min; in the Mg 2+SCP was degraded about 100% in 7 min; in the presence of Ca 2+ SCP was degraded about 97.93% in 7 min. The corresponding graph is shown in Fig. 2. Figure 8 a.

[0067] 4. Influence of different water quality

[0068] The catalytic degradation of SCP in different water quality was studied, Figure 8 It can be seen from Fig. 3 that SCP can be almost completely degraded in 15 min in ultrapure water, tap water and deionized water. The corresponding graph is shown in Fig. 3. Figure 8 b.

[0069] 5. Degradation effect of different pollutants

[0070] The catalytic degradation of different kinds of sulfonamide pollutants in the presence of PMS was studied, Figure 9 It can be seen from Fig. 4 that sulfachloropyridazine (SCP), sulfamethoxazole (SMZ), sulfathiazole (STZ), sulfadimethoxine (SM2), sulfamethoxypyridazine (SMP) and sulfamethoxazole (SMT) can be completely degraded in 5 min, and sulfamethoxazole (SMR) can be degraded about 90% in 5 min and can be completely degraded eventually. The degradation rate is SMZ>SMT>SM2>STZ>SCP>SMR.

[0071] 6. Degradation effect of different bisphenol pollutants

[0072] The catalytic degradation of different kinds of bisphenol pollutants in the presence of PMS was studied. Bisphenol A (BPA), bisphenol B (BPB), 4,4'-dihydroxydiphenyl sulfone (BPS), bisphenol AF (BPAF) can be completely degraded in 5 min, and 4,4'-dihydroxydiphenyl methane (BPF) can be degraded about 77% in 15 min in the presence of PMS, Figure 9 It can be seen from Fig. 5 that the degradation rate is BPAF>BPS>BPB>BPA>BPF.

[0073] The above description of disclosed embodiments enables one of ordinary skill in the art to make or use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a novel Prussian blue bimetallic derivative catalyst, characterized in that: The steps include: Dissolve nickel salt and sodium citrate in deionized water to form solution A, and dissolve cobalt salt in deionized water to form solution B; Solution A and solution B are mixed under magnetic stirring at room temperature, the resulting mixed solution is aged at room temperature, the precipitate is separated and dried, the dried product is collected, and the collected product is ground into a fine powder to obtain blue Ni-Co PBA, which is then calcined at high temperature to obtain oxide cubes Co3O4 / NiO, namely the novel Prussian blue bimetallic derivative catalyst.

2. The preparation method according to claim 1, characterized in that The nickel salt is one or a combination of nickel nitrate, nickel sulfate, and nickel chloride; the cobalt salt is potassium hexacyanocobaltate; and the molar ratio of the sodium citrate, nickel salt, and cobalt salt is 9:6:

4.

3. The preparation method according to claim 1, characterized in that The high temperature calcination operation is as follows: heating to 300°C at a heating rate of 4°C min -1 , the insulation time is 2h.

4. The preparation method according to claim 1, characterized in that The specific operation of separation and drying is: centrifuging the reactant at 8000-10000 rpm for 3-5 minutes, then washing with pure water 2-3 times, washing with ethanol 3-4 times, and then drying the product at 60-80° C. for 6-8 hours.

5. A novel Prussian blue bimetallic derivative catalyst, characterized in that: The catalyst is prepared by the method according to claim 1, and the catalyst is an oxide cube Co3O4 / NiO.

6. Application of a novel Prussian blue bimetallic derivative catalyst, characterized in that: Application of the catalyst in the field of water pollution control.

7. The use according to claim 6, characterized in that The catalyst is used in a sulfate radical advanced oxidation process to degrade sulfonamide pollutants and bisphenol pollutants in water.

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