CN116943736A - Preparation method and application of hierarchical pore ZIF-67/biochar composite thermal photocatalyst - Google Patents
Preparation method and application of hierarchical pore ZIF-67/biochar composite thermal photocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 235000017060 Arachis glabrata Nutrition 0.000 claims abstract description 21
- 241001553178 Arachis glabrata Species 0.000 claims abstract description 21
- 235000010777 Arachis hypogaea Nutrition 0.000 claims abstract description 21
- 235000018262 Arachis monticola Nutrition 0.000 claims abstract description 21
- 235000020232 peanut Nutrition 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
The invention discloses a preparation method and application of a hierarchical pore ZIF-67/biochar composite thermal photocatalyst, which comprises the following specific steps: pretreatment of peanut shells, preparation of peanut shell carbon PC, preparation of ZIF-67/PC and preparation of ZIF-67. The invention aims to realize efficient thermal photocatalysis CO under continuous process 2 Conversion and C-C coupling to catalysisThe design requirement of the agent is that the MOF material is compounded with the biochar, and the biochar and the MOF material are fully utilized to realize high CO 2 Adsorption activation ability and excellent photoelectric characteristics, and can efficiently convert CO in a fixed bed reactor by a continuous process 2 And H 2 Conversion of O to C 2 H 4 Thermal photocatalyst of the product. The invention has the advantages of simple synthesis method, easily controlled reaction conditions, and the obtained catalyst enriches CO 2 The kind of catalyst for thermal photocatalytic conversion is also used for establishing high-efficiency and high-throughput catalytic conversion of CO 2 The technology provides important scientific basis.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method and application of a hierarchical porous ZIF-67/biochar composite thermal photocatalyst.
Background
At present, the main greenhouse gas CO is reduced 2 And fuelling an ever-increasing global population, remains one of the biggest technical challenges in our age. CO realization by thermo-photocatalysis 2 The high value utilization of (c) provides a very promising solution for establishing sustainable economies, and has become one of the research hotspots in the field of global chemistry and chemical industry.
Compared with metal-based catalysts and other carbon-based catalysts, the biochar is natural, has adjustable morphology and pore structure, larger specific surface area, rich surface groups (C-O, C=O, COOH, OH and the like), various hetero-atom doping (O, N, P, S and the like) and various inorganic components (Ca, K, na, si, mg and the like), and the characteristics endow the biochar with better catalytic performance, and can provide a platform with cost effectiveness and sustainable development for the development of new-generation functional materials. And the application of the biochar functional material is considered as a sustainable process, because the biochar functional material can not only trap and catalyze CO 2 The conversion of waste biomass into biochar can reduce artificial CO 2 Is arranged in the air. Co-based metal organic framework materials (Co-MOFs) are used for photocatalytic CO due to their simple preparation, high photoactivity, good stability, and the like 2 And (3) transformation. Compounding MOFs and biochar material for thermal photocatalysis CO 2 Conversion, utilizing strong photoresponse, carrier generation and transfer capability and CO of material 2 Capture and activation Capacity to catalyst at H 2 Thermo-photo continuous catalytic CO with O as proton source 2 For pushing thermo-optical CO 2 Development of the transformation fieldThe sense is great. However, at present, the CO is thermally photo-catalyzed 2 The conversion catalyst has the problems of low catalytic performance, complicated preparation and unfavorable mass production.
Therefore, the method can use green and economical biomass and high specific surface area MOF materials as raw materials, realize the compounding of the carbon material and the MOF material by utilizing the characteristics of rich natural biomass element composition, rich pore structure and the like, and simply and green prepare the MOF/biochar composite material, so that the problem to be solved by the person skilled in the art is needed to be solved.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a hierarchical pore ZIF-67/biochar composite thermal photocatalyst.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the hierarchical pore ZIF-67/biochar composite thermal photocatalyst is characterized by comprising the following steps of:
step one: pretreatment of peanut shells: firstly grinding peanut shells, performing pretreatment operation, and then drying for later use;
step two: the preparation method of the peanut shell carbon PC comprises the following steps: roasting the pretreated peanut shells in a tube furnace, grinding and washing for three times to obtain PC;
step three: the preparation method of ZIF-67/PC comprises the following steps: firstly mixing PC with 40mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min, then adding cobalt nitrate hexahydrate, continuing ultrasonic dispersion for 1h, then slowly adding 40mL of absolute ethyl alcohol solution dissolved with 2-methylimidazole into PS mixed solution, stirring for 30min, standing for 24h, finally performing centrifugal washing with absolute ethyl alcohol for three times, performing vacuum drying overnight, and grinding to obtain ZIF-67/PC;
step four: the preparation method of ZIF-67 comprises the following steps: firstly, mixing and stirring 150mL of absolute ethyl alcohol solution dissolved with 2-methylimidazole and 75mL of absolute ethyl alcohol dissolved with cobalt nitrate hexahydrate for 3 hours, then centrifugally washing for three times by using the absolute ethyl alcohol, drying overnight in vacuum, and grinding to obtain ZIF-67.
Preferably, the specific method of the pretreatment operation in the first step is as follows: 15g of peanut shells were sonicated in 150mL of absolute ethanol for 30min, then the ethanol solution was changed and stirred at room temperature for 1h.
Preferably, the drying temperature in the first step is 60 ℃.
Preferably, the roasting condition in the second step is as follows: roasting under the inert atmosphere argon atmosphere, wherein the roasting temperature is 800 ℃, the roasting time is 3 hours, and the heating rate is 6 ℃/min.
Preferably, in the third step, the mass of the added PC is 0.1g, the mass of the added cobalt nitrate hexahydrate is 0.146g, and the mass of the added 2-methylimidazole is 0.164g.
Preferably, the temperature of the vacuum drying in the third step and the fourth step is 80 ℃.
Preferably, the mass of the 2-methylimidazole added in the fourth step is 7.5g, and the mass of the cobalt nitrate hexahydrate added is 0.5g.
Preferably, the ZIF-67/PC composite thermal photocatalyst obtained by the preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst is prepared by using a method of preparing the hierarchical porous ZIF-67/biochar composite thermal photocatalyst in CO 2 Use in a conversion process.
Compared with the prior art, the invention has the following technical effects:
the invention adopts peanut shells as a charcoal source, and the precursors are simply mixed and dried, so that the required powder thermal photocatalysis/photoelectrocatalysis material can be synthesized in a large scale; results of X-ray powder diffraction combined with X-ray photoelectron spectroscopy, scanning electron microscope and N 2 The adsorption and desorption test and other results show that ZIF-67 is loaded on the surface of peanut shell carbon in a dodecahedron form, co in ZIF-67/PC mainly exists in a divalent form due to the reducibility of peanut shell carbon, the obtained material ZIF-67/PC mainly presents a microporous and mesoporous coexisting hierarchical pore structure, the generation and separation efficiency of carriers are improved after the two materials are compounded, and the thermal photocatalysis CO is integrally promoted 2 Conversion properties.
Drawings
FIG. 1 is an SEM and EDSmaping diagram of a hierarchical pore ZIF-67/biochar composite thermal photocatalyst preparation method and applied ZIF-67/PC.
FIG. 2 shows XRD patterns of a hierarchical porous ZIF-67/biochar composite thermal photocatalyst, PC, ZIF-67 and ZIF-67/PC used in the preparation method.
FIG. 3 is a fine spectrogram of Co in ZIF-67 and ZIF-67/PC used in the preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst.
FIG. 4 shows a preparation method of a hierarchical porous ZIF-67/biochar composite thermal photocatalyst and N of ZIF-67/PC applied to the same 2 Adsorption and desorption test chart.
FIG. 5 shows a preparation method of a hierarchical porous ZIF-67/biochar composite thermal photocatalyst and an applied PC, ZIF-67 and ZIF-67/PC thermal photocatalysis CO 2 Conversion performance results are shown.
FIG. 6 is a graph of photocurrent density of a material under monochromatic light of a PC, ZIF-67 and ZIF-67/PC, used in the preparation method of a hierarchical porous ZIF-67/biochar composite thermal photocatalyst of the present invention.
FIG. 7 is a graph showing the impedance of a hierarchical porous ZIF-67/biochar composite thermal photocatalyst and PC, ZIF-67 and ZIF-67/PC used in the method.
FIG. 8 is a XPS valence band diagram of a hierarchical pore ZIF-67/biochar composite thermal photocatalyst, PC, ZIF-67 and ZIF-67/PC used in the preparation method of the hierarchical pore ZIF-67/biochar composite thermal photocatalyst.
FIG. 9 is a graph of the forbidden bandwidths of ZIF-67 and ZIF-67/PC from IPCE, for a method for preparing a hierarchical porous ZIF-67/biochar composite thermal photocatalyst and PC used in the method.
FIG. 10 is a photo-generated current diagram of PC, ZIF-67 and ZIF-67/PC used in the preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst of the invention.
FIG. 11 is a graph of photoelectric conversion efficiency of a hierarchical porous ZIF-67/biochar composite thermal photocatalyst, PC, ZIF-67 and ZIF-67/PC, and a method for preparing the same.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The invention discloses a preparation method and application of a hierarchical pore ZIF-67/biochar composite thermal photocatalyst, which are shown in figures 1-11, and comprise the following steps:
step one: pretreatment of peanut shells: firstly grinding peanut shells, performing pretreatment operation, and then drying for later use;
step two: the preparation method of the peanut shell carbon PC comprises the following steps: roasting the pretreated peanut shells in a tube furnace, grinding and washing for three times to obtain PC;
step three: the preparation method of ZIF-67/PC comprises the following steps: firstly mixing PC with 40mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min, then adding cobalt nitrate hexahydrate, continuing ultrasonic dispersion for 1h, then slowly adding 40mL of absolute ethyl alcohol solution dissolved with 2-methylimidazole into PS mixed solution, stirring for 30min, standing for 24h, finally performing centrifugal washing with absolute ethyl alcohol for three times, performing vacuum drying overnight, and grinding to obtain ZIF-67/PC;
step four: the preparation method of ZIF-67 comprises the following steps: firstly, mixing and stirring 150mL of absolute ethyl alcohol solution dissolved with 2-methylimidazole and 75mL of absolute ethyl alcohol dissolved with cobalt nitrate hexahydrate for 3 hours, then centrifugally washing for three times by using the absolute ethyl alcohol, drying overnight in vacuum, and grinding to obtain ZIF-67.
The specific method of the pretreatment operation in the first step is as follows: 15g of peanut shells were sonicated in 150mL of absolute ethanol for 30min, then the ethanol solution was changed and stirred at room temperature for 1h.
The drying temperature in the first step was 60 ℃.
The roasting conditions in the second step are as follows: roasting under the inert atmosphere argon atmosphere, wherein the roasting temperature is 800 ℃, the roasting time is 3 hours, and the heating rate is 6 ℃/min.
In the third step, 0.1g of PC was added, 0.146g of cobalt nitrate hexahydrate was added, and 0.164g of 2-methylimidazole was added.
The temperature of vacuum drying in the third step and the fourth step is 80 ℃.
In the fourth step, 7.5g of 2-methylimidazole was added, and 0.5g of cobalt nitrate hexahydrate was added.
Example 2
Thermal photocatalytic CO for PC 2 Conversion performance evaluation: accurately weighing 15mg of PC in the second step, wherein the reaction pressure is 0.2MPa, the flow rate of reaction gas is 10mL/min, the reaction set temperature is 350 ℃, the surface temperature of the catalyst is 280 ℃, the light source is a 300W xenon lamp, and the power is 450 mW.cm -2 CO from PC in a fixed bed reactor by a continuous process 2 Photo-thermal catalysis performance test.
Example 3
Thermal photocatalytic CO of ZIF-67 2 Conversion performance evaluation: accurately weighing 15mg of ZIF-67 in the third step, wherein the reaction pressure is 0.2MPa, the flow rate of reaction gas is 10mL/min, the reaction set temperature is 350 ℃, the surface temperature of the catalyst is 280 ℃, the light source is a 300W xenon lamp, and the power is 450 mW.cm -2 CO from ZIF-67 in a fixed bed reactor by continuous process 2 Photo-thermal catalysis performance test.
Example 4
Thermal photocatalytic CO for ZIF-67/PC 2 Conversion performance evaluation: accurately weighing 15mg of ZIF-67/PC in the fourth step, wherein the reaction pressure is 0.2MPa, the flow rate of reaction gas is 10mL/min, the reaction set temperature is 350 ℃, the surface temperature of the catalyst is 280 ℃, the light source is a 300W xenon lamp, and the power is 450mW cm -2 CO is carried out on ZIF-67/PC by adopting a continuous process in a fixed bed reactor under the reaction condition 2 Photo-thermal catalysis performance test.
Example 5
And step two, testing the photo current response of the PC prepared in the step three, the ZIF-67 prepared in the step four and the ZIF-67/PC prepared in the step four. The xenon lamp corrected by solar spectrum is used for simulating sunlight, and the light intensity is 100mW/cm 2 Testing was performed using a standard three-electrode photoelectrolysis cell system with a side quartz glass entrance window, with a platinum sheet as the counter electrode, an Ag/AgCl electrode as the reference electrode, and a working electrode of 1X 1cm fabricated on FTO conductive glass 2 Thin film electrode of sample at 0.1mol/LNa 2 SO 4 Is an electrolyte. In a typical test procedure, the generated photocurrent/voltage curve is monitored and recorded using an Shanghai Chen Hua electrochemical workstation. In summary, the present invention is illustrated by the results of the above examples and fig. 1: after being compounded, ZIF-67 is relatively uniformly distributed on peanut shell carbon in a dodecahedron configuration with the size of less than 100nm, and the main elements of the composite material are C, N, O and Co; the results from the above examples and fig. 2 show that: ZIF-67 was successfully compounded with PC; the results from the above examples and fig. 3 show that: ZIF-67/PC has higher Co 2+ The proportion is favorable for improving the catalytic performance of the catalyst; the results from the above examples and fig. 4 show that: ZIF-67/PC is a hierarchical pore structure with coexisting mesopores and micropores; the results from the above examples and fig. 5 show that: after ZIF-67 and PC are compounded, the catalyst has higher catalytic performance; the results from the above examples and fig. 6 show that: the composite material has stronger light absorption capacity at 400-600 nm; the results from the above examples and fig. 7 show that: the conductivity of ZIF-67 can be improved after the materials are compounded; the results from the above examples and fig. 8 show that: the valence band top positions of PC, ZIF-67 and ZIF-67/PC are 2.13, 1.10 and 1.31eV, respectively; the results from the above examples and fig. 9 show that: the forbidden bandwidths of PC, ZIF-67 and ZIF-67/PC are 2.16, 2.07 and 2.14eV respectively; the results from the above examples and fig. 10 show that: the composite material ZIF-67/PC has stronger photo-generated current; the results from the above examples and fig. 11 show that: the composite material ZIF-67/PC has stronger photoelectric conversion efficiency.
The foregoing is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so any minor modifications, equivalent variations and modifications made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the hierarchical pore ZIF-67/biochar composite thermal photocatalyst is characterized by comprising the following steps of:
step one: pretreatment of peanut shells: firstly grinding peanut shells, performing pretreatment operation, and then drying for later use;
step two: the preparation method of the peanut shell carbon PC comprises the following steps: roasting the pretreated peanut shells in a tube furnace, grinding and washing for three times to obtain PC;
step three: the preparation method of ZIF-67/PC comprises the following steps: firstly mixing PC with 40mL of absolute ethyl alcohol, performing ultrasonic treatment for 30min, then adding cobalt nitrate hexahydrate, continuing ultrasonic dispersion for 1h, then slowly adding 40mL of absolute ethyl alcohol solution dissolved with 2-methylimidazole into PS mixed solution, stirring for 30min, standing for 24h, finally performing centrifugal washing with absolute ethyl alcohol for three times, performing vacuum drying overnight, and grinding to obtain ZIF-67/PC;
step four: the preparation method of ZIF-67 comprises the following steps: firstly, mixing and stirring 150mL of absolute ethyl alcohol solution dissolved with 2-methylimidazole and 75mL of absolute ethyl alcohol dissolved with cobalt nitrate hexahydrate for 3 hours, then centrifugally washing for three times by using the absolute ethyl alcohol, drying overnight in vacuum, and grinding to obtain ZIF-67.
2. The preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst according to claim 1, wherein the specific method of the pretreatment operation in the first step is as follows: 15g of peanut shells were sonicated in 150mL of absolute ethanol for 30min, then the ethanol solution was changed and stirred at room temperature for 1h.
3. The method for preparing the hierarchical porous ZIF-67/biochar composite thermal photocatalyst according to claim 1, wherein the drying temperature in the first step is 60 ℃.
4. The preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst according to claim 1, wherein the roasting condition in the second step is as follows: roasting under the inert atmosphere argon atmosphere, wherein the roasting temperature is 800 ℃, the roasting time is 3 hours, and the heating rate is 6 ℃/min.
5. The preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst according to claim 1, wherein the mass of the added PC in the third step is 0.1g, the mass of the added cobalt nitrate hexahydrate is 0.146g, and the mass of the added 2-methylimidazole is 0.164g.
6. The method for preparing the hierarchical porous ZIF-67/biochar composite thermal photocatalyst according to claim 1, wherein the vacuum drying temperature in the third step and the fourth step is 80 ℃.
7. The preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst according to claim 1, wherein the mass of 2-methylimidazole added in the fourth step is 7.5g, and the mass of cobalt nitrate hexahydrate added in the fourth step is 0.5g.
8. The preparation method of the hierarchical porous ZIF-67/biochar composite thermal photocatalyst according to claim 1, wherein the ZIF-67/PC composite thermal photocatalyst is prepared by the preparation method in CO 2 Use in a conversion process.
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