CN115254091B - Indium oxyhydroxide/biomass porous carbon composite photocatalyst, and preparation method and application thereof - Google Patents
Indium oxyhydroxide/biomass porous carbon composite photocatalyst, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 239000002028 Biomass Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- -1 Indium oxyhydroxide Chemical compound 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002159 nanocrystal Substances 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
An indium oxyhydroxide/biomass porous carbon composite photocatalyst, a preparation method and application thereof, and relates to the technical fields of composite material preparation and photocatalysis application. Firstly, preparing Biomass Porous Carbon (BPC) by utilizing orange peel through hydrothermal reaction and KOH activation and high-temperature calcination treatment, and then, reacting on the Biomass Porous Carbon (BPC) to generate indium hydroxide (InOOH) nanocrystalline. In the structure, inOOH nanocrystalline uniformly grows on the surface of BPC, the BPC presents a three-dimensional honeycomb structure, and the particle size of the InOOH nanocrystalline grown on the BPC is between 10 and 20nm. The indium oxyhydroxide/biomass porous carbon composite photocatalyst prepared by the invention has rich active sites and large specific surface area, is favorable for separation of photogenerated carriers, enhances the photocatalytic activity, and has excellent effect in preparing methane by photocatalytic reduction of carbon dioxide.
Description
Technical Field
The invention relates to the technical field of preparation of composite materials and photocatalysis application, in particular to an indium oxyhydroxide/biomass porous carbon composite photocatalyst, a preparation method thereof and application thereof in methane preparation by photocatalytic carbon dioxide reduction reaction.
Background
The high industrialization accelerates the consumption of fossil energy by human beings, and the large amount of fossil energy such as petroleum, natural gas and the like is combusted to cause C in the atmosphereO 2 The dominant greenhouse gases are dramatically increased, exacerbating the energy crisis and greenhouse effect. Through the photocatalysis reduction technology, solar energy can be directly utilized to convert CO 2 Conversion to renewable chemical fuels, e.g. CO, CH 4 C x H y O z Realize CO 2 The energy crisis is solved and the environmental problem caused by greenhouse effect is reduced while the conversion of the added value is high. Although TiO 2 As a commonly used photocatalyst, but in the photocatalytic reduction of CO 2 The conversion efficiency of (c) is still low in practical applications. Thus, CO is irradiated by sunlight 2 Technology for efficient conversion to hydrocarbons has been of great interest.
InOOH is a wide-bandgap n-type semiconductor material, and InOOH with different structures can be synthesized by a solvothermal method, a chemical precipitation method, a sol-gel method, a microemulsion method and the like. InOOH was commonly used as In past studies 2 O 3 Most of the precursors of (c) are used in gas-sensitive research, while little is done on the properties of itself and the photocatalytic performance applications. Li and the like synthesize InOOH nanocrystals with the particle diameter of about 20nm from indium nitrate and ethylenediamine by a simple solvothermal method, and the prepared InOOH is utilized to carry out photocatalytic degradation on benzene vapor under the irradiation of ultraviolet light of 300nm, so that the InOOH has catalytic activity equivalent to that of P25, has higher mineralization degree, is more stable than that of P25 in long-time operation, and shows excellent photocatalytic degradation performance on benzene. (Li Z, xie Z, zhang Y, et al, wide band gap p-block metal oxyhydroxide InOOH: anew durable photocatalyst for benzene degradation. Journal of Physical Chemistry C,2007,111 (49): 18348-18352.).
The invention introduces agricultural wastes as raw materials and processes the agricultural wastes into porous carbon materials. The porous carbon material has a large specific surface, and the unique porous structure not only can increase the light energy utilization rate, but also has excellent conductivity, thereby being beneficial to the conduction of photo-generated electrons. The indium oxyhydroxide/biomass porous carbon composite photocatalyst prepared by utilizing one-step microwave liquid phase synthesis reaction has novel microstructure, and indium oxyhydroxide nanocrystals uniformly grow on porous carbon in a three-dimensional honeycomb shapeOn the surface, the composite photocatalyst has high photocatalytic activity and can obviously improve CO 2 The efficiency of photocatalytic reduction to methane is not reported at present in the photocatalytic reduction of carbon dioxide by a composite experiment of indium oxyhydroxide and biomass porous carbon.
Disclosure of Invention
The invention aims to solve the technical problems of low reaction efficiency and the like in the reaction of catalyzing and reducing carbon dioxide to generate methane in the prior art, provides an indium oxyhydroxide/biomass porous carbon (InOOH/BPC) composite photocatalyst with high catalytic activity, and simultaneously provides a simple, convenient, quick and efficient preparation method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an indium oxyhydroxide/biomass porous carbon composite photocatalyst has a structure that indium oxyhydroxide (InOOH) nanocrystals are uniformly grown on the surface of Biomass Porous Carbon (BPC), the Biomass Porous Carbon (BPC) has a three-dimensional honeycomb structure, and the particle size of the indium oxyhydroxide (InOOH) nanocrystals grown on the Biomass Porous Carbon (BPC) is between 10 and 20nm.
The preparation method of the indium oxyhydroxide/biomass porous carbon composite photocatalyst comprises the steps of firstly preparing Biomass Porous Carbon (BPC) by utilizing orange peel through hydrothermal reaction and KOH activation and high-temperature calcination treatment, and then reacting on the Biomass Porous Carbon (BPC) to generate indium oxyhydroxide (InOOH) nanocrystalline, wherein the preparation method comprises the following specific steps:
(1) preparation of biomass porous carbon
Firstly, grinding and sieving dried orange peel by using a grinder, then adding a proper amount of distilled water and pore-assisting agent, uniformly stirring, performing hydrothermal reaction, and washing and drying after the reaction is completed to obtain a product A; adding a proper amount of KOH and distilled water into the product A, uniformly stirring, and then putting into a baking oven for baking to obtain a product B; calcining the product B in a tube furnace, cooling to room temperature, washing, and drying to obtain a sample, namely Biomass Porous Carbon (BPC);
(2) reaction on porous carbon to produce indium oxyhydroxide (InOOH) nanocrystals
Dispersing 50-100mg porous carbon with distilled water and DMF, adding 0.1-0.5mmol InNO 3 ·4H 2 O, stirring and dissolving; and then placing the reaction liquid in a microwave oven for microwave heating to react, cooling and standing overnight after the reaction is finished, and finally carrying out solid-liquid separation, washing and drying to obtain the indium hydroxide/biomass porous carbon (InOOH/BPC) composite photocatalyst.
As a preferable technical scheme of the preparation method, the hydrothermal process in the step (1) uses ammonium chloride as a pore-assisting agent, and the addition amount of the pore-assisting agent is 3-8% of the weight of the sieved orange peel powder. The reaction temperature in the hydrothermal process is 140-180 ℃ and the reaction time is 3-8h. Adding KOH and distilled water, stirring uniformly, and then placing into a baking oven at 90-110 ℃ for baking for 3-5h. Product B was placed in a tube furnace at N 2 Calcining under atmosphere, wherein the temperature rising rate is 4-6 ℃/min, the calcining temperature is 600-800 ℃, and the calcining time is 50-100 min.
As the preferable technical scheme of the preparation method, the mixed solution in the step (2) is placed in a 800W household microwave oven and heated for 20-40min by a low fire gear.
Compared with the prior art, the invention has the beneficial effects that:
1) The micro-structure of the indium oxyhydroxide/biomass porous carbon composite photocatalyst prepared by the invention is that InOOH nanocrystalline uniformly grows on the surface of the BPC which is three-dimensional honeycomb, and the particle size of the InOOH nanocrystalline grown on the BPC is 10-20nm. The InOOH/BPC composite photocatalyst has rich active sites and large specific surface area, is favorable for separation of photo-generated carriers, enhances the photocatalytic activity, and has excellent effect in preparing methane by photocatalytic reduction of carbon dioxide.
2) The preparation method of the indium oxyhydroxide/biomass porous carbon composite photocatalyst has the advantages of simple process equipment, simple and convenient operation, good repeatability, low-cost and easily-obtained raw materials, and suitability for industrial production.
3) The biomass orange peel which is low in cost and easy to obtain is used as a carbon source, so that reasonable utilization of waste is realized, and resources are saved.
Drawings
Fig. 1 is an X-ray diffraction analysis (XRD) spectrum of the pure indium oxyhydroxide prepared in step (2) in example 1 and the indium oxyhydroxide/biomass porous carbon composite photocatalyst prepared in examples 1, 2, and 3.
FIG. 2 is a field emission scanning electron microscope (FE-SEM) photograph of the porous carbon prepared in step (1) of example 1.
Fig. 3, 4 and 5 are field emission scanning electron microscope (FE-SEM) photographs of the indium oxyhydroxide/biomass porous carbon composite photocatalyst prepared in examples 1, 2 and 3, respectively.
FIG. 6 is photocatalytic CO of pure indium oxyhydroxide and indium oxyhydroxide/biomass porous carbon composite photocatalyst in example 4 2 Reduced methane yield plot (a) and corresponding methane yield plot (b).
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
(1) Preparation of porous carbon
Firstly, grinding dried orange peel by using a grinder, sieving the obtained powder by using a 100-mesh sieve, weighing 5g of orange peel powder, adding 45mL of distilled water and 0.25g of ammonium chloride, uniformly stirring, then carrying out heat preservation reaction for 5 hours at 160 ℃, cooling to room temperature, and washing and drying to obtain a product A; adding KOH with the mass twice of that of the product A, adding distilled water with the same volume as powder, stirring, and then placing the mixture into a 100 ℃ oven for 3 hours to dry to obtain a product B; product B was placed in a tube furnace at N 2 Heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere, calcining for 1h, taking out after the reaction is finished and the temperature is reduced to room temperature, washing with deionized water, and drying to obtain a sample, namely the Biomass Porous Carbon (BPC).
Referring to fig. 2, the prepared biomass porous carbon mainly has a three-dimensional honeycomb structure, has a smooth surface and has no other particles.
(2) React on biomass porous carbon to generate InOOH nanocrystalline
Taking a conical flask, adding 50mg of porous carbon, 1mL of distilled water and 29mL of LDMF, performing ultrasonic dispersion for 15min, and then adding 0.1mmol of InNO 3 ·4H 2 O, stirring for 4h at room temperature; converting the reaction solution intoMoving to a household microwave oven (800W), heating for 30min by using low-fire gear (power 18%) microwave, and then carrying out suction filtration while the mixture is hot, washing, drying and collecting a sample to obtain the InOOH/BPC composite photocatalyst, wherein the InOOH/BPC composite photocatalyst is marked as InOOH/BPC-1;
the same method was used to prepare pure InOOH samples without the addition of porous carbon.
Referring to FIG. 1, the peak positions of spectral lines in the diagram are in one-to-one correspondence with all diffraction crystal faces of a JCDF standard card (71-2277), and are indicated as InOOH crystals with orthogonal phases, and a space group P2 1 N mm, lattice constant
Referring to fig. 3, it can be clearly seen that: a large number of InOOH nanocrystals grow on the surface of the original smooth biomass porous carbon, and the particle size of the InOOH nanocrystals is about 10-20nm. InOOH nanocrystals were grown substantially uniformly on the nanoplatelet surface, but the surface was partially exposed and not covered by InOOH nanocrystals.
Example 2
A conical flask was taken, 50mg of the porous carbon prepared in step (1) of example 1, 1mL of distilled water and 29mL of LDMF were added, and the mixture was sonicated for 15min, followed by 0.3mmol of InNO 3 ·4H 2 O, stirring for 4h at room temperature; transferring the reaction solution into a household microwave oven (800W), heating for 30min by using low-fire-level (power 18%) microwave, and then carrying out suction filtration while the reaction solution is hot, washing, drying and collecting a sample to obtain the InOOH/BPC composite photocatalyst, wherein the InOOH/BPC composite photocatalyst is marked as InOOH/BPC-2.
Referring to FIG. 1, it can be seen that all spectral peaks are also fully consistent with the X-ray powder diffraction analysis (XRD) spectra of the pure InOOH and InOOH/BPC-1 composite photocatalyst prepared as described in the procedure of example 1.
Referring to fig. 4, it can be clearly seen that: a large number of InOOH nanocrystals are grown on the surface of the original smooth biomass porous carbon, and the InOOH nanocrystals grow more uniformly and almost uniformly on the surface of the porous carbon.
Example 3
A conical flask was taken, 50mg of porous carbon prepared in step (1) of example 1, 1mL of distilled water and 29mL of DMF were added, and the mixture was sonicated for 15min, followed by 0.5mmol of InNO 3 ·4H 2 O, stirring for 4h at room temperature; transferring the reaction solution into a household microwave oven (800W), heating for 30min by using low-fire-level (power 18%) microwave, and then carrying out suction filtration while the reaction solution is hot, washing, drying and collecting a sample to obtain the InOOH/BPC composite photocatalyst, wherein the InOOH/BPC composite photocatalyst is marked as InOOH/BPC-3.
Referring to FIG. 1, it can be seen that all spectral peaks are also fully consistent with the X-ray powder diffraction analysis (XRD) spectra of the pure InOOH and InOOH/BPC-1 composite photocatalyst prepared as described in the procedure of example 1.
Referring to fig. 5, it can be clearly seen that: a large number of InOOH nanocrystals are grown on the surface of the original smooth porous carbon, but the particle size of the InOOH nanocrystals is increased, and aggregation and accumulation phenomena exist.
Example 4 (indium oxyhydroxide/Biomass porous carbon composite photocatalyst photocatalytic CO 2 Reduction
The prepared catalyst was tested for photocatalytic CO in an on-line photocatalytic reaction system (MC-SPB 10-AG) designed by Beijing magnesium Ruiyan Co 2 Reduction activity. 10mg of catalyst and 1mL of distilled water were added to the centrifuge tube and the sonication was continued for 15min until the catalyst was completely dispersed uniformly. Then evenly dripping the mixture on a sieve plate, placing the mixture in a glass reactor, connecting the glass reactor to a photocatalytic reaction system, and introducing high-purity CO 2 (99.999%) as a reaction gas, and CO was stopped when the number of barometer was 15kpa 2 The purge was repeated three times until the system pressure stabilized. A300W xenon lamp (MC-XF 300) was used as a light source. The reactor temperature was controlled at about 6℃by a circulating condensed water device throughout the photoreaction stage, and the amount of the reducing gas product produced was analyzed by an on-line gas chromatograph (GC 9790 II) equipped with a FID detector and a TCD detector every 1 hour.
Referring to FIG. 6, the InOOH/BPC composite photocatalyst prepared in 3 examples is higher than pure InOOH photocatalytic CO 2 Reduction to methaneThe yield of (a) is greatly improved (FIG. 6 a), in particular by adding 0.3mmol of InNO 3 ·4H 2 Photocatalytic CO of InOOH/BPC-2 Complex photocatalyst prepared by O (example 2) 2 The reduction performance is optimal. Meanwhile, the production rate of the InOOH/BPC-2 composite photocatalyst prepared in example 2 is highest (shown in FIG. 6 b), reaching 94.68. Mu. Mol.g -1 ·h -1 About 122.9 times that of pure InOOH.
The example proves that the indium hydroxide/biomass porous carbon composite photocatalyst prepared by the method has excellent photocatalytic CO 2 The methane preparation performance by reduction is simple, the preparation process is simple, and a large amount of synthesis possibility is provided.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (2)
1. The preparation method of the indium oxyhydroxide/biomass porous carbon composite photocatalyst is characterized by comprising the following steps of:
(1) preparation of porous carbon
Firstly, grinding dried orange peel by using a grinder, sieving the obtained powder by using a 100-mesh sieve, weighing 5g of orange peel powder, adding 45mL of distilled water and 0.25g of ammonium chloride, uniformly stirring, then carrying out heat preservation reaction at 160 ℃ for 5h, cooling to room temperature, washing and drying to obtain a product A; adding KOH with the mass twice of that of the product A, adding distilled water with the same volume as powder, stirring, and then placing the mixture into a 100 ℃ oven for 3 hours to dry to obtain a product B; product B was placed in a tube furnace at N 2 Heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere, calcining for 1h, taking out after the reaction is finished and the temperature is reduced to room temperature, washing with deionized water, and drying to obtain a sample, namely the biomass porous carbon BPC; the prepared biomass porous carbon BPC has a three-dimensional honeycomb structure, the surface is smooth, and no other particles exist;
(2) react on biomass porous carbon to generate InOOH nanocrystalline
Taking a conical flask, adding 50mg of biomass porous carbon BPC, 1mL of distilled water and 29mL of LDMF, performing ultrasonic dispersion for 15min, and then adding 0.3mmol of InNO 3 ·4H 2 O, stirring at room temperature 4h; transferring the reaction solution into a household 800W microwave oven, heating for 30min by using 18% low-fire grade microwaves, filtering while the reaction solution is hot, washing, drying and collecting a sample to obtain the InOOH/BPC composite photocatalyst; a large number of InOOH nanocrystals are grown on the surface of the biomass porous carbon, the particle size of the InOOH nanocrystals is 10-20nm, and the InOOH nanocrystals uniformly grow on the surface of the nanosheets.
2. The application of the indium oxyhydroxide/biomass porous carbon composite photocatalyst prepared by the method according to claim 1 in preparing methane by photocatalytic carbon dioxide reduction reaction, wherein 10mg catalyst and 1mL distilled water are added into a centrifuge tube, and ultrasound is continued for 15min until the catalyst is completely and uniformly dispersed; then evenly dripping the mixture on a sieve plate, placing the mixture in a glass reactor, connecting the glass reactor to a photocatalytic reaction system, and introducing 99.999% high-purity CO 2 As a reaction gas, CO was stopped when the number of barometer was 15kpa 2 Repeating the gas washing for three times until the system pressure is stable; using a 300W xenon lamp as a light source; the reactor temperature was controlled at 6℃by a circulating condensed water device throughout the photoreaction stage, and the amount of the reducing gas product produced was analyzed by on-line gas chromatography equipped with FID and TCD detectors every 1. 1 h.
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