WO2018205539A1 - 一种三维木质素多孔碳/氧化锌复合材料及其制备和在光催化领域中的应用 - Google Patents
一种三维木质素多孔碳/氧化锌复合材料及其制备和在光催化领域中的应用 Download PDFInfo
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- WO2018205539A1 WO2018205539A1 PCT/CN2017/111338 CN2017111338W WO2018205539A1 WO 2018205539 A1 WO2018205539 A1 WO 2018205539A1 CN 2017111338 W CN2017111338 W CN 2017111338W WO 2018205539 A1 WO2018205539 A1 WO 2018205539A1
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- Prior art keywords
- lignin
- zinc oxide
- zinc
- porous carbon
- dimensional
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 229920005610 lignin Polymers 0.000 title claims abstract description 125
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229910002090 carbon oxide Inorganic materials 0.000 title claims abstract description 52
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 16
- 150000003751 zinc Chemical class 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000000356 contaminant Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011667 zinc carbonate Substances 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 235000014676 Phragmites communis Nutrition 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 240000004658 Medicago sativa Species 0.000 claims description 2
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 74
- 239000007787 solid Substances 0.000 description 12
- 229910021389 graphene Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000272186 Falco columbarius Species 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/36—Biochemical methods
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Definitions
- the invention belongs to the technical field of organic/inorganic hybrid materials, and particularly relates to a three-dimensional lignin porous carbon/zinc oxide composite material and its preparation and application in the field of photocatalysis.
- lignin As the second largest component in plants, lignin is rich in aromatic rings with a three-dimensional network structure. The polymer has a carbon content of more than 50%.
- lignin and its derivatives have been reported as template-modified zinc oxide nanoparticles.
- Chinese patent CN 103183372 A published on July 23, 2013, a template method for solid phase preparation of nano zinc oxide. The method is prepared by first preparing alkali lignin by Mannich reaction to obtain ligninamine, and then using the obtained ligninamine as a template, physically grinding and compounding with solid sodium carbonate and zinc salt, and then placing the horse on the horse.
- the ligninamine in the invention acts only as a template, and the lignin component in the final product is pyrolyzed by high temperature, and the main component carbon element in lignin is not fully utilized.
- the Chinese invention patent application CN106024423A of the present invention discloses a "lignin-based graphene/zinc oxide hybrid composite material, a preparation method and application thereof", and the invention firstly performs carboxylation graft modification of lignin to improve The dispersibility of lignin in aqueous solution, the modified lignin is compounded with zinc oxalate, and then carbonized to prepare a lignin-based graphene/zinc oxide composite material having a sheet-like graphene structure with a nanometer thickness. .
- the present invention directly utilizes a high carbon content of lignin and a three-dimensional network structure to prepare a three-dimensional lignin porous carbon/zinc oxide composite material, which is used as a photocatalyst to degrade organic dye contaminants, and can fully utilize a three-dimensional lignin porous carbon structure.
- the developed interstitial structure adsorbs organic dye contaminants, significantly improves the degradation efficiency and degradation rate of zinc oxide, and has potential application value in the field of photocatalytic degradation of organic pollutants.
- the primary object of the present invention is to provide a three-dimensional wood. Porous carbon/zinc oxide composite.
- Another object of the present invention is to provide a method for preparing the above three-dimensional lignin porous carbon/zinc oxide composite material.
- the method of the invention adopts industrial lignin as a dispersing agent and a carbon source, and prepares a three-dimensional lignin porous carbon/zinc oxide composite material having uniform structure by a two-step method under high temperature conditions, and the raw materials used are easy to obtain, the cost is low, and the industrial production is favorable. .
- Still another object of the present invention is to provide the use of the above three-dimensional lignin porous carbon/zinc oxide composite material in the field of photocatalysis.
- a method for preparing a three-dimensional lignin porous carbon/zinc oxide composite material is a two-step method.
- the first step is to prepare a lignin and zinc oxide precursor composite by a hydrothermal method from a zinc salt, a weak alkali salt and an industrial lignin.
- a three-dimensional lignin porous carbon/zinc oxide composite was prepared by high temperature calcination of lignin and zinc oxide precursor composite.
- the amount of each reactant used is as follows:
- the industrial lignin is selected from the group consisting of wood pulp alkali lignin, bamboo pulp alkali lignin, wheat straw alkali lignin, reed pulp alkali lignin, bagasse alkali lignin, alfalfa grass alkali lignin and biorefinery enzyme. Decomposing at least one of lignin;
- the zinc salt is at least one of zinc oxalate, zinc acetate, zinc nitrate, zinc chloride, zinc carbonate and zinc sulfate; preferably at least one of zinc oxalate, zinc nitrate and zinc acetate; more preferably nitric acid Zinc.
- the weak base salt is at least one of sodium oxalate, sodium carbonate and sodium hydrogencarbonate; preferably sodium hydrogencarbonate.
- the mass concentration of the zinc salt solution in the step (1) is preferably from 20 to 40%.
- the mass concentration of the weak base salt solution in the step (1) is preferably from 20 to 40%.
- the industrial lignin After adding the industrial lignin to the zinc oxide precursor as described in the step (2), it is preferably stirred for 10 to 30 minutes to be uniform.
- the heat preservation in the step (2) is preferably carried out by placing the system in a hydrothermal reaction vessel.
- the separation and drying described in the step (3) are carried out by suction filtration of the lignin and zinc oxide precursor complex, and the filter cake is dried; more preferably, drying at 40 to 60 ° C for 3 to 6 hours.
- the invention also provides a three-dimensional lignin porous carbon/zinc oxide composite material prepared by the above method.
- the composite material has a three-dimensional pore structure, and its structure is regular.
- the zinc oxide nanoparticles are uniformly embedded in the three-dimensional lignin porous carbon, and are applied to the field of photocatalysis, especially as a photocatalyst for photocatalytic degradation of organic dye pollutants. It can significantly improve the degradation efficiency and degradation rate, and has potential application value in the field of photocatalytic degradation of organic pollutants.
- the method of the invention uses the cheap industrial lignin as a raw material to make the industrial lignin obtain high value utilization, and the method of the invention has the advantages that the process flow is simple and easy to operate, the cost is low, and the industrial production is suitable.
- the present invention has the following advantages and beneficial effects:
- the method of the invention adopts industrial lignin as a dispersing agent and a carbon source, and prepares a three-dimensional lignin porous carbon/zinc oxide composite by two-step calcination under high temperature conditions, and the oxygen-containing group of industrial lignin is removed during the calcination process, and the zinc salt is decomposed. Zinc oxide is formed, leaving a void, and the resulting product is a three-dimensional lignin porous carbon/zinc oxide composite.
- the method of the invention has the advantages of simple process, easy control, easy availability of raw materials and low production cost, and the obtained three-dimensional lignin porous carbon/zinc oxide composite material has good photocatalytic effect and is suitable for industrial production.
- Example 1 is a scanning electron micrograph of a three-dimensional lignin porous carbon/zinc oxide composite prepared in Example 2.
- Example 2 is a transmission electron micrograph of a three-dimensional lignin porous carbon/zinc oxide composite prepared in Example 2.
- Example 4 is a Raman spectrum of a three-dimensional lignin porous carbon/zinc oxide composite prepared in Example 4.
- Example 5 is a photocatalytic degradation of a three-dimensional lignin porous carbon/zinc oxide composite prepared in Example 2. The experimental results of the concentration change of Danming B.
- the crystal structure of the prepared three-dimensional lignin porous carbon/zinc oxide composite was measured by Bruker D8 Advance X-ray powder diffractometer according to the method described in the specification; using LabRAMAramis Micro-Raman spectrometer determines the carbonization effect of lignin in the prepared three-dimensional lignin porous carbon/zinc oxide composite according to the method of the specification; the microstructure of the prepared three-dimensional lignin porous carbon/zinc oxide composite is scanned electron Microscopy (SEM, Merlin, Zeiss) and transmission electron microscopy (TEM, JEM ⁇ 2100F, JEOL) were characterized, and the carbonization effect was characterized by Raman spectroscopy (LabRAMAramis, France).
- FIG. 3 is an XRD pattern of the three-dimensional lignin porous carbon/zinc oxide composite prepared in Examples 1 to 5. It can be seen from the figure that zinc oxide in the prepared composite material is a typical hexagonal wurtzite structure, and the results show that During the preparation of the hybrid structure, the addition of industrial lignin did not alter the nanostructured crystalline form of zinc oxide.
- Example 4 is a Raman spectrum of the three-dimensional lignin porous carbon/zinc oxide composite prepared in Example 4. From the figure, the characteristic peak of zinc oxide at 200-400 cm -1 and the characteristic peak D of the carbon material can be seen. G peak, which proves that the three-dimensional lignin porous carbon/zinc oxide composite material has been successfully obtained.
- Example 5 is an experimental result of the photocatalytic degradation of rhodamine B in the three-dimensional lignin porous carbon/zinc oxide composite prepared in Example 2.
- Three sets of three-dimensional lignin porous carbon/zinc oxide composite materials prepared in Example 3 were weighed separately. 60mg, 60mg of each group of pure zinc oxide were weighed separately, and the weighed three-dimensional lignin porous carbon/zinc oxide composite and pure zinc oxide were added to 100mL of methyl orange solution with a concentration of 15mg/L. Under the irradiation of simulated sunlight (500W xenon lamp), a group of solutions were taken at intervals to determine the concentration, and a set of blank comparison experiments without adding any catalyst was placed. The experimental results show that the obtained three-dimensional lignin porous carbon/zinc oxide composite has excellent photocatalytic degradation of methyl orange, and its photocatalytic degradation rate is about 5.1 times higher than that of pure zinc oxide.
Abstract
一种三维木质素多孔碳/氧化锌复合材料及其制备和在光催化领域中的应用。第一步由锌盐、弱碱盐和工业木质素通过水热法制备木质素与氧化锌前驱体复合物，第二步通过高温锻烧木质素与氧化锌前驱体复合物制备三维木质素多孔碳/氧化锌复合材料。复合材料具有三维孔状结构，其结构规整，氧化锌纳米颗粒均匀的嵌在三维木质素多孔碳纳米片层之间，将其应用于光催化领域，特别是用做光催化剂光催化降解有机染料污染物，可显著提高降解效率和降解速率，在光催化降解有机污染物领域具有潜在的应用价值。
Description
本发明属于有机/无机杂化材料技术领域，特别涉及一种三维木质素多孔碳/氧化锌复合材料及其制备和在光催化领域中的应用。
针对目前资源和能源紧缺和环境污染的问题，合理地开发可再生资源，合成一些高附加值的功能性环保材料具有重要意义。另一方面，我国是纺织大国，印染工业体系庞大，年产纺织印染废水至少1.5亿吨，而纺织印染废水中含有大量有机污染物，成分复杂，在自然环境下难以自行降解，属于难以处理的工业废水之一。目前以半导体为催化剂，利用光催化氧化降解有机污染物已经成为环境保护科学研究的一个热点。纳米氧化锌具有较宽的禁带宽度，较大的激子束缚能，同时又具有低毒，化学、光学性质稳定，光催化效率高等优良特性，其应用已涉及光电子器件、气体传感器、防晒剂、抗菌材料、光催化等方面，因此在多个领域尤其是光催化领域具有很大的发展潜力。
但氧化锌作为光催化剂降解有机物的过程中，由于载流子的复合等因素，其光催化活性非常低，显著降低了降解的速率和效率。目前已有大量研究表明通过负载适量石墨烯可以有效提高氧化锌的光催化降解效率和速率，Weng B等[Weng,B.Yang,M.Q.Zhang,N.Xu,Y.J.Toward the enhanced photoactivity and photostability of ZnOnanospheres via intimate surface coating with reduced graphene oxide[J].J.Mater.Chem.A 2(2014)9380-9389.]报道了一种通过氧化锡负载到单层石墨烯上制备出结构均一的石墨烯/氧化锌复合材料，将其应用于光催化降解罗丹明B污染物表现出优异的性能。
木质素作为植物中的第二大组分，是富含有芳香环的具有三维网络结构的
高分子，其含碳量高达50％以上。近年来，将木质素及其衍生物作为模板改性氧化锌纳米颗粒的研究已有报道，如中国专利CN 103183372 A 2013年7月23日公布了《一种模板法固相制备纳米氧化锌的方法》，其制备方法是先将碱木质素通过曼尼希反应制备得到木素胺，再将所得木质素胺作为模板，将其与固体碳酸钠和锌盐进行物理研磨复合，然后置于马弗炉中在空气氛围下煅烧，除去木质素胺，得到固体氧化锌纳米颗粒，所制备的氧化锌纳米颗粒的光催化性质有所提高。该发明中的木质素胺仅仅起着模板的作用，最终产品中木质素成分都被高温煅烧裂解了，木质素中的主要成分碳元素没有得到充分利用。
目前石墨烯/氧化锌复合材料存在的不足之处：在制备过程中，使用价格昂贵的石墨烯或氧化石墨烯原料，且需要使用强酸或者强碱对石墨烯或氧化石墨烯进行有效分散，原材料成本太高，限制了其商业应用前景。工业木质素主要来源于造纸制浆和生物炼制产业，我国每年产生约2千万吨，工业木质素高值化利用对于资源和环境具有重要的意义。本发明申请人前期的中国发明专利申请CN106024423A公布了一种《木质素基石墨烯/氧化锌杂化复合材料及制备方法和应用》，该发明首先对木质素进行羧基化接枝改性，提高木质素在水溶液中的分散性，将改性后的木质素与草酸锌进行复合，再将其进行碳化制备具有纳米级厚度的片层类石墨烯结构的木质素基石墨烯/氧化锌复合材料。但是，光催化领域的碳复合材料需要大量且规整的孔道结构，这些孔道结构有利于吸附染料有机污染物，而片层类石墨烯结构缺乏这些大量且规整的孔道结构，不利于其在光催化领域的应用。因此，本发明直接利用木质素高碳含量和三维网络结构制备一种三维木质素多孔碳/氧化锌复合材料，将其用做光催化剂降解有机染料污染物，可充分利用三维木质素多孔碳结构中发达的空隙结构吸附有机染料污染物，显著提高氧化锌的降解效率和降解速率，在光催化降解有机污染物领域具有潜在的应用价值。
发明内容
为了克服上述现有技术中氧化锌在光催化过程中由于载流子复合等因素导致光催化活性降低的缺点与不足，本发明的首要目的在于提供一种三维木质
素多孔碳/氧化锌复合材料。
本发明另一目的在于提供一种上述三维木质素多孔碳/氧化锌复合材料的制备方法。本发明方法采用工业木质素作为分散剂和碳源，通过两步法在高温条件煅烧制备结构均一的三维木质素多孔碳/氧化锌复合材料，使用的原料易于得到，成本低廉，有利于工业化生产。
本发明再一目的在于提供上述三维木质素多孔碳/氧化锌复合材料在光催化领域中的应用。
本发明的目的通过下述方案实现：
一种三维木质素多孔碳/氧化锌复合材料的制备方法，为两步法，第一步由锌盐、弱碱盐和工业木质素通过水热法制备木质素与氧化锌前驱体复合物，第二步通过高温煅烧木质素与氧化锌前驱体复合物制备三维木质素多孔碳/氧化锌复合材料。
具体包括以下步骤：
(1)往锌盐溶液中加入弱碱盐溶液，得到氧化锌前驱液；
(2)往氧化锌前驱液中加入工业木质素，搅拌均匀后，70～150℃保温1～8h，得到木质素与氧化锌前驱体复合物；
(3)将步骤(2)得到的木质素与氧化锌前驱体复合物分离、干燥，研磨成粉，在惰性气体氛围下500～750℃煅烧1.5～3h，得到三维木质素多孔碳/氧化锌复合材料；
以重量分数计，各反应物用量如下：
工业木质素10份；锌盐5～30份；弱碱盐5～30份。
所述的工业木质素选自木浆碱木质素、竹浆碱木质素、麦草浆碱木质素、芦苇浆碱木质素、蔗渣浆碱木质素、龙须草浆碱木质素和生物炼制酶解木质素中的至少一种；
所述的锌盐为草酸锌、醋酸锌、硝酸锌、氯化锌、碳酸锌和硫酸锌中的至少一种；优选为草酸锌、硝酸锌和醋酸锌中的至少一种；更优选为硝酸锌。
所述的弱碱盐为草酸钠、碳酸钠和碳酸氢钠中的至少一种；优选为碳酸氢钠。
步骤(1)中所述锌盐溶液的质量浓度优选为20～40％。
步骤(1)中所述弱碱盐溶液的质量浓度优选为20～40％。
步骤(2)中所述往氧化锌前驱液中加入工业木质素后，优选搅拌10～30min至均匀。
步骤(2)中所述保温优选将体系置于水热反应釜中进行。
步骤(3)中所述的分离、干燥优选将木质素与氧化锌前驱体复合物进行抽滤，滤饼烘干；更优选为在40～60℃下烘干3～6h。
本发明还提供上述方法制备得到的三维木质素多孔碳/氧化锌复合材料。该复合材料具有三维孔状结构，其结构规整，氧化锌纳米颗粒均匀的嵌在三维木质素多孔碳之间，将其应用于光催化领域，特别是用做光催化剂光催化降解有机染料污染物，可显著提高降解效率和降解速率，在光催化降解有机污染物领域具有潜在的应用价值。本发明方法以廉价的工业木质素为原料，使工业木质素得到了高值化利用，且本发明方法具有工艺流程简单易操作，成本低廉以及适合工业化生产等优点。
本发明相对于现有技术，具有如下的优点及有益效果：
本发明方法采用工业木质素作为分散剂和碳源，通过两步法在高温条件煅烧制备三维木质素多孔碳/氧化锌复合材料，煅烧过程中工业木质素的含氧基团去除，锌盐分解成氧化锌，留下空隙，生成的产物为三维木质素多孔碳/氧化锌复合材料。本发明方法流程简单，易于控制，原料易得，生产成本低，制得的三维木质素多孔碳/氧化锌复合材料光催化效果良好，适合工业化生产。
图1为实施例2制备的三维木质素多孔碳/氧化锌复合材料的扫描电镜图。
图2为实施例2制备的三维木质素多孔碳/氧化锌复合材料的透射电镜图。
图3为实施例1～5制备的三维木质素多孔碳/氧化锌复合材料的X射线衍射图谱。
图4为实施例4制备的三维木质素多孔碳/氧化锌复合材料的拉曼光谱。
图5为实施例2制备的三维木质素多孔碳/氧化锌复合材料光催化降解罗
丹明B的浓度变化实验结果。
图6为实施例3制备的三维木质素多孔碳/氧化锌复合材料光催化降解甲基橙的浓度变化实验结果。
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
下列实施例中使用的物料均可从商业渠道获得。
实施例1
将5g硝酸锌和5g碳酸氢钠分别溶于水中配制成质量浓度为20％的溶液，随后将碳酸氢钠溶液加入到硝酸锌溶液中，在室温下搅拌。然后加入10g木浆碱木质素固体粉末，搅拌10min，将其转移至水热反应釜中70℃保温8h，得到木质素与氧化锌前驱体复合物，将其进行抽滤，把得到的滤饼置于低温烘箱内干燥，干燥温度为40℃，干燥时间为3h。将得到的固体研磨成粉末，然后在500℃下N2保护条件下煅烧3h，冷却至室温，获得三维木质素多孔碳/氧化锌复合材料。
实施例2
将30g氯化锌和30g碳酸钠分别溶于水中配制成质量浓度为40％的溶液，随后将碳酸钠溶液加入到氯化锌溶液中，在室温下搅拌。然后加入10g竹浆碱木质素固体粉末，搅拌30min，将其转移至水热反应釜中90℃保温8h，得到木质素与氧化锌前驱体复合物，将其进行抽滤，把得到的滤饼置于低温烘箱内干燥，干燥温度为60℃，干燥时间为4h。将得到的固体研磨成粉末，然后在750℃下N2保护条件下煅烧1.5h，冷却至室温，获得三维木质素多孔碳/氧化锌复合材料。
实施例3
将15g草酸锌和15g碳酸氢钠分别溶于水中配制成质量浓度为30％的溶
液，随后将碳酸氢钠溶液加入到草酸锌溶液中，在室温下搅拌。然后加入10g麦草浆碱木质素固体粉末，搅拌20min，将其转移至水热反应釜中120℃保温2h，得到木质素与氧化锌前驱体复合物，将其进行抽滤，把得到的滤饼置于低温烘箱内干燥，干燥温度为40℃，干燥时间为5h。将得到的固体研磨成粉末，然后在650℃下N2保护条件下煅烧2h，冷却至室温，获得三维木质素多孔碳/氧化锌复合材料。
实施例4
将10g碳酸锌和10g草酸钠分别溶于水中配制成质量浓度为30％的溶液，随后将草酸钠溶液加入到碳酸锌溶液中，在室温下搅拌。然后加入10g芦苇浆碱木质素固体粉末，搅拌20min，将其转移至水热反应釜中130℃保温5h，得到木质素与氧化锌前驱体复合物，将其进行抽滤，把得到的滤饼置于低温烘箱内干燥，干燥温度为50℃，干燥时间为3h。将得到的固体研磨成粉末，然后在750℃下N2保护条件下煅烧2h，冷却至室温，获得三维木质素多孔碳/氧化锌复合材料。
实施例5
将20g硝酸锌和20g碳酸氢钠分别溶于水中配制成25％的溶液，随后将碳酸氢钠溶液加入到硝酸锌溶液中，在室温下搅拌。然后加入10g酶解木质素固体粉末，搅拌20min，将其转移至水热反应釜中150℃保温3h，冷却至室温后得到木质素与氧化锌前驱体复合物，将复合液进行抽滤，把得到的滤饼置于低温烘箱内干燥，干燥温度为50℃，干燥时间为4h。将得到的固体研磨成粉末，然后在750℃下N2保护条件下煅烧1.5h，冷却至室温，获得三维木质素多孔碳/氧化锌复合材料。
实施例效果说明
用布鲁克D8 Advance X射线粉末衍射仪按照其说明书描述的方法测定所制备的三维木质素多孔碳/氧化锌复合材料的晶型结构；用LabRAMAramis显
微拉曼光谱仪按照其说明书的方法测定所制备的三维木质素多孔碳/氧化锌复合材料中木质素的碳化效果；所制备的三维木质素多孔碳/氧化锌复合材料的微观形貌用扫描电子显微镜(SEM，Merlin，Zeiss)和透射电子显微镜(TEM，JEM～2100F，JEOL)进行了表征，碳化效果用拉曼光谱(LabRAMAramis,France)进行了表征。
从图1的扫描电子显微镜图可以看出氧化锌纳米颗粒与高温碳化所得三维木质素多孔碳非常紧密地复合在一起形成了三维木质素多孔碳/氧化锌纳米复合结构；从图2中可以明显看出氧化锌纳米粒子与三维木质素多孔碳复合在一起。
图3是实施例1～5制备的三维木质素多孔碳/氧化锌复合材料的XRD图谱，从图中可以看出所制备的复合材料中的氧化锌是典型的六方纤锌矿结构，结果表明在制备杂化结构的过程中，工业木质素的添加没有改变氧化锌的纳米结构晶型。
图4是实施例4所制备的三维木质素多孔碳/氧化锌复合材料的拉曼光谱图，从图可以看到200～400cm-1处氧化锌的特征峰和碳材料的特征峰D峰、G峰，证明已经成功获得三维木质素多孔碳/氧化锌复合材料。
图5是实施例2制备的三维木质素多孔碳/氧化锌复合材料光催化降解罗丹明B的浓度变化实验结果。
图6是实施例3制备的三维木质素多孔碳/氧化锌复合材料光催化降解甲基橙的浓度变化实验结果。
分别称取6组实施例2所制备的三维木质素多孔碳/氧化锌复合材料各60mg，同时分别称取6组纯的氧化锌各60mg，分别将所称取的三维木质素多孔碳/氧化锌复合材料和纯氧化锌加入到100mL质量浓度为15mg/L的罗丹明B溶液中，在模拟太阳光(500W氙灯)的照射下，每隔一段时间取出一组溶液测定其浓度，同时放一组不添加任何催化剂的空白对比实验。实验结果表明，所得到的三维木质素多孔碳/氧化锌复合材料具有优异的光催化降解罗丹明B的性能，其光催化降解速率相对于纯的氧化锌提高了约2.7倍。
分别称取6组实施例3所制备的三维木质素多孔碳/氧化锌复合材料各
60mg，同时分别称取6组纯的氧化锌各60mg，分别将所称取的三维木质素多孔碳/氧化锌复合材料和纯氧化锌加入到100mL质量浓度为15mg/L的甲基橙溶液中，在模拟太阳光(500W氙灯)的照射下，每隔一段时间取出一组溶液测定其浓度，同时放一组不添加任何催化剂的空白对比实验。实验结果表明，所得到的三维木质素多孔碳/氧化锌复合材料具有优异的光催化降解甲基橙的性能，其光催化降解速率相对于纯的氧化锌提高了约5.1倍。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
- 一种三维木质素多孔碳/氧化锌复合材料的制备方法，其特征在于为两步法，第一步由锌盐、弱碱盐和工业木质素通过水热法制备木质素与氧化锌前驱体复合物，第二步通过高温煅烧木质素与氧化锌前驱体复合物制备三维木质素多孔碳/氧化锌复合材料。
- 根据权利要求1所述的三维木质素多孔碳/氧化锌复合材料的制备方法，其特征在于具体包括以下步骤：(1)往锌盐溶液中加入弱碱盐溶液，得到氧化锌前驱液；(2)往氧化锌前驱液中加入工业木质素，搅拌均匀后，70～150℃保温1～8h，得到木质素与氧化锌前驱体复合物；(3)将步骤(2)得到的木质素与氧化锌前驱体复合物分离、干燥，研磨成粉，在惰性气体氛围下500～750℃煅烧1.5～3h，得到三维木质素多孔碳/氧化锌复合材料；以重量分数计，各反应物用量如下：工业木质素10份；锌盐5～30份；弱碱盐5～30份。
- 根据权利要求1或2所述的三维木质素多孔碳/氧化锌复合材料的制备方法，其特征在于：所述的工业木质素选自木浆碱木质素、竹浆碱木质素、麦草浆碱木质素、芦苇浆碱木质素、蔗渣浆碱木质素、龙须草浆碱木质素和生物炼制酶解木质素中的至少一种；所述的锌盐为草酸锌、醋酸锌、硝酸锌、氯化锌、碳酸锌和硫酸锌中的至少一种；所述的弱碱盐为草酸钠、碳酸钠和碳酸氢钠中的至少一种。
- 根据权利要求1或2所述的三维木质素多孔碳/氧化锌复合材料的制备方法，其特征在于：所述的锌盐为草酸锌、硝酸锌和醋酸锌中的至少一种；所述的弱碱盐为碳酸氢钠。
- 根据权利要求2所述的三维木质素多孔碳/氧化锌复合材料的制备方法，其特征在于：步骤(1)中所述锌盐溶液的质量浓度为20～40％；所述弱碱盐 溶液的质量浓度为20～40％。
- 根据权利要求2所述的三维木质素多孔碳/氧化锌复合材料的制备方法，其特征在于：步骤(2)中所述往氧化锌前驱液中加入工业木质素后搅拌10～30min至均匀；所述保温为将体系置于水热反应釜中进行。
- 根据权利要求2所述的三维木质素多孔碳/氧化锌复合材料的制备方法，其特征在于：步骤(3)中所述的分离、干燥为将木质素与氧化锌前驱体复合物进行抽滤，滤饼烘干。
- 一种三维木质素多孔碳/氧化锌复合材料，其特征在于根据权利要求1所述的制备方法得到。
- 权利要求8所述的三维木质素多孔碳/氧化锌复合材料在光催化领域中的应用。
- 权利要求8所述的三维木质素多孔碳/氧化锌复合材料在光催化降解有机染料污染物中的应用。
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