CN114085826B - Photoelectric methane-generating biocatalyst with sandwich structure and preparation method and application thereof - Google Patents
Photoelectric methane-generating biocatalyst with sandwich structure and preparation method and application thereof Download PDFInfo
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- CN114085826B CN114085826B CN202111327225.4A CN202111327225A CN114085826B CN 114085826 B CN114085826 B CN 114085826B CN 202111327225 A CN202111327225 A CN 202111327225A CN 114085826 B CN114085826 B CN 114085826B
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- biocatalyst
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- methane
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- 108090000790 Enzymes Proteins 0.000 title claims abstract description 59
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 59
- 239000011942 biocatalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 239000004065 semiconductor Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 244000005700 microbiome Species 0.000 claims abstract description 13
- 230000000813 microbial effect Effects 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 40
- 229910003322 NiCu Inorganic materials 0.000 claims description 30
- 230000000696 methanogenic effect Effects 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 6
- 235000018417 cysteine Nutrition 0.000 claims description 6
- 241000202970 Methanobacterium formicicum Species 0.000 claims description 5
- 241000202985 Methanobrevibacter smithii Species 0.000 claims description 5
- 241000872955 Methanosaeta harundinacea Species 0.000 claims description 5
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- 235000013619 trace mineral Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 3
- 229910016897 MnNi Inorganic materials 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229940082569 selenite Drugs 0.000 claims description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 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
- 241000202987 Methanobrevibacter Species 0.000 claims 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 8
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- 229910052980 cadmium sulfide Inorganic materials 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 27
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 241000205275 Methanosarcina barkeri Species 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000002609 medium Substances 0.000 description 17
- 241000205276 Methanosarcina Species 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 239000006228 supernatant Substances 0.000 description 14
- 239000001963 growth medium Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000004108 freeze drying Methods 0.000 description 9
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- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229960002433 cysteine Drugs 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 150000001879 copper Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 241000080590 Niso Species 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 239000008239 natural water Substances 0.000 description 5
- 150000002815 nickel Chemical class 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241001648836 Methanobrevibacter ruminantium Species 0.000 description 4
- 241000205263 Methanospirillum hungatei Species 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000243 photosynthetic effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 4
- 235000019254 sodium formate Nutrition 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 3
- 239000007995 HEPES buffer Substances 0.000 description 3
- 108010020056 Hydrogenase Proteins 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 239000000725 suspension Substances 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- PQDPFQKKQAYNSU-UHFFFAOYSA-N [S-2].[Cd+2].[Ni+2].[S-2] Chemical compound [S-2].[Cd+2].[Ni+2].[S-2] PQDPFQKKQAYNSU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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- 238000003384 imaging method Methods 0.000 description 2
- 238000000707 layer-by-layer assembly Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Tropical Medicine & Parasitology (AREA)
- Virology (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a photoelectric methane-generating biocatalyst with a sandwich structure, a preparation method and application thereof, and the photoelectric methane-generating biocatalyst sequentially comprises: a microbial core, wherein the microorganism is methanogen; the bimetal intermediate layer is coated on the surface of the microbial core; the nanometer semiconductor shell is arranged on one side of the bimetal intermediate layer far away from the microorganism core through electrostatic attraction. The photoelectric methane-generating biocatalyst with the sandwich structure can use ubiquitous sunlight as a driving force, overcomes the defects of low interfacial electron transfer efficiency, insufficient photoelectric conversion efficiency, low quantum efficiency and the like of the traditional biological photoelectric system, and has the maximum quantum efficiency of more than 13.0 percent. In addition, the prepared photoelectric methane-generating biocatalyst with the sandwich structure can normally operate under the natural environment condition, and has higher universality and popularization value.
Description
Technical Field
The invention belongs to the field of biocatalysts, and particularly relates to a photoelectric methane-generating biocatalyst with a sandwich structure, and a preparation method and application thereof.
Background
Carbon dioxide (CO) 2 ) The continued conversion to high value added low carbon biofuels is an important strategy to alleviate global carbon emission pressures and energy shortages. Bioelectrochemical methanogenesis (Biophotoelectrochemical methanogenesis, BPEC) is the specific conversion of solar energy into methane by exploiting the high specific catalytic capacity of non-photosynthetic organisms and the superior light capturing properties of photosensitizers. However, the prior art can not effectively solve the problems of transfer and utilization efficiency of photo-generated electrons at the interface of non-photosynthetic microorganisms and photosensitizers, so that the methane generation efficiency and the sustainability are low, and the biological light can not be realizedPopularization and application of electrochemical methane production.
In recent years, various methods have been widely used to improve the optoelectronic characteristics of nano-semiconductors, such as heterojunction construction, surface sensitization, element doping, metal loading, etc. Among these methods, metal doping is relatively one of the most effective methods of improving the electron-hole separation efficiency. For example, the invention patent No. CN202011055193.2 provides a construction method and application of a transition metal-mediated semi-artificial photosynthesis system, and the transition metal is utilized to strengthen the combination of a semiconductor and a photoelectric microorganism. However, in the related art, the metal catalyst still has the huge technical defects that the catalytic site is single, the schottky barrier is too high or too low to cause insufficient photocatalytic activity, and the non-photosynthetic organisms need to have the function of directly receiving the photo-generated electrons. In addition, most of the metal catalysts used tend to be noble metals (such as expensive and rare Au, ag, pt, pd), and have the disadvantages of high preparation and use costs, and the like, so that the possibility of large-scale practical use of the metal catalysts in photoelectrochemistry is greatly limited.
Therefore, the development of a low-cost and high-efficiency methane-producing biocatalyst has great significance for the development of photoelectrochemical energy conversion.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a sandwich-structured photoelectric methanogenic biocatalyst, a preparation method and application thereof. The photoelectric methane-generating biocatalyst with the sandwich structure takes the bimetallic layer as an electronic bridge and a catalytic site to promote photoelectron transfer and surface catalysis hydrogen reaction, thereby improving methane output.
In a first aspect of the present invention, there is provided a photoelectric methanogenic biocatalyst of a sandwich structure for photoelectric methanogenesis, the sandwich structure comprising in order:
a microbial core, wherein the microorganism is methanogen;
the bimetal intermediate layer is coated on the surface of the microorganism core through electrostatic adsorption and other effects;
the nano semiconductor shell is deposited on one side of the bimetal intermediate layer far away from the microorganism core through the actions of self-precipitation and the like.
The sandwich structured photo-methanogenic biocatalyst of claim 1, wherein said methanogenic bacteria comprise at least one of the methanogenic bacteria Methanosarcina barkeri, methanobacterium formicicum, methanosaeta harundinacea, methanobrevibacter smithii, methanobrevibacter ruminantium and Methanospirillum hungatei.
In the present invention, the methanogen means a bacterium capable of utilizing hydrogen and producing methane. Because the photoelectric methane-generating biocatalyst with the sandwich structure is provided with the bimetallic layer, photoelectrons can be transferred to the surface of the bimetallic layer to carry out catalytic hydrogen-generating reaction. H 2 The inner metal layer has stronger adsorption energy, the Gibbs free energy is lower, and the Gibbs free energy is relatively easy to generate; and H is 2 The adsorption energy on the outer metal is lower and easy to desorb, so that the combination of the two can promote the generation and desorption transfer of hydrogen catalyzed by the metal active site. Therefore, as long as the methanogen selected has hydrogenase, the hydrogen generated by the bimetallic layer can be captured, and thus the CO generated in the body can be further captured 2 The function of reducing into methane is achieved.
In some preferred embodiments of the present invention, the methanogen has an effective viable count of 1.0X10 6 /mg～3.0×10 6 /mg。
According to a first aspect of the present invention, in some embodiments of the present invention, the bimetal intermediate layer comprises any one of a bimetal material such as NiCu, feCu, mnNi.
In contrast, inexpensive metal Cu is a promising electron transfer material, its intrinsic electron transfer energy is-0.15 eV, close to Pt, and Cu has a lower work function, which can effectively prevent electron reflux. In contrast, niThe nano semiconductor has higher work function among metals, and can be driven to generate stronger electron transfer. At the same time H 2 The catalyst has stronger adsorption energy on Ni and lower adsorption energy on Cu, so that the combination energy of the catalyst and the catalyst can obtain controllable Schottky barrier to highly enhance charge separation, promote hydrogen transfer, provide more catalytic reaction sites for the photoelectric methanogenic biocatalyst with a sandwich structure, overcome the mismatch of electron generating capacity and electron receiving capacity in the traditional scheme, and further can not realize efficient conduction of interfacial electron transfer efficiency between microorganisms and semiconductors, and greatly influence the methanogenic efficiency. Iron has a high work function similar to nickel, has stronger metal activity, and has wider sources of iron, such as acid mine wastewater and red mud, and the waste is used for reducing the generated iron, so that the cost is low and the raw material yield is high. Moreover, the ferromagnetism of the iron is favorable for recycling the bimetal material, and the cost is further reduced.
In some preferred embodiments of the present invention, the bimetallic intermediate layer is a NiCu or FeCu bimetallic material.
In some preferred embodiments of the present invention, the method for preparing the NiCu bimetallic material comprises:
and (3) dropwise adding a reducing agent into the nickel salt solution under the stirring condition until no bubbles exist in the solution and the color of the solution is changed from green to colorless, then dropwise adding copper salt into the mixture to change the color of the mixture solution from blue to colorless, centrifuging to remove the supernatant, washing and drying to obtain the NiCu bimetallic material.
In some more preferred embodiments of the present invention, the nickel salt comprises at least one of nickel acetate, nickel nitrate, nickel sulfate, and nickel chloride.
In some more preferred embodiments of the present invention, the copper salt comprises at least one of copper acetate, copper nitrate, copper sulfate, and copper chloride.
In some more preferred embodiments of the invention, the reducing agent comprises potassium borohydride or sodium borohydride. The addition amount of the reducing agent is larger than that of the nickel salt.
In some more preferred embodiments of the invention, the molar ratio of nickel salt to copper salt is from 0 to 10:0 to 10.
In some more preferred embodiments of the present invention, the method for preparing the NiCu bimetallic material comprises:
0.8mmol of NiSO 4 ·6H 2 O is dissolved in 150mL of ultrapure water, potassium borohydride is dripped under the mechanical stirring condition of 100-300 rpm at 15-40 ℃ to react for 5-60 min until no bubble exists in the solution and the color is changed from green to colorless, which indicates Ni in the solution 2+ Is completely reduced to Ni 0 . Thereafter, 0.64mmol of CuSO was added dropwise to the mixture 4 ·5H 2 O is partially substituted for Ni 0 . Standing for reaction for 30-60 min, and changing the color of the mixture solution from blue to colorless to show Cu in the solution 2+ The reaction was complete. Centrifuging at 2000-8000 rpm for 5-20 min, removing supernatant, washing with ultrapure water for 3 times, and freeze-drying for 30-60 h to obtain the NiCu bimetallic material.
In some preferred embodiments of the present invention, the FeCu bimetallic material is prepared by:
and (3) dropwise adding a reducing agent into the ferrite solution under the stirring condition until no bubbles exist in the solution and the color of the solution is changed from light green to colorless, then dropwise adding copper salt into the mixture to change the color of the mixture solution from blue to colorless, centrifuging to remove the supernatant, washing and drying to obtain the FeCu bimetallic material.
In some more preferred embodiments of the present invention, the ferrous salt includes at least one of ferrous acetate, ferrous sulfate, ferrous carbonate, and ferrous chloride.
In some more preferred embodiments of the present invention, the copper salt comprises at least one of copper acetate, copper nitrate, copper sulfate, and copper chloride.
In some more preferred embodiments of the invention, the reducing agent comprises potassium borohydride or sodium borohydride. The addition amount of the reducing agent is larger than that of ferrous salt.
In some more preferred embodiments of the invention, the molar ratio of the ferrous salt to the copper salt is from 0 to 10:0 to 10.
In some more preferred embodiments of the present invention, the FeCu bimetallic material is prepared by:
0.8mmol of FeSO 4 ·7H 2 O is dissolved in 150mL of ultrapure water, potassium borohydride is dripped under the mechanical stirring condition of 100-300 rpm at 15-40 ℃ to react for 5-60 min until no bubble exists in the solution and the color is changed from light green to colorless, which indicates Fe in the solution 2+ Is completely reduced to Fe 0 . Thereafter, 0.64mmol of CuSO was added dropwise to the mixture 4 ·5H 2 O is partially substituted for Fe 0 . Standing for reaction for 30-60 min, and changing the color of the mixture solution from blue to colorless to show Cu in the solution 2+ The reaction was complete. Centrifuging at 2000-8000 rpm for 5-20 min, removing supernatant, washing with ultrapure water for 3 times, and freeze-drying for 30-60 h to obtain FeCu bimetallic material.
According to a first aspect of the present invention, in some embodiments of the present invention, the material of the nano-semiconductor shell comprises CdS, tiO 2 Nano-semiconductors such as ZnS.
In some preferred embodiments of the invention, the semiconductor shell is a CdS semiconductor.
In some preferred embodiments of the present invention, the CdS semiconductor is prepared by:
mixing Cd salt with 3-mercaptopropionic acid (MPA), adjusting pH to alkaline, and adding S under anaerobic condition 2- Condensing and refluxing salt, precipitating with ethanol, centrifuging to remove supernatant, and freeze-drying.
In some more preferred embodiments of the present invention, the CdS semiconductor is prepared by:
10mmol of CdCl was weighed out 2 And 17mmol of 3-mercaptopropionic acid (MPA, CAS: 107-96-0) were dispersed in 200mL of water, and the pH was adjusted to 10 by the addition of 5M sodium hydroxide. Transfer to 500mL three-necked flask, purge the top air by argon for 10min, and slowly add 1mmol Na dropwise with stirring 2 S solution. The mixture was then heated to 100 ℃ under reflux and maintained at temperature for 30min to promote dispersion of the quantum dots. Adding absolute ethanol after heat preservation to form precipitate, centrifugingThe supernatant was removed, washed 3 times with ultrapure water, and freeze-dried for 48 hours to obtain a CdS semiconductor.
According to a first aspect of the invention, in some embodiments of the invention, the mass ratio of the microbial core, the bimetallic intermediate layer solution and the semiconductor shell is: 1-20: 1-30: 1 to 60.
In some preferred embodiments of the invention, the mass ratio of the microbial core, the bimetallic intermediate layer solution and the semiconductor shell is: 1:2.2:4.4.
in a second aspect of the present invention, there is provided a method for preparing a sandwich structured photo-methanogenic biocatalyst according to the first aspect of the present invention, comprising the steps of:
and adding the microbial core into the bimetallic intermediate layer solution, adding the semiconductor shell, and performing light-shielding reaction.
According to a second aspect of the invention, in some embodiments of the invention, the microorganism is methanogen; in some preferred embodiments of the invention, the methanogen comprises at least one of the hydrogen forms of methanogens Methanosarcina barkeri, methanobacterium formicicum, methanosaeta harundinacea, methanobrevibacter smithii, methanobrevibacter ruminantium, and Methanospirillum hungatei.
According to a second aspect of the present invention, in some embodiments of the present invention, the bimetal intermediate layer comprises any one of a bimetal material such as NiCu, feCu, mnNi.
In some preferred embodiments of the present invention, the bimetallic intermediate layer is a NiCu or FeCu bimetallic material.
In the conventional technology, organisms are generally combined with semiconductors in a surface self-deposition combination mode, which takes a long time and has low deposition efficiency. In addition, if the nano-semiconductor is directly deposited on the surface of the Methanosarcina bacteria, the quantum efficiency is also greatly reduced, thereby limiting the large-scale practical application thereof. The invention utilizes the bimetal layer to effectively adjust the structure/performance of the biological-non-biological interface, thereby further improving the photoelectron induction rate and the hole separation efficiency.
According to a second aspect of the present invention, in some embodiments of the present invention, the material of the semiconductor housing comprises CdS, tiO 2 Any one of ZnS nano semiconductors.
In some preferred embodiments of the invention, the semiconductor shell is a CdS semiconductor.
In some preferred embodiments of the present invention, the preparation method of the photoelectric methanogenic biocatalyst with the sandwich structure specifically comprises the following steps:
mixing Methanosarcina barkeri bacterial suspension with inorganic culture medium (MgCl) containing NiCu or FeCu bimetallic material 2 ·6H 2 O 0.4g/L、CaCl 2 ·2H 2 O 0.1g/L、NH 4 Cl 0.1g/L、KH 2 PO 4 0.2g/L、KCl 0.5g/L、HEPES 7.16g/L、NaHCO 3 2.52g/L, cysteine-HCl 0.5wt%, trace element solution SL-10 1mL, selenite-tungastate solution mL, and Vitamin solution 3 mL) are mixed, cdS semiconductor is added into the culture medium, and the culture medium is placed in an incubator for 24h in a dark place to obtain the compound.
Because the bimetallic material, methanosarcina barkeri and CdS semiconductor have different Zeta potentials, the bimetallic material, methanosarcina barkeri and CdS semiconductor can be firmly combined through electrostatic adsorption, and the photoelectric methanogenic biocatalyst with a Methanosarcina barkeri-bimetallic @ CdS sandwich structure and stable structure is formed.
According to a second aspect of the invention, in some embodiments of the invention, the mass ratio of the microbial core, the bimetallic intermediate layer solution and the semiconductor shell is: 1-20:1-30:1-60.
In some preferred embodiments of the invention, the mass ratio of the microbial core, the bimetallic intermediate layer solution and the semiconductor shell is: 1:2.2:4.4
In some preferred embodiments of the present invention, the Methanosarcina barkeri effective viable count is 2.5X10 6 /cm 2 。
In a third aspect of the invention, there is provided a methane production process comprising the steps of:
mixing the photoelectric methanogenic biocatalyst with the sandwich structure according to the second aspect of the invention with the solution, adding 0.1-0.7wt% of cysteine, and carrying out anaerobic reaction under the irradiation of a light source to obtain the photoelectric methanogenic biocatalyst.
According to a third aspect of the invention, in some embodiments of the invention, the solution comprises at least a trace element, selenite solution, mgCl 2 、CaCl 2 、NH 4 Cl、KCl、NaHCO 3 And the like.
In the embodiment of the invention, the inventor respectively uses an inorganic culture medium and sterilized natural water for comparison test, and discovers that the methane yield in different solutions does not generate obvious difference, which indicates that the photoelectric methane-generating biocatalyst in the embodiment of the invention has better applicability to different solution systems.
According to a third aspect of the invention, in some embodiments of the invention, the light source comprises a natural light source and an artificial light source.
In some preferred embodiments of the invention, the light source is at least one of sunlight, an LED lamp, a xenon lamp, and a mercury lamp.
In some preferred embodiments of the present invention, the visible light has an intensity of 0.5 to 10mW/cm 2 。
In a fourth aspect, the invention provides an application of the sandwich-structured photo-methanogenic biocatalyst in the conversion of photoelectrochemical energy.
The beneficial effects of the invention are as follows:
the invention overcomes the defects of low interfacial electron transfer efficiency, low quantum efficiency and the like of the existing photoelectric methanogenesis biocatalyst, and the quantum efficiency reaches more than 13.0 percent and is more than 10 times of the photosynthetic efficiency of the traditional plants.
The photoelectric methanogenesis biocatalyst with the sandwich structure is not limited by special reaction conditions, can take ubiquitous sunlight as driving force, does not need to construct a complex circuit system, has simple and easy operation of electrostatic self-assembly, and has higher universality and popularization value.
The photoelectric methanogenic biocatalyst with the sandwich structure has excellent environmental compatibility and light stability, which shows that the photoelectric methanogenic biocatalyst has superiority in the aspects of actual energy production and recovery, and can be applied to large-scale practical application.
Drawings
FIG. 1 is a schematic diagram of the synthesis steps of a photo-methanogenic biocatalyst of the Methanosarcina barkeri-NiCu@CdS sandwich structure in the examples.
FIG. 2 is a graph showing the characterization of a photo-methanogenic biocatalyst of the Methanosarcina barkeri-NiCu@CdS sandwich structure in the examples. Wherein a is a catalyst SEM image, the small image part is a Methanosarcina barkeri pure bacteria SEM image, and the scale mark is 1 mu m; b is a TEM image; c is an energy spectrum image marked by cadmium (Cd) element; d is a sulfur (S) element marked energy spectrum image; e is an energy spectrum image marked by nickel (Ni) element; f is an energy spectrum image marked by copper (Cu) element; b-f are all 500nm; g is a laser confocal image of the photoelectric methanogenic biocatalyst with a Methanosarcina barkeri-NiCu@CdS sandwich structure, and the scale mark is 10 mu m.
FIG. 3 is a graph showing electron transfer between a photo-methanogenic biocatalyst with a Methanosarcina barkeri-NiCu@CdS sandwich structure and a single metal catalyst under no illumination and illumination in the examples.
Detailed Description
In order to make the objects, technical solutions and technical effects of the present invention more clear, the present invention will be described in further detail with reference to the following specific embodiments. It should be understood that the detailed description is presented herein for purposes of illustration only and is not intended to limit the invention.
The experimental materials and reagents used, unless otherwise specified, are those conventionally available commercially.
In the following examples, strain information used is shown in table 1: methanosarcina barkeri, methanobacterium formicicum, methanosaeta harundinacea, methanobrevibacter smithii, methanobrevibacter ruminantium and Methanospirillum hungatei.
TABLE 1 Strain information Table
Example 1
The photoelectric methane-generating biocatalyst with the sandwich structure is prepared in the embodiment.
In this embodiment, methanosarcina barkeri is adopted as a typical methanogen to prepare a photo-methanogenic biocatalyst with a sandwich structure, and the specific preparation method is as follows:
(1) Pretreatment and material preparation:
(1) culturing strains:
preparation of a carbon-containing Medium (MgCl) 2 ·6H 2 O 0.4g/L、CaCl 2 ·2H 2 O 0.1g/L、NH 4 Cl 0.1g/L、KH 2 PO 4 0.2g/L、KCl 0.5g/L、HEPES 7.16g/L、NaHCO 3 2.52g/L、Na 2 S·9H 2 O0.24 g/L, naAc 2.788g/L, cysteine-HCl 0.5wt%, trace element solution SL-10 1mL, selenite-tungastate solution mL, vitamin solution 3 mL), and then Methanosarcina barkeri was inoculated into a medium for cultivation (temperature 37 ℃ C., cultivation time: 6 d) to obtain a bacterial liquid. Wherein, the volume ratio of the inoculation amount of Methanosarcina barkeri to the culture medium is 1:10.
(2) preparing a nickel-copper bimetallic material:
0.8mmol of NiSO 4 ·6H 2 O was dissolved in 150mL of ultrapure water, and under mechanical stirring at 25℃and 180rpm, potassium borohydride (KBH 4 0.03 mol) until no bubbles are present in the solution and the color changes from green to colorless, indicating Ni in the solution 2+ Is completely reduced to Ni 0 . Thereafter, 0.64mmol of CuSO was added dropwise to the mixture 4 ·5H 2 O is partially substituted for Ni 0 . Standing for 20min, and changing the color of the mixture solution from blue to colorless to indicate Cu in the solution 2+ The reaction was complete. Centrifuging at 5000rpm for 10min, removing supernatant, washing with ultrapure water for 3 times,and then freeze-drying for 48 hours to obtain the NiCu bimetallic material.
(3) Preparation of cadmium sulfide (CdS) semiconductor material:
10mmol of CdCl was weighed out 2 And 17mmol of 3-mercaptopropionic acid (MPA, CAS: 107-96-0) were dispersed in 200mL of water, and the pH was adjusted to 10 by the addition of 5M sodium hydroxide. Transfer to 500mL three-necked flask, purge the top air by argon for 10min, and slowly add 1mmol Na dropwise with stirring 2 S solution. The mixture was then heated to 100 ℃ under reflux and maintained at temperature for 30min to promote dispersion of the quantum dots. And (3) adding absolute ethyl alcohol after heat preservation is finished to form a precipitate, centrifuging, removing supernatant, washing with ultrapure water for 3 times, and freeze-drying for 48 hours to obtain the CdS semiconductor.
(2) Assembling the photoelectric methanogenesis biocatalyst with the sandwich structure:
taking the bacterial liquid (effective viable count is 2.5X10) obtained in the step (1) 6 /cm 2 ) Centrifuge at 7500rpm for 6min, remove supernatant, add 5mL physiological saline to resuspend. The suspension was centrifuged again 3 times. Then 5mL of the strain suspension was added to an inorganic medium (MgCl) containing 2.2mg of the NiCu bimetallic material obtained in step (2) 2 ·6H 2 O 0.4g/L、CaCl 2 ·2H 2 O 0.1g/L、NH 4 Cl 0.1g/L、KH 2 PO 4 0.2g/L、KCl 0.5g/L、HEPES 7.16g/L、NaHCO 3 2.52g/L, cysteine-HCl 0.5wt%, trace element solution SL-10 1mL, selenite-tungastate solution mL and Vitamin solution 3 mL), after 24h of reaction, adding 4.4mg of CdS semiconductor obtained in the step (3) into the culture medium, and placing the culture medium in an incubator to be cultivated for 24h in a dark place, thus obtaining the photoelectric methanogenic biocatalyst (Methanosarcina barkeri-NiCu@CdS) with a sandwich structure. As shown in FIG. 1, due to the fact that ZETA potentials of the NiCu bimetallic material, the Methanosarcina barkeri and the CdS semiconductor are different, the NiCu bimetallic material, the Methanosarcina barkeri and the CdS semiconductor can be firmly combined through electrostatic adsorption, and Methanosarcina barkeri-NiCu@CdS with stable structure is formed.
FIG. 1 is a schematic diagram of the synthesis steps of a Methanosarcina barkeri-NiCu@CdS photo-methanogenic biocatalyst with a sandwich structure in the example, and the synthesized Methanosarcina barkeri-NiCu@CdS is characterized, and the result is shown in FIG. 2.
FIGS. 2a and 2b are SEM and TEM characterization images of a Methanosarcina barkeri-NiCu@CdS photo-methanogenic biocatalyst, respectively, of a sandwich structure in an embodiment of the invention. The results show that compared with Methanosarcina barkeri pure bacteria (small diagram in fig. 2 a), methanosarcina barkeri surfaces in the photoelectric methanogenic biocatalyst are uniformly covered with a layer of coarse particles with the diameter of 10-100 nm; it was found by EDS analysis (fig. 2a, 2 c-2 f) that these particles consisted mainly of the elements Cd, S, ni and Cu; imaging using a laser scanning confocal microscope (Carl Zeiss LSM 880) was found to show the yellow fluorescence possessed by CdS semiconductor on the imaging map (fig. 2 g). Thus, it can be confirmed that both the NiCu bimetallic material and the CdS semiconductor are successfully coated on the surface of Methanosarcina barkeri.
The application method of the Methanosarcina barkeri-NiCu@CdS photoelectric methanogenic biocatalyst in the embodiment comprises the following steps: adding 0.5wt% (vs. medium) of cysteine to a medium containing Methanosarcina barkeri-NiCu@CdS, and then irradiating with visible light (light intensity of 0.5-10 mW/cm 2 Can be used in a range), and then anaerobic reaction is carried out to generate methane.
Example 2
The preparation method in example 2 is the same as in example 1, except that: replacing the inorganic medium in step (2) with an equal amount of sterilized natural water from rice fields (area Jin Shanjiao of the university of farm and forestry, fujian).
Example 3
The preparation method in example 3 is the same as in example 1, except that: replacing the inorganic medium in step (2) with an equal amount of sterilized natural water from the wetland (Fujian city, fuzhou, fujian county).
Example 4
The preparation method in example 4 is the same as in example 1, except that: replacing the inorganic culture medium in the step (2) with an equal amount of sterilized natural water body taken from the estuary (oolong river side of Fujian, fujian province).
Example 5
The preparation method in example 5 is the same as in example 1, except that: and (3) replacing the inorganic culture medium in the step (2) with an equivalent amount of sterilized natural water body which is taken from a sewage treatment plant (Fujian city, fuzhou, fujian and Ind) to flow out.
Example 6
The preparation method in example 6 is the same as in example 1, except that: the strain in step (1) was replaced with Methanobacterium formicicum, and the carbon source medium was replaced with equal amount of HCOONa with NaAc.
Example 7
The preparation method in example 7 is the same as in example 1, except that: replacing the strain in the step (1) with Methanosaeta harundinacea, and replacing the carbon source culture Medium with an equivalent DSMZ Medium 334b; the inorganic Medium in step (2) is replaced with an equivalent amount of DSMZ Medium 334b from which the organic carbon source is removed.
Example 8
The preparation method in example 8 is the same as in example 1, except that: the strain in step (1) was replaced with Methanobrevibacter smithii, and the carbon source medium was replaced with equal amount of HCOONa with NaAc.
Example 9
The preparation method in example 9 is the same as in example 1, except that: the strain in step (1) was replaced with Methanobrevibacter ruminantium, and the carbon source medium was replaced with equal amount of HCOONa with NaAc.
Example 10
The preparation method in example 10 is the same as in example 1, except that: the strain in step (1) was replaced with Methanospirillum hungatei, and the carbon source medium was replaced with equal amount of HCOONa with NaAc.
Example 11
The preparation method in example 11 is the same as in example 1, except that: step (2) substitution of nickel salt with ferrous salt (FeSO 4 ·7H 2 O) to obtain FeCu bimetallic material.
Wherein, the step (2) specifically comprises:
0.8mmol of FeSO 4 ·7H 2 O is dissolved in 150mL of ultrapure water at 15-40 ℃ and 100-300 rpm, dropwise adding potassium borohydride under the condition of mechanical stirring, reacting for 5-60 min until no bubble exists in the solution and the color is changed from light green to colorless, indicating Fe in the solution 2+ Is completely reduced to Fe 0 . Thereafter, 0.64mmol of CuSO was added dropwise to the mixture 4 ·5H 2 O is partially substituted for Fe 0 . Standing for reaction for 30-60 min, and changing the color of the mixture solution from blue to colorless to show Cu in the solution 2+ The reaction was complete. Centrifuging at 2000-8000 rpm for 5-20 min, removing supernatant, washing with ultrapure water for 3 times, and freeze-drying for 30-60 h to obtain FeCu bimetallic material.
Example 12
The preparation method in example 12 is the same as in example 1, except that: step (2) substitution of Nickel salt with manganese salt (Mn (OAc) 2 ·4H 2 O), the copper salt is replaced by nickel salt (NiSO 4 ·6H 2 O) obtaining the MnNi bimetallic material.
Comparative example 1
This example prepared a single metal biocatalyst.
In the embodiment, the biological single-metal catalyst is prepared by adopting the methanosarcina as a biological raw material, and the specific preparation method comprises the following steps:
(1) Pretreatment and material preparation:
(1) the strain culturing procedure was the same as in example 1.
(2) Preparation of nickel cadmium sulfide (Ni: cdS):
10mmol of CdCl was weighed out 2 ，0.02mmol NiCl 2 ·6H 2 O and 17mmol MPA were mixed and dispersed in 200mL water and the pH was adjusted to 10 by the addition of 5M NaOH. Transfer to 500mL three-necked flask, purge the top air by argon for 10min, and slowly add 1mmol Na dropwise with stirring 2 S solution. The mixture was then heated to 100 ℃ under reflux and maintained at temperature for 30min to promote dispersion of the quantum dots. And (3) adding absolute ethyl alcohol after heat preservation is finished to form a precipitate, centrifuging, removing supernatant, washing with ultrapure water for 3 times, and freeze-drying for 48 hours to obtain the nickel cadmium sulfide.
(2) Assembling of the single metal biocatalyst:
the bacterial liquid obtained in the step (1) in the same amount as in example 1 was taken, 0.1wt% of cysteine and 4.4mg of Ni: cdS obtained in the step (2) were added, and the culture was carried out in a dark place for 24 hours. Centrifuge at 7500rpm for 6min, remove supernatant, add 5mL physiological saline to resuspend. The centrifugation was repeated three times. Adding 48mL of inorganic culture medium, and placing in an incubator for continuous light-shielding culture for 24 hours to obtain the single-metal biocatalyst.
The application method of the biological single-metal catalyst in the embodiment comprises the following steps: to the medium containing the monometallic biocatalyst obtained in comparative example 1, 0.5wt% (vs. medium) of cysteine was added, and then anaerobic reaction was performed under visible light.
Comparative example 2
The preparation method in comparative example 2 is the same as in example 1, except that: step (2) adding no CuSO 4 ·5H 2 O。
The step (2) in comparative example 2 is specifically:
0.8mmol of NiSO 4 ·6H 2 O was dissolved in 150mL of ultrapure water, and under mechanical stirring at 25℃and 180rpm, potassium borohydride (KBH 4 0.03 mol) until no bubbles are present in the solution and the color changes from green to colorless, indicating Ni in the solution 2+ Is completely reduced to Ni 0 . Centrifuging at 5000rpm for 10min, removing supernatant, washing with ultrapure water for 3 times, and freeze-drying for 48h to obtain Ni metal material.
Comparative example 3
The preparation method in comparative example 3 is the same as in example 1, except that: step (2) adding no NiSO 4 ·6H 2 O。
The step (2) in the comparative example 3 is specifically:
0.64mmol of CuSO 4 ·5H 2 O was dissolved in 150mL of ultrapure water, and under mechanical stirring at 25℃and 180rpm, potassium borohydride (KBH 4 0.03 mol). Centrifuging at 5000rpm for 10min, removing supernatant, washing with ultrapure water for 3 times, and freeze-drying for 48h to obtain Cu metal material.
Comparative example 4
The preparation method in comparative example 4 is the same as in example 1, except that: no nickel-copper bimetallic material is added.
Comparative example 5
The preparation method in comparative example 5 is the same as in example 1, except that: the photoelectric methanogenesis biocatalyst with the sandwich structure is not irradiated.
Comparative example 6
The preparation method in comparative example 6 is the same as in example 1, except that: in the assembly step of the photoelectric methanogenic biocatalyst with the sandwich structure, methanosarcina barkeri bacterial liquid inactivated at 121 ℃ for 15min is used as a preparation raw material.
Comparative example 7
The preparation method in comparative example 7 is the same as in example 1, except that: and in the assembly step of the photoelectric methanogenesis biocatalyst with the sandwich structure, a CdS semiconductor is not added.
Comparative example 8
The preparation method in comparative example 8 is the same as in example 1, except that: the photoelectric methanogenesis biocatalyst with the sandwich structure is not added with cysteine.
Effect verification experiment
Equal amounts of the biometallic catalysts of examples 1 to 12 and comparative examples 1 to 8 were taken respectively, subjected to anaerobic reaction under visible light (comparative example 5, light-shielding treatment, other conditions being the same), for 6d, and methane content was measured by gas chromatography at 0, 2, 4 and 6d, respectively. The gas chromatography assay is referred to as being conventional in the art.
The results are shown in Table 2.
TABLE 2 methane production in the systems of examples 1-12 and comparative examples 1-8
Comparative example 1 and comparative examples 1 to 8, it can be found that methane production in examples 1 to 12The prepared photoelectric methanogenesis biocatalyst with the sandwich structure shows higher CH 4 Production efficiency, compared to CH obtained by singly using CdS semiconductor (comparative example 4), natural deposition of monometal ion doped CdS (comparative example 1), and hybrid system obtained by electrostatic self-assembly of monometal CdS (comparative examples 2 to 3) 4 The yield is high, which illustrates the superiority of the photoelectric methanogenic biocatalyst with the sandwich structure in the examples 1-12, and the highest quantum efficiency can reach 13.0%, which is greatly higher than any photoelectric methanogenic biocatalyst in the prior art and is more than 10 times of the photosynthesis of general plants.
When the inventors replaced Methanosarcina barkeri in example 1 with other methanogenic bacteria having hydrogenase (examples 6 to 10), the resulting sandwich structured photo-methanogenic biocatalyst was also capable of producing methane, which had a slightly lower methane production effect than example 1, but did not substantially change (no significant difference) from the methane production of the protocol in examples 1 to 5 as a whole, thus demonstrating that any methanogenic bacteria having hydrogenase could achieve equivalent replacement effects for the sandwich structured photo-methanogenic biocatalyst in the examples of the present invention.
Comparison of examples 1-12 with comparative examples 2-3 shows that the methane production efficiency of the sandwich structured photo-methanogenic biocatalysts of examples 1-12 is higher than that of the Methanosarcina barkeri bio-mono-metal catalyst hybrid system obtained by doping with mono-metal ions, probably due to the fact that the hybrid system obtained by doping with ions is more completely coated and more stable in the electrostatically self-assembled metal state, can protect the strain from ROS and dissolved ions, and can provide more catalytic sites and electron transfer sites.
Meanwhile, the inventors have also found that, after using the FeCu bimetal material (example 11) instead of the NiCu bimetal material (example 1), the relative output efficiency and output amount of methane are both up-regulated, indicating that the FeCu bimetal material has an advantage over the NiCu bimetal material because the FeCu bimetal material has a more excellent Schottky than the NiCu bimetal materialThe base potential barrier height can more effectively promote the separation efficiency of charge and holes, has stronger metal activity, is used as a catalytic site, is easier to react and is suitable for H 2 The transfer capacity is higher, thus further illustrating that the sandwich structure photo-methanogenic biocatalyst in the above embodiment is based on H 2 Is a catalyst for the delivery of (a) a biological catalyst. The FeCu bimetallic material has stronger magnetism, is easier to recycle and reuse, and has wide and easily available sources of manufacturing raw materials, such as acid mine wastewater and red mud, thereby further reducing the cost.
In order to evaluate the convenience and cost effectiveness of the operation, it was found that CH of examples 2 to 5 in a non-medium environment was used after irradiation of visible light for 6 days in comparison with examples 1 and examples 2 to 5 4 Yield is relatively stable, CH 4 The yield is about 88% of that of example 1 in the environment of the culture medium, which shows that the Methanosarcina barkeri-NiCu@CdS photoelectric methanogenic biocatalyst prepared in examples 1-5 can realize the effect of producing methane in different systems, and the yield does not generate significant difference due to the change of the systems, thus the photocatalyst has wide applicability and diversity in the aspects of actual energy production and recovery.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (7)
1. An optoelectronic methanogenic biocatalyst, characterized in that the optoelectronic methanogenic biocatalyst comprises, in order:
a microbial core, wherein the microorganism is methanogen;
the bimetal intermediate layer is coated on the surface of the microbial core;
the nano semiconductor shell is deposited on one side of the bimetal intermediate layer far away from the microorganism core;
wherein the methanogen comprisesMethanosarcina barkeri、Methanobacterium formicicum、 Methanosaeta harundinacea、Methanobrevibacter smithii、Methanobrevibacter ruminantiumAndMethanospirillum hungateiat least one of (a) and (b);
the bimetal intermediate layer comprises any one of NiCu, feCu and MnNi;
the nano semiconductor shell is made of CdS;
the mass ratio of the microbial core to the bimetal intermediate layer solution to the semiconductor shell is as follows: 1-20:1-30:1-60;
the effective viable count in the microorganism core is 1.0X10 6 /mg~3.0×10 6 /mg。
2. The method for preparing the photoelectric methanogenic biocatalyst of claim 1, comprising the steps of:
adding the bimetal intermediate layer into the microorganism core solution, adding the nano semiconductor shell, and performing light-shielding reaction.
3. A method of methane production comprising the steps of:
mixing the photoelectric methanogenic biocatalyst of claim 1 with a carbon-free medium, adding 0.1-0.7wt% of cysteine, and carrying out CO under the irradiation of a light source 2 And (3) reducing a methanogenesis process.
4. The method according to claim 3, wherein the carbon-free medium comprises trace elements, selenite solution, mgCl 2 、CaCl 2 、NH 4 Cl, KCl and NaHCO 3 。
5. A method according to claim 3, wherein the light source comprises a natural light source and an artificial light source.
6. The method of claim 5, wherein the light source is at least one of sunlight, an LED lamp, a xenon lamp, and a mercury lamp.
7. Use of the photoelectromethanogenic biocatalyst of claim 1 in photoelectrochemical energy conversion.
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