CN116435566A - Multifunctional aldehyde-nitrate chemical battery - Google Patents
Multifunctional aldehyde-nitrate chemical battery Download PDFInfo
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- CN116435566A CN116435566A CN202310339151.9A CN202310339151A CN116435566A CN 116435566 A CN116435566 A CN 116435566A CN 202310339151 A CN202310339151 A CN 202310339151A CN 116435566 A CN116435566 A CN 116435566A
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- nitrate
- aldehyde
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- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 title claims abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 48
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 238000006722 reduction reaction Methods 0.000 claims abstract description 28
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 17
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 32
- 239000006260 foam Substances 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229920000557 Nafion® Polymers 0.000 claims description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
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- 239000000758 substrate Substances 0.000 claims description 9
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- 239000000843 powder Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 5
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 claims description 4
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 239000006262 metallic foam Substances 0.000 claims description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- CWRKZMLUDFBPAO-VOTSOKGWSA-N (e)-dec-4-enal Chemical compound CCCCC\C=C\CCC=O CWRKZMLUDFBPAO-VOTSOKGWSA-N 0.000 claims description 2
- OFHHDSQXFXLTKC-UHFFFAOYSA-N 10-undecenal Chemical compound C=CCCCCCCCCC=O OFHHDSQXFXLTKC-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- BSAIUMLZVGUGKX-UHFFFAOYSA-N 2-Nonenal Natural products CCCCCCC=CC=O BSAIUMLZVGUGKX-UHFFFAOYSA-N 0.000 claims description 2
- BSAIUMLZVGUGKX-FPLPWBNLSA-N 2-nonenal Chemical compound CCCCCC\C=C/C=O BSAIUMLZVGUGKX-FPLPWBNLSA-N 0.000 claims description 2
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 claims description 2
- QUWBEVVGEOTKOX-UHFFFAOYSA-N 7,7-dimethyloct-2-enal Chemical compound CC(C)(C)CCCC=CC=O QUWBEVVGEOTKOX-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 2
- 229940073505 ethyl vanillin Drugs 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- UHUFTBALEZWWIH-UHFFFAOYSA-N tetradecanal Chemical compound CCCCCCCCCCCCCC=O UHUFTBALEZWWIH-UHFFFAOYSA-N 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012141 vanillin Nutrition 0.000 claims description 2
- 229940117960 vanillin Drugs 0.000 claims description 2
- 238000010248 power generation Methods 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 27
- 239000000376 reactant Substances 0.000 description 21
- 239000002105 nanoparticle Substances 0.000 description 20
- 239000012528 membrane Substances 0.000 description 16
- 235000019253 formic acid Nutrition 0.000 description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000011056 performance test Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003011 anion exchange membrane Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- OWQHJMYFQUOKPI-UHFFFAOYSA-N methylidenenickel Chemical compound [Ni]=C OWQHJMYFQUOKPI-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 230000000052 comparative effect Effects 0.000 description 2
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- JSTRKGVXPIJSLB-UHFFFAOYSA-N formaldehyde nitric acid Chemical compound C=O.[N+](=O)(O)[O-] JSTRKGVXPIJSLB-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a multifunctional aldehyde-nitrate radical chemical battery, nitrate radical ion compound is added into electrolyte in a cathode electrolytic cell, and ammonia is collected from a reaction output end or the electrolyte after reaction; aldehyde compounds are added into the anolyte, and acid products are collected in a reaction output end or the electrolyte after reaction; the anode spontaneously performs aldehyde oxidation reaction, the cathode generates nitrate radical reduction reaction, and the potential difference between the oxidation of anode formaldehyde and the reduction of cathode nitrate radical ions generates directionally moving electrons to form current in an external circuit. The invention utilizes anodic aldehyde oxidation reaction and coupling cathode nitrate ion reduction reaction to realize a novel functional chemical battery integrating power generation, aldehyde oxidation and nitrate reduction under mild conditions.
Description
Technical Field
The invention belongs to the field of chemical batteries related to chemical conversion and pollutant removal, and relates to a multifunctional aldehyde-nitrate chemical battery.
Background
Formaldehyde (HCHO) is a highly toxic substance, readily soluble in water, identified by the world health organization as a carcinogenic, teratogenic substance, commonly found in indoor air pollution and industrial wastewater. Currently, the modes for removing formaldehyde mainly comprise adsorption (activated carbon, alumina and ceramic materials), photocatalytic oxidation, plasma technology, fenton reagent oxidation method and the like. Wherein, the adsorbent such as activated carbon and the like is limited by factors such as the maximum adsorption capacity, relative humidity or water absorption deactivation of the material for HCHO physical adsorption; photocatalytic oxidation may lead to toxicityByproducts; the Fenton reagent method is the most adopted method for pretreatment of high-concentration HCHO wastewater, but the Fenton oxidation method consumes a large amount of oxidant, has high cost and also has the problem of secondary pollution. Conversion of HCHO to formic acid (HCOOH) by electrocatalytic oxidation without formation of harmful byproducts or secondary pollutants, can also be directly oxidized to CO by screening suitable catalysts 2 To effectively remove HCHO contaminants in the air. Thus, electrocatalytic oxidation of HCHO is a very promising way to remove HCHO contaminants. In addition, catalytic oxidation of other aldehydes to acids is also widely used, for example, patent CN114653390a converts 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid by electrocatalytic oxidation; the electrocatalytic formaldehyde oxidation is used for replacing the anode oxygen evolution reaction in the water electrolysis process, and hydrogen can be produced at both the anode and the cathode under the condition of consuming less electric energy (Nature Communication 2023,14,525). Compared with a thermal catalysis method, the electrocatalytic HCHO oxidation technology has the advantages of mild reaction conditions, simplicity in operation, high energy utilization rate and the like.
Ammonia (NH) 3 ) Is a multipurpose basic compound in the modern society, and relates to the fields of chemical synthesis, fertilizers, fuels, clean energy carriers and the like. Annual industrial production of NH by statistics 3 Exceeding 1.5 million tons and its demand is increasing. The current industrial ammonia synthesis method is to use gas phase N 2 And H 2 The synthesis ammonia process (Haber-Bosch process) as a raw material, however, the Haber-Bosch process has severe conditions (500 ℃ C.),>100 atm), high requirements on equipment, high energy consumption, low conversion rate and the like, and the energy consumption exceeds 2% of annual global energy consumption. Electrocatalytic N 2 Reduction synthesis of NH 3 Is a clean way of synthesizing ammonia, but due to the high stability of N≡N, electrocatalytic N 2 Reduction synthesis of NH 3 Is low in comparison with the yield and current density of n=o bond dissociation energy (204 kJ mol -1 ) By electrocatalytic nitrate reduction (NO 3 - RR) can achieve faster NH 3 The production rate (Nature Nanotechnology2022,17, 759-767) was mild, equipment simplified, and very little carbon emissions. Nitrate radical (NO) 3 - ) Is a rich nitrogen source in industrial wastewater and polluted groundwater, nitrate in water will have adverse effect on human beings and environment, thus, the electrocatalytic NO is utilized 3 - The reduction can simultaneously relieve the production pressure faced by industrial synthetic ammonia and treat nitrate pollution in water.
Although electrocatalytic aldehyde oxidation and nitrate reduction have many advantages, a process that consumes a large amount of electrical energy is still involved. Meanwhile, renewable energy power generation has the problems of dependence on geographical environment, weather conditions, instability and the like. Because the aldehydes have higher oxidation potential and the reduction potential of nitrate is lower, the potential difference between the oxidation of aldehydes and the reduction of nitrate can be utilized to form an aldehyde-nitrate chemical battery, and the anode spontaneously performs aldehyde oxidation reaction R-CHO+H 2 O→RCOOH+2H + +2e - Or 2R-CHO+4OH - →2R-COO - +2H 2 O+H 2 +2e - Nitrate radical reduction reaction NO occurs at cathode 3 - +9H + +9e - →NH 3 +3H 2 O or NO 3 - +6H 2 O+8e - →NH 3 +9OH - And simultaneously, the electrochemical conversion and the electric energy output of the aldehyde compound and nitrate are realized.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a multifunctional aldehyde-nitrate radical chemical battery, which is based on the high importance of environmental pollution at the present stage and the requirement of novel energy devices.
The invention consists of an aldehyde oxidation anode, a nitrate ion reduction cathode, an ion exchange membrane and a battery shell. The aldehyde compound of the battery anode contacts with the catalyst through a conductive electrode or a membrane electrode to perform oxidation reaction: R-CHO+H 2 O→RCOOH+2H + +2e - Or 2R-CHO+4OH - →2R-COO - +2H 2 O+H 2 +2e - Releasing electrons; simultaneously, nitrate of the cathode is contacted with the catalyst through the conductive electrode or the membrane electrode to obtain electrons, and the electrons undergo reduction reaction: NO (NO) 3 - +9H + +e - →NH 3 +3H 2 O or NO 3 - +6H 2 O+8e - →NH 3 +9OH - An electric current is formed in an external circuit, thereby forming a multifunctional aldehyde-nitrate chemical battery. Under the condition of no external power supply, the electrocatalytic oxidation of aldehydes to acids, electrocatalytic synthesis of ammonia from nitrate radical and power generation are realized simultaneously, and the method has the obvious advantages of mild condition, environment friendliness, safety, low cost, high efficiency and the like.
One of the technical problems to be solved by the invention is the design and performance test of an aldehyde-nitrate chemical battery device for continuously oxidizing aldehyde compounds and reducing nitrate.
The second technical problem to be solved by the invention is to design and screen the aldehyde oxidation and nitrate reduction electrocatalyst with high activity and high stability.
Technical proposal
A multifunctional aldehyde-nitrate chemical battery comprising a cathode, a cathode and an electrolyte; the method is characterized in that: adding nitrate ion compound into electrolyte in a cathode electrolytic cell, and collecting product ammonia at the reaction output end or in the electrolyte after reaction; aldehyde compounds are added into the anolyte, and acid products are collected in a reaction output end or the electrolyte after reaction; the anode spontaneously performs aldehyde oxidation reaction, the cathode generates nitrate radical reduction reaction, and the potential difference between the oxidation of anode formaldehyde and the reduction of cathode nitrate radical ions generates directionally moving electrons to form current in an external circuit.
The catholyte and anolyte are acidic, neutral, alkaline or solid electrolytes, including but not limited to: 0.01-5M HCl, 0.01-5M H 2 SO 4 0.01-5M KCl solution and 0.01-10M KHCO 3 Solution or 0.01-10M KOH solution.
The aldehyde compounds include, but are not limited to, gaseous or liquid aldehyde group-containing compounds or mixtures of aldehyde group-containing compounds such as formaldehyde, acetaldehyde, propionaldehyde, furfural, lauraldehyde, myristyl aldehyde, 2-nonenal, trans-4-decenal, undecylenal, nondienal, benzaldehyde, phenylacetaldehyde, phenylpropionaldehyde, cinnamaldehyde, vanillin, ethylvanillin, hydroxycitronellal, trimethylheptenal, and the like.
The nitrate ion compound raw materials include, but are not limited to, nitrate ion-containing compounds or nitrate ion-containing mixtures such as sodium nitrate, potassium nitrate, ammonium nitrate, calcium nitrate, lead nitrate, cerium nitrate, and the like.
The electrolytic cell adopts a flow type electrolytic cell or an H-type electrolytic cell.
And an ion exchange membrane is arranged between the cathode and the anode for isolation.
The cathode is: spraying the catalyst A on the conductive substrate or the ion exchange membrane to ensure that the loading capacity after spraying is 0.001-100 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The powder of the catalyst A comprises, but is not limited to, a single metal and a bimetallic catalyst based on Ni, cu, fe, co, pt, pd, au, ag and the like, a metal phthalocyanine catalyst, a metal carbene and the like and a metal organic complex catalyst.
The anode is: spraying a catalyst B on the conductive substrate or the ion exchange membrane to ensure that the loading capacity after spraying is 0.001-100 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The powders of catalyst B include, but are not limited to, pt, pd, au, ag, ir, ru-based catalysts and non-noble metal-based catalysts based on Fe, co, ni.
The slurry of the catalyst A or B is: uniformly dispersing the catalyst powder into a solvent, fully ultrasonically mixing, adding Nafion solution, and vibrating for 10-120 min by using an ultrasonic bath to obtain catalyst slurry; the solvent includes, but is not limited to, isopropyl alcohol.
The conductive substrate includes, but is not limited to, metal foam, carbon paper, or carbon cloth; the metal foam includes, but is not limited to, copper foam or nickel foam.
When the foam metal is used as a cathode, the preparation method comprises the steps of firstly cleaning foam nickel with dilute hydrochloric acid, ionized water and absolute ethyl alcohol in sequence and drying in vacuum at 60 ℃. Then immersing the mixture into precursor solution prepared by nickel nitrate hexahydrate and hexamethylenetetramine HMT, and carrying out hydrothermal treatment at the temperature of 90-100 ℃ for 8 hours. Taking out the mixture after cooling, ultrasonically cleaning the mixture by using ionized water, and finally transferring the mixture into a vacuum drying oven to be dried for 10 hours at 80 ℃ and taking out the mixture; other metal arrays grown on the foam metal can be prepared by adopting corresponding methods.
Advantageous effects
The invention provides a multifunctional aldehyde-nitrate radical chemical battery, wherein nitrate radical ion compound is added into electrolyte in a cathode electrolytic cell, and ammonia is collected from a reaction output end or the electrolyte after reaction; aldehyde compounds are added into the anolyte, and acid products are collected in a reaction output end or the electrolyte after reaction; the anode spontaneously performs aldehyde oxidation reaction, the cathode generates nitrate radical reduction reaction, and the potential difference between the oxidation of anode formaldehyde and the reduction of cathode nitrate radical ions generates directionally moving electrons to form current in an external circuit.
The aldehyde compound of the battery anode contacts with the catalyst through the conductive electrode or the membrane electrode, obtains oxygen atoms from the electrolyte, and performs oxidation reaction: R-CHO+H 2 O→RCOOH+2H + +2e - Or 2R-CHO+4OH - →2R-COO - +2H 2 O+H 2 +2e - The method comprises the steps of carrying out a first treatment on the surface of the Simultaneously, nitrate ions of the cathode are contacted with the catalyst through a conductive electrode or a membrane electrode, electrons and hydrogen ions are respectively obtained from the anode and electrolyte, and reduction reaction is carried out: NO (NO) 3 - +9H + +9e - →NH 3 +3H 2 O or NO 3 - +6H 2 O+8e - →NH 3 +9OH - Thereby forming a dual-function formaldehyde-nitrate chemical battery. The battery can realize the efficient generation of aldehyde electrocatalytic oxidation and nitrate ion electrocatalytic reduction synthesis ammonia while generating electric energy, achieves the multiple targets of chemical upgrading conversion and pollutant treatment power generation, creates higher economic value and meets the technical requirements of green chemical industry.
The invention utilizes anodic aldehyde oxidation reaction and coupling cathode nitrate ion reduction reaction to realize a novel functional chemical battery integrating power generation, aldehyde oxidation and nitrate reduction under mild conditions.
The innovation of the invention is that:
(1) In the method, anodic aldehyde oxidation reaction is coupled with cathodic nitrate reduction reaction, so that electric energy can be spontaneously generated, and two important industrial reactions can be efficiently realized;
(2) Compared with the traditional thermocatalytic aldehyde acid preparation method, the electrocatalytic aldehyde oxidation reaction does not form harmful byproducts or secondary pollutants;
(3) In the method, the bond energy of nitrate is smaller, the reduction energy consumption is low, nitrate is a main nitrogenous water pollutant, and the electroreduction product ammonia is an important chemical product;
in the method, the aldehyde oxidation and nitrate reduction reactions are carried out at normal temperature and normal pressure, so that the safety is improved, and no extra energy is consumed.
Drawings
FIG. 1 shows the structure and discharge mechanism of a flow cell dual function aldehyde-nitrate ion battery (HCOH as the anode material and KNO as the cathode material) 3 Electrolyte 1M KOH for example);
FIG. 2 is a graph having a length of 1cm 2 Electrode area HCHO-KNO 3 A discharge curve and a power density curve of the battery.
Detailed Description
The invention will now be further described with reference to examples, figures:
the performance of the assembled battery, the content of product components at the outlet of the anode and the cathode, the conversion rate, the selectivity and the like are tested by combining specific aldehyde compounds, nitrate and catalysts to assemble the aldehyde-nitrate chemical battery.
The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments of the application. When the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or groups thereof. The technical scheme of the invention is described below with reference to examples.
[ example 1 ]
(1) Preparation of a foam nickel catalyst: a. ultrasonic treating the foam nickel with 1M diluted hydrochloric acid for 15min, washing with deionized water and absolute ethanol, and vacuum drying at 60deg.C.
(2) The foam nickel is used as the cathode and anode of the electrolytic cell, and both the catholyte and the anolyte are adoptedThe chambers are separated by anion exchange membranes using 1M KOH aqueous solution. Adding 5mL of 0.5M reactant HCOH into the anolyte, adding 5mL of 0.5M KNO into the catholyte 3 An aqueous solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst foam nickel is characterized by a constant current method, and after the catalyst foam nickel is reacted for 1 hour, the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
[ example 2 ]
(1) Preparing a foam copper-based catalyst: a. cleaning foam copper, respectively adopting 1M hydrochloric acid, acetone and ethanol to ultrasonically clean for 5-10min, and drying with nitrogen; b. preparing a sodium hydroxide and ammonium persulfate solution with a certain concentration, and immersing the dried foam copper into the solution for 20-50 min to uniformly grow copper hydroxide; c. reducing hydrogen into copper in a tube furnace at 100-300 ℃ to obtain the foam copper-based catalyst.
(2) The foam copper is used as the cathode and anode of the electrolytic cell, the cathode electrolyte and the anode electrolyte are both 1M KOH solution, and the cathode and anode chambers are isolated by a proton exchange membrane. Adding 5mL of 0.5M reactant HCOH into the anolyte, adding 5mL of 0.5M KNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst foam copper is characterized by a constant current method, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum after reactants at the anode and the cathode react for 1 hour.
[ example 3 ]
(1) Preparing Ni nano particle slurry: 25mg of Ni nanoparticles were dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) The Ni nano particle slurry is uniformly sprayed on a carbon fiber paper conductive substrate to serve as the anode and cathode of an electrolytic cell, electrolyte of the anode and cathode is 1M KOH solution, and the anode and cathode chambers are isolated by a proton exchange membrane. Adding 5mL of 0.5M reactant HCOH into the anolyte, adding 5mL of 0.5M KNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst Ni nano particles is characterized by a constant current method, reactants at the anode and the cathode react for 1 hour, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
[ example 4 ]
(1) Preparing Ni nano particle slurry: 25mg of Ni nanoparticles were dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) The Ni nano particle slurry is uniformly sprayed on the surface of a proton exchange membrane by a precise spraying device to serve as the anode and cathode of an electrolytic cell, electrolyte of the anode and the cathode is 1M KOH solution, and the anode and the cathode are isolated by the proton exchange membrane. Adding 5mL of 0.5M reactant HCOH into the anolyte, and adding 5mL of 0.5M NaNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst Ni nano particles is characterized by a constant current method, reactants at the anode and the cathode react for 1 hour, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
[ example 5 ]
(1) Preparation of Pd/graphite catalyst slurry: 25mg of Pd/graphite catalyst powder was dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) The Pd/graphite slurry is uniformly sprayed on the surface of a proton exchange membrane by a precise spraying device to serve as the anode and cathode of the electrolytic cell, electrolyte of the anode and the cathode is 1M KOH solution, and the anode and the cathode are isolated by an anion exchange membrane. Adding 5mL of 0.5M reactant HCOH into the anolyte, and adding 5mL of 0.5M NaNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the Pd/graphite catalyst is characterized by a constant current method, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum after reactants at the anode and the cathode react for 1 hour.
[ example 6 ]
(1) Preparing a carbene nickel catalyst slurry: 25mg of the carbene nickel catalyst was dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) Uniformly spraying the carbene nickel slurry on a carbon fiber paper conductive substrate to serve as a cathode and an anode of an electrolytic cell, wherein electrolyte of the cathode and the anode is 1M KHCO 3 The solution and the yin and yang chambers are separated by a proton exchange membrane. Adding 5mL of 0.5M reactant benzaldehyde into the anolyte, and adding 5mL of 0.5M NaNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst carbene nickel is characterized by a constant current method, reactants at the anode and the cathode react for 1 hour, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
[ example 7 ]
(1) Preparing a catalyst slurry: 25mg of nickel phthalocyanine catalyst was dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) Uniformly spraying nickel phthalocyanine catalyst slurry on a carbon fiber paper conductive substrate to serve as the anode and cathode of an electrolytic cell, wherein both the catholyte and the anolyte are 1M KHCO 3 The yin and yang chambers are separated by proton exchange membranes. Adding 5mL of 0.5M reactant benzaldehyde into the anolyte, adding 5mL of 0.5M KNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst nickel phthalocyanine is characterized by a constant current method, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum after reactants at the anode and the cathode react for 1 hour.
[ example 8 ]
(1) Preparing Pt nano particle slurry: 25mg of Pt nanoparticles were dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) Uniformly spraying Pt nano particle slurry on a proton exchange membrane to serve as the anode and cathode of an electrolytic cell, wherein both the catholyte and the anolyte are 0.5M H 2 SO 4 The solution and the yin and yang chambers are separated by a proton exchange membrane. Adding 5mL of 0.5M reactant benzaldehyde into the anolyte, and adding 5mL of 0.5M KNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the Pt nano-particles of the catalyst is characterized by a constant current method, reactants at the anode and the cathode react for 1 hour, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
[ example 9 ]
(1) Preparing Ag nano particle slurry: 25mg of Ag nanoparticles were dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) Uniformly spraying Ag nano particle slurry on a proton exchange membrane to serve as the anode and cathode of an electrolytic cell, wherein both the catholyte and the anolyte are 0.5M H 2 SO 4 The solution and the yin and yang chambers are separated by a proton exchange membrane. Adding 5mL of 0.5M reactant acetaldehyde into the anolyte, adding 5mL of 0.5M KNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst Ag nano-particles is characterized by a constant current method, reactants at the anode and the cathode react for 1 hour, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
[ example 10 ]
(1) Preparing a Ni-based alloy catalyst: the alloy catalyst with active components of metallic nickel, metallic copper and metallic zinc is prepared by adopting a sol-gel method.
(2) Ni alloy catalyst is used as the cathode and anode of the electrolytic cell, and the cathode and anode are electrolyzedThe liquid is 0.5. 0.5M H 2 SO 4 The solution and the yin and yang chambers are separated by a proton exchange membrane. Adding 5mL of 0.5M reactant acetaldehyde into the anolyte, adding 5mL of 0.5M KNO into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The constant current method characterizes the catalytic activity of the catalyst Ni-based alloy, and the liquid phase product formic acid and the gas phase product ammonia are analyzed through chromatography or ultraviolet absorption spectrum after reactants at the anode and the cathode react for 1 hour.
[ comparative example 1 ]
(1) Preparation of a foam nickel catalyst: a. ultrasonic treating the foam nickel with 1M diluted hydrochloric acid for 15min, washing with deionized water and absolute ethanol, and vacuum drying at 60deg.C.
(2) The foam nickel is used as the cathode and anode of the electrolytic cell, the catholyte and the anolyte are both 1M KOH solution, and the cathode and anode chambers are isolated by an anion exchange membrane. Aldehyde compound is not added into the anolyte, and 5mL of 0.5M KNO is added into the catholyte 3 A solution.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the catalyst foam nickel is characterized by a constant current method, and after the catalyst foam nickel is reacted for 1 hour, the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
[ comparative example 2 ]
(1) Preparing Pt nano particle catalyst slurry: 25mg of Pt nanoparticles were dispersed in 15mL of isopropanol, then 75. Mu.L of Nafion solution (5 wt%) was added, stirred and sonicated for 90min.
(2) The Pt nano particle slurry is uniformly sprayed on an anion exchange membrane to serve as the cathode and anode of an electrolytic cell, the catholyte and the anolyte are 1M KOH solution, and the cathode and anode are isolated by the anion exchange membrane. 5mL of 0.5M reactant HCOH was added to the anolyte and no nitrate was added to the catholyte.
(3) The electrochemical performance test is carried out by an electrochemical workstation by adopting a flowing type electrolytic cell of a two-electrode system. The catalytic activity of the Pt nano-particles of the catalyst is characterized by a constant current method, reactants at the anode and the cathode react for 1 hour, and the liquid-phase product formic acid and the gas-phase product ammonia are analyzed by chromatography or ultraviolet absorption spectrum.
The specific evaluation results are shown in Table 1
Claims (10)
1. A multifunctional aldehyde-nitrate chemical battery comprising a cathode, an anode and an electrolyte; the method is characterized in that: adding nitrate ion compound into electrolyte in a cathode electrolytic cell, and collecting product ammonia at the reaction output end or in the electrolyte after reaction; aldehyde compounds are added into the anolyte, and acid products are collected in a reaction output end or the electrolyte after reaction; the anode spontaneously performs aldehyde oxidation reaction, the cathode generates nitrate radical reduction reaction, and the potential difference between the oxidation of anode formaldehyde and the reduction of cathode nitrate radical ions generates directionally moving electrons to form current in an external circuit.
2. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the catholyte and anolyte are acidic, neutral, alkaline or solid electrolytes, including but not limited to: 0.01-5M HCl, 0.01-5M H 2 SO 4 0.01-5M KCl solution and 0.01-10M KHCO 3 Solution or 0.01-10M KOH solution.
3. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the aldehyde compounds include, but are not limited to, gaseous or liquid aldehyde group-containing compounds or mixtures of aldehyde group-containing compounds such as formaldehyde, acetaldehyde, propionaldehyde, furfural, lauraldehyde, myristyl aldehyde, 2-nonenal, trans-4-decenal, undecylenal, nondienal, benzaldehyde, phenylacetaldehyde, phenylpropionaldehyde, cinnamaldehyde, vanillin, ethylvanillin, hydroxycitronellal, trimethylheptenal, and the like.
4. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the nitrate ion compound raw materials include, but are not limited to, nitrate ion-containing compounds or nitrate ion-containing mixtures such as sodium nitrate, potassium nitrate, ammonium nitrate, calcium nitrate, lead nitrate, cerium nitrate, and the like.
5. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the electrolytic cell adopts a flow type electrolytic cell or an H-type electrolytic cell.
6. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: and an ion exchange membrane is arranged between the cathode and the anode for isolation.
7. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the cathode is: spraying the catalyst A on the conductive substrate or the ion exchange membrane to ensure that the loading capacity after spraying is 0.001-100 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The powder of the catalyst A comprises, but is not limited to, a single metal and a bimetallic catalyst based on Ni, cu, fe, co, pt, pd, au, ag and the like, a metal phthalocyanine catalyst, a metal carbene and the like and a metal organic complex catalyst.
8. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the anode is: spraying a catalyst B on the conductive substrate or the ion exchange membrane to ensure that the loading capacity after spraying is 0.001-100 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The powders of catalyst B include, but are not limited to, pt, pd, au, ag, ir, ru-based catalysts and non-noble metal-based catalysts based on Fe, co, ni.
9. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the slurry of the catalyst A or B is: uniformly dispersing the catalyst powder into a solvent, fully ultrasonically mixing, adding Nafion solution, and vibrating for 10-120 min by using an ultrasonic bath to obtain catalyst slurry; the solvent includes, but is not limited to, isopropyl alcohol.
10. The multi-functional aldehyde-nitrate chemical cell according to claim 1, wherein: the conductive substrate includes, but is not limited to, metal foam, carbon paper, or carbon cloth; the metal foam includes, but is not limited to, copper foam or nickel foam.
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| CN114959771A (en) * | 2022-04-19 | 2022-08-30 | 南京信息工程大学 | Nickel-based electrocatalyst and electrolytic cell for degrading formaldehyde wastewater by hydrogen production |
| CN114959771B (en) * | 2022-04-19 | 2023-10-20 | 南京信息工程大学 | Nickel-based electrocatalyst and hydrogen production synergistic formaldehyde wastewater degradation electrolytic cell |
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