CN114574881B - Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances - Google Patents
Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances Download PDFInfo
- Publication number
- CN114574881B CN114574881B CN202210222136.1A CN202210222136A CN114574881B CN 114574881 B CN114574881 B CN 114574881B CN 202210222136 A CN202210222136 A CN 202210222136A CN 114574881 B CN114574881 B CN 114574881B
- Authority
- CN
- China
- Prior art keywords
- alditol
- carbon felt
- substances
- electrocatalytic
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 42
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 24
- 150000005846 sugar alcohols Chemical class 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 36
- 150000003624 transition metals Chemical class 0.000 claims abstract description 36
- -1 nitrogen-oxygen free radical compounds Chemical class 0.000 claims abstract description 35
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 29
- 239000008103 glucose Substances 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract 2
- 150000003839 salts Chemical class 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011734 sodium Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 17
- 229910052753 mercury Inorganic materials 0.000 claims description 17
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002484 cyclic voltammetry Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 11
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 11
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 10
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 claims description 3
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 claims description 3
- 206010056474 Erythrosis Diseases 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 46
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 18
- 239000002243 precursor Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000000174 gluconic acid Substances 0.000 description 12
- 235000012208 gluconic acid Nutrition 0.000 description 12
- 239000002028 Biomass Substances 0.000 description 11
- 239000003011 anion exchange membrane Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000004811 liquid chromatography Methods 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 125000003172 aldehyde group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 150000007519 polyprotic acids Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229940097043 glucuronic acid Drugs 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 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
- 229910052737 gold Inorganic materials 0.000 description 2
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910002545 FeCoNi Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241000746966 Zizania Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000009229 glucose formation Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/05—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances belongs to the technical field of electrocatalytic materials, wherein a carbon felt loaded with transition metal is used as an anode, a platinum sheet electrode is used as a cathode, an anion membrane separates two poles of an electrolytic cell to form an electrocatalytic reactor, and the alditol substances are subjected to electrocatalytic oxidation to prepare the polycarboxylic acid by direct-current low-voltage under the electrolyte containing nitrogen-oxygen free radical compounds or derivatives thereof, alditol substances and inorganic salts. Taking glucose as an example, compared with the existing strong base electrocatalytic system, the system provided by the invention can effectively reduce the occurrence of side reactions such as anti-aldol and the like under weak alkaline mild conditions, remarkably improve the selectivity of glucaric acid, and simultaneously coproduce hydrogen.
Description
Technical Field
The invention relates to the field of electrochemical catalysis, in particular to a method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances.
Background
The high oxygen content of biomass resources is an ideal raw material for preparing oxygen-containing chemicals. Among them, cellulose has a very important role in the field of catalytic conversion of biomass. Based on the hydrolysis of cellulose to prepare glucose, the oxidation of glucose to prepare glucaric acid by gluconic acid, and the hydrogenolysis of glucaric acid to prepare important chemical raw material adipic acid are a conversion path with economic benefit. In addition, 5-Hydroxymethylfurfural (HMF) is a platform chemical prepared by acid-catalyzed dehydration of glucose or fructose or hydrolysis-dehydration of polysaccharides. The hydroxyl or aldehyde groups on HMF are oxidized to produce valuable chemicals, especially 2, 5-furandicarboxylic acid (FDCA), which are considered to be alternatives to terephthalic acid in synthetic polymeric materials due to their structure and properties similar to terephthalic acid. Also, the preparation of the xylonic diacid by oxidation of xylose and the preparation of the glyceric acid by oxidation of glycerol have great application prospect.
To achieve the core objective of preparing polybasic acid by oxidizing the biomass molecules, it is common to achieve selective oxidation of aldehyde functional groups and hydroxyl functional groups, so that a set of oxidation schemes for preparing polybasic carboxylic acid with high selectivity are required to be designed.
However, the existing method for preparing the polycarboxylic acid has the problems of low selectivity, complex side reaction and the like. Glucose production of glucaric acid is exemplified by glucose. The existing methods for producing the glucaric acid have the defects of long fermentation time (more than 2 days), low selectivity (the yield of the glucaric acid is less than 20%), difficult separation of products (the co-production of a large amount of microbial biomass and hundreds of byproducts with similar properties) and the like.
Chemical oxidation is the main industrial method for producing glucaric acid, chemical oxidation is either using HNO in the absence of a catalyst 3 Stoichiometric oxidation of glucose, either by oxidation with O in the presence of noble metals such as Au, pt, pd and Ru at 45-120deg.C 2 (air) catalytic oxidation of glucose. For example, zizania et al studied glucose oxidation on Au-based catalysts at 120 ℃ at 0.3MPa oxygen with a gluconic acid yield of 92% and a glucaric acid yield of less than 5%. Gold et al reported that the bimetallic PtCu catalyst oxidizes glucose to glucaric acid at 45℃and 0.1MPa oxygen with a yield of 45%. The traditional catalytic oxidation of glucose to glucaric acid has several disadvantages: (1) A large amount of toxic oxidant (more than twice the stoichiometric ratio) is required; (2) The selectivity to glucaric acid is low (selectivity to glucaric acid is less than 60%); (3) Producing a variety of chemical properties that are similarByproducts (such as tartaric acid, glycolic acid, hydroxy malonic acid, and oxalic acid); (4) using high pressure oxygen to conceal the security risk; (5) The scarcity of noble metal (e.g., pt, ru, rh, and Pd) based catalysts brings high costs. Therefore, development of a green and efficient preparation method of glucaric acid has important application value.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances, which uses glucose as a representative compound, couples a transition metal-based catalyst with a nitroxide free radical compound, and performs electrocatalytic oxidation of glucose at an anode to realize high-selectivity preparation of glucaric acid, and simultaneously performs high-efficiency hydrogen evolution at an cathode. The system has the advantages of mild reaction conditions, normal temperature and normal pressure, extremely high catalytic efficiency, simple operation, low raw material cost, low reaction energy consumption and the like, and has industrial application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substance uses carbon felt loaded with transition metal as anode, platinum sheet electrode as cathode, and uses anionic membrane to separate two poles of electrolytic cell so as to form electrocatalytic reactor, and uses direct-current low-voltage electrocatalytic oxidation of alditol substance to prepare polycarboxylic acid under the condition of electrolyte containing nitroxide free radical compound or its derivative, alditol substance and inorganic salt.
The preparation method of the transition metal-loaded carbon felt comprises the following steps: dissolving urea and nitrate in deionized water, adding absolute ethyl alcohol, stirring, ultrasonic treatment, adding pretreated carbon felt, performing hydrothermal reaction, preserving heat for a certain time at a certain temperature, taking out, washing with ethanol and water in sequence, and finally drying and calcining.
The pretreated carbon felt treatment method comprises the following steps: sequentially carrying out ultrasonic treatment on the carbon felt under absolute ethyl alcohol and distilled water, washing to remove surface impurities, taking the carbon felt as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and NaOH solution as an electrolyte, carrying out oxidation treatment by adopting a chronopotentiometric method, and washing the carbon felt with a large amount of distilled water by ultrasonic treatment to remove residual NaOH after the treatment is completed.
The certain temperature is 150-200 ℃, the certain time is 12-24 hours, and the calcination temperature is 300-500 ℃; the molar ratio of the urea to the nitrate is 1:1-1:5.
The transition metal comprises at least one of Fe, co, ni, cu, zn and Mn.
The nitroxide radical or its derivative comprises 2, 6-tetramethyl piperidine 1-oxyl radical 4-oxo-2, 6-tetramethylpiperidine-1-oxyl, 4-amino-2, 6-tetramethylpiperidine-1-oxyl 4-cyano-2, 6-tetramethylpiperidine 1-oxyl radical, 4-hydroxy-2, 6-tetramethylpiperidine 1-oxyl radical at least one of 4-carboxyl-2, 6-tetramethyl piperidine 1-oxygen free radical and 4-acetamido-2, 6-tetramethyl piperidine 1-oxygen free radical.
The alditol substances comprise at least one of glucose, 5-hydroxymethylfurfural, xylose, cellulose, hemicellulose, erythrose, glycerol and glycolaldehyde.
The concentration of the alditol substances is 10-2000 mmol/L, and the molar ratio of the nitroxide free radical compound or the derivative thereof to the alditol substances is 1:10-1:1000.
The inorganic salt comprises at least one of sodium hydroxide, potassium hydroxide, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium carbonate and sodium bicarbonate, and the concentration of the electrolyte is 0.1-1 mol/L.
The transition metal-loaded carbon felt needs to be activated in a reaction system before being used, and the activation treatment comprises the following steps: the carbon felt loaded with transition metal is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and Na 2 CO 3 The solution is electrolyte solution, and adopts cyclic voltammetry activation treatment, the potential range is 0.7-1.7V (vs. RHE), the cycle times are 50-100 times, and the scanning frequency is 50-100 mV s -1 。
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the invention can realize the regulation and control of the respective yields of the gluconic acid and the glucaric acid by coupling the two catalysts under the condition that the total yield of the gluconic acid and the glucaric acid is unchanged (> 91%). The transition metal-loaded carbon felt catalyst oxidizes glucose to produce gluconic acid, and the gluconic acid is further oxidized into glucaric acid under the action of a nitrogen-oxygen free radical or derivative catalyst, so that the purpose of regulating and controlling the respective yields of the gluconic acid and the glucaric acid is achieved.
2. The transition metal-loaded carbon felt is prepared by in-situ growth by a hydrothermal method, for example, spherical FeOx metal nano particles are grown and loaded on a carbon felt CF, the preparation process of the catalyst is simple, the preparation cost is low, the catalytic system is simple and easy to control, the catalytic efficiency is extremely high, and the industrialization is easy.
3. The transition metal-loaded carbon felt catalyst prepared by the invention has the advantages of large specific surface area of a multi-stage structure, multiple active sites, excellent conductivity of the aggregate carbon felt, contribution to charge transfer, enhanced catalytic efficiency, oxidation resistance, corrosion resistance and excellent stability.
4. The catalytic system can be carried out at normal temperature and low voltage, the equipment requirements on reaction temperature and pressure in the traditional process are not needed, and the process is simpler.
Drawings
Fig. 1 is a schematic view of the structure of the device of the present invention.
FIG. 2 is a product profile of an electrocatalytic system containing nitroxide-only compounds.
Fig. 3 is a product profile of an electrocatalytic system with transition metal LDH nanoplatelets alone.
FIG. 4 is a product profile of a coupled electrocatalytic system containing noble metals and nitroxide compounds.
FIG. 5 is a product profile of an electrocatalytic system containing transition metal and nitroxide compound separation.
Fig. 6 is an SEM image of the carbon felt supported transition metal Ni LDH (a, b) and its pre-reaction (c), post-reaction (d).
FIG. 7 is a carbon felt (a), carbon felt supported transition metal precursor Ni (OH) 2 (b) Before (c), after (d), and regeneration of Ni-CFXRD pattern of the latter (e).
FIG. 8 is a cyclic voltammogram of a TEMPO, carbon felt supported transition metal Ni-CF, and TEMPO coupling system.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
As shown in figure 1, the electrocatalytic reaction of the invention uses an H-type two-chamber electrochemical electrolytic cell, the two chambers are separated by an anion exchange membrane, a lead is connected with an electrochemical workstation to serve as a power supply and a testing instrument, a carbon felt loaded with transition metal is used as an anode, the carbon felt is fixed in the anode chamber, a platinum sheet electrode is used as a cathode, the platinum sheet electrode is fixed in the cathode chamber, and under the electrolyte of the anode chamber containing a nitroxide free radical compound or a derivative thereof, an alditol substance and inorganic salt, the alditol substance is catalyzed and oxidized at the tail end aldehyde group and hydroxyl group step by using two combined catalysts in the system through direct current at low voltage, so that the high selectivity preparation of the polycarboxylic acid is realized, and meanwhile, the hydrogen is co-produced at the cathode.
Example 1 a method for constructing an electrocatalytic system in which Fe LDH nanoplatelets of polyacids are prepared by oxidation of biomass and nitroxide free radical compounds are coupled.
Pretreating a carbon felt: sequentially carrying out ultrasonic treatment on commercial carbon felt under absolute ethyl alcohol and distilled water for 4min, washing to remove surface impurities, taking the carbon felt as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and a 1M NaOH solution as an electrolyte, carrying out oxidation treatment by adopting a chronopotentiometric method, and after the treatment is completed, carrying out ultrasonic washing on the carbon felt with a large amount of distilled water for 30min to remove residual NaOH. The chronopotentiometry, the potential was 1.9V (vs. rhe), the treatment time was 10min.
Dissolving 0.2g of urea and 0.1g of ferric nitrate in deionized water, adding absolute ethyl alcohol, stirring, and carrying out ultrasonic treatment for 10min to uniformly mix to obtain a yellow clear solution. Transferring the solution to a polytetrafluoroethylene lining, putting a piece of pretreated carbon felt into the lining, sealing the lining in a hydrothermal autoclave, and preserving the heat for 12 hours at 150 ℃. Cooling, sequentially washing with ethanol and distilled water for several times to obtain precursor, and treating the precursor with waterDrying in a 60 ℃ oven for 1h, calcining the precursor in a muffle furnace, programming the temperature to 300 ℃ at a speed of 5 ℃/min under air atmosphere, and maintaining for 4h to obtain the final Fe 2 O 3 -CF catalyst. The Fe is 2 O 3 -CF catalyst, wherein Fe 2 O 3 Is spherical in shape, and uniformly and compactly grows on the carbon felt substrate.
Before the catalyst is used formally, it is necessary to perform an activation treatment in the reaction system. The Fe is 2 O 3 The polarization curve of the material does not find obvious change before and after 1000 times of CV circulation of the CF catalyst, which shows that the catalyst has good stability.
Fe prepared by the method 2 O 3 -CF is coupled with 4-acetamido-2, 6-tetramethylpiperidine 1-oxyl radical (ACT) to construct a catalytic system for preparing glucaric acid. The system uses an H-shaped two-chamber electrochemical electrolytic cell, the two chambers are separated by an anion exchange membrane, a lead is connected with an electrochemical workstation as a power supply and a testing instrument, fe 2 O 3 The CF catalyst is used as a working electrode and fixed in an anode chamber, and the electrolyte in the anode chamber is 0.1M Na 2 CO 3 A mixture of 0.1mM ACT and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, fe 2 O 3 The CF catalyst is subjected to an activation treatment. By Fe 2 O 3 CF is the working electrode, platinum sheet is the counter electrode, mercury/oxidized mercury electrode is the reference electrode, 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 。
The product was analyzed by liquid chromatography, and the glucose conversion in example 1 was 97.6%, the glucaric acid yield was 82.1%, and the faraday efficiency was 79.3%.
Example 2 construction method of an electrocatalytic System in which Ni LDH nanosheets and nitroxide free radical Compounds of polybasic acids are coupled to each other by Biomass Oxidation
Dissolving 1g of urea and 1g of nickel nitrate in deionized water, adding absolute ethyl alcohol, stirring, and carrying out ultrasonic treatment for 10min to uniformly mix, thereby obtaining a green clear solution. Transfer the solution to a polytetrafluoroethylene liner, place a piece of carbon felt, seal in a hydrothermal autoclave, and keep warm at 160 ℃ for 16h. And (3) cooling, sequentially washing with ethanol and distilled water for multiple times to obtain a precursor, drying the precursor in a baking oven at 60 ℃ for 1h, placing the precursor in a muffle furnace for calcination, and programming the temperature to 400 ℃ at a speed of 5 ℃/min under the air atmosphere and keeping the temperature for 4h to obtain the final NiO-CF catalyst. Before the catalyst is used formally, it is necessary to perform an activation treatment in the reaction system.
The NiO-CF prepared above is coupled with 4-acetamido-2, 6-tetramethyl piperidine 1-oxyl radical (ACT) to construct a catalytic system for preparing glucaric acid. The system uses an H-shaped two-chamber electrochemical electrolytic cell, two chambers are separated by an anion exchange membrane, a lead is connected with an electrochemical workstation as a power supply and a testing instrument, a NiO-CF catalyst is used as a working electrode and is fixed in an anode chamber, and the electrolyte in the anode chamber is 0.1M Na 2 CO 3 A mixture of 0.1mM ACT and 200mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, the NiO-CF catalyst is subjected to activation treatment. NiO-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 。
The product was analyzed by liquid chromatography, and in example 2, the conversion of glucose was 98.1%, the yield of glucaric acid was 83.7%, and the Faraday efficiency was 81.3%.
Example 3 construction method of Co LDH nanosheets and nitroxide free radical Compound coupled electrocatalysis System for preparing polybasic acid by Biomass oxidation
Dissolving 1.5g of urea and 1g of cobalt nitrate in deionized water, adding absolute ethyl alcohol, stirring, and carrying out ultrasonic treatment for 10min to uniformly mix to obtain a red clear solution. Transferring the solution into a polytetrafluoroethylene lining, placing a piece of carbon felt, and sealing in a hydrothermal autoclavePreserving the heat for 20 hours at 170 ℃. Cooling, sequentially washing with ethanol and distilled water for multiple times to obtain a precursor, drying the precursor in a 60 ℃ oven for 1h, calcining the precursor in a muffle furnace, and heating to 450 ℃ at a speed of 5 ℃/min under air atmosphere and maintaining for 4h to obtain the final Co 3 O 4 -CF catalyst. Before the catalyst is used formally, it is necessary to perform an activation treatment in the reaction system.
Co as described above 3 O 4 -CF coupled with 2, 6-tetramethylpiperidine 1-oxyl (TEMPO) to build an electrocatalytic system. The system uses an H-shaped two-chamber electrochemical electrolytic cell, the two chambers are separated by an anion exchange membrane, a wire is connected with an electrochemical workstation as a power supply and a testing instrument, co 3 O 4 The CF catalyst is used as a working electrode and fixed in an anode chamber, and the electrolyte in the anode chamber is 0.1M Na 2 CO 3 A mixture of 0.1mM TEMPO and 500mM xylose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before formal reaction, co 3 O 4 The CF catalyst is subjected to an activation treatment. By Co 3 O 4 CF is the working electrode, platinum sheet is the counter electrode, mercury/oxidized mercury electrode is the reference electrode, 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 。
The product was analyzed by liquid chromatography, and in example 3, the xylose conversion was 98.6%, the xylose diacid yield was 89.7%, and the faraday efficiency was 86.4%.
Example 4 construction method of an electrocatalytic System in which Cu LDH nanosheets and nitroxide free radical Compounds of polybasic acids are coupled by Biomass Oxidation
Dissolving 2g of urea and 2g of copper nitrate in deionized water, adding absolute ethyl alcohol, stirring, and carrying out ultrasonic treatment for 10min to uniformly mix, thereby obtaining a blue clear solution. Transferring the solution to a polytetrafluoroethylene lining, putting a piece of carbon felt into the lining, sealing the lining in a hydrothermal autoclave, and preserving the temperature for 24 hours at 180 ℃. And (3) cooling, sequentially washing with ethanol and distilled water for multiple times to obtain a precursor, drying the precursor in a baking oven at 60 ℃ for 1h, placing the precursor in a muffle furnace for calcination, and programming the temperature to 500 ℃ at a speed of 5 ℃/min under the air atmosphere and keeping the temperature for 2h to obtain the final CuO-CF catalyst. Before the catalyst is used formally, it is necessary to perform an activation treatment in the reaction system.
The prepared CuO-CF is coupled with 4-carboxyl-2, 6-tetramethyl piperidine 1-oxyl free radical (CBT) to construct an electrocatalytic system. The system uses an H-type two-chamber electrochemical electrolytic cell, two chambers are separated by an anion exchange membrane, a lead is connected with an electrochemical workstation as a power supply and a testing instrument, a CuO-CF catalyst is used as a working electrode and is fixed in an anode chamber, and the electrolyte in the anode chamber is 0.1M Na 2 CO 3 A mixture of 1mM CBT and 1000mM 5-Hydroxymethylfurfural (HMF); the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, the CuO-CF catalyst is subjected to activation treatment. CuO-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 。
The product was analyzed by liquid chromatography, with 99.4% HMF conversion, 96.8% FDCA yield, and 92.9% faraday efficiency in example 4.
Example 5 construction method of FeCoNi LDHs nanosheets and nitroxide free radical compound coupled electro-catalytic System for preparing polybasic acid by Biomass oxidation
Dissolving 2g of urea, 1g of ferric nitrate, 1g of cobalt nitrate and 1g of nickel nitrate in deionized water, adding absolute ethyl alcohol, stirring, and carrying out ultrasonic treatment for 10min to uniformly mix, thereby obtaining a red clear solution. Transfer the solution to a polytetrafluoroethylene liner, place a piece of carbon felt, seal in a hydrothermal autoclave, and keep the temperature at 190 ℃ for 24 hours. Cooling, sequentially washing with ethanol and distilled water for multiple times to obtain a precursor, drying the precursor in a 60 ℃ oven for 1h, placing the precursor in a muffle furnace for calcination, and programming the temperature to 500 ℃ at a speed of 5 ℃/min under air atmosphere and keeping for 2h to obtain the final FeCoNiO x -CF catalyst. Catalytic actionBefore the chemical agent is formally used, it is necessary to perform an activation treatment in the reaction system.
The FeCoNiO prepared by the method x -CF is coupled with 4-acetamido-2, 6-tetramethylpiperidine 1-oxyl radical (ACT) to build an electrocatalytic system. The system uses an H-shaped two-chamber electrochemical electrolytic cell, the two chambers are separated by an anion exchange membrane, a wire is connected with an electrochemical workstation as a power supply and a testing instrument, and FeCoNiO x The CF catalyst is used as a working electrode and fixed in an anode chamber, and the electrolyte in the anode chamber is 0.1M Na 2 CO 3 A mixture of 2mM ACT and 1000mM xylose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, feCoNiO x The CF catalyst is subjected to an activation treatment. By FeCoNiO x CF is the working electrode, platinum sheet is the counter electrode, mercury/oxidized mercury electrode is the reference electrode, 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 。
The product was analyzed by liquid chromatography, and in example 5, the xylose conversion was 98.9%, the xylose diacid yield was 91.2%, and the faraday efficiency was 86.7%.
Comparative example 1 electrocatalytic System of Nitrogen-oxygen-containing radical Compound alone
The electrocatalytic system of nitrogen-oxygen-containing free radical compound only uses H-type two-chamber electrochemical electrolytic cell, two chambers are separated by anion exchange membrane, and the wire is connected with electrochemical workstation as power supply and test instrument, carbon felt as working electrode is fixed in anode chamber, and the electrolyte in anode chamber is 0.1M Na 2 CO 3 A mixture of 1mM TEMPO and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, the carbon felt needs to be activated. Carbon felt is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE)The number of loops was 50 times, the sweep frequency was 50mV s -1 The product was then subjected to liquid chromatography.
As shown in FIG. 2, the comparative example was conducted by adjusting the molar ratio of TEMPO to glucose and examining the effect of TEMPO on the reaction. The distribution of the product is shown in figure 2, the final product of the electrocatalytic reaction system of the nitrogen-oxygen-containing free radical compound is mainly composed of gluconic acid and byproducts, and the final glucaric acid selectivity is not high in the reaction system.
Comparative example 2 electrocatalytic System with transition Metal LDH nanosheets only
Electrocatalytic systems containing transition metal LDH nanoplatelets (M-CF) alone. The system uses an H-type two-chamber electrochemical electrolytic cell, two chambers are separated by an anion exchange membrane, a lead is connected with an electrochemical workstation as a power supply and a testing instrument, M-CF is used as a working electrode and is fixed in an anode chamber, and electrolyte in the anode chamber is 0.1M Na 2 CO 3 And 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, M-CF is subjected to an activation treatment. M-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 The product was then subjected to liquid chromatography.
As shown in fig. 3, this comparative example examined the effect of different metals on the reaction. The distribution of the product is shown in figure 3, and the transition metal LDH nanosheets (M-CF) can selectively oxidize aldehyde groups to an intermediate product gluconic acid, so that the final product of the reaction system is mainly gluconic acid. However, since the effect of the oxidation of hydroxyl groups is poor, the glucaric acid is hardly obtained in the reaction system at last.
Comparative example 3 coupled electrocatalytic System containing noble Metal and nitroxide Compounds
A coupled electrocatalytic system comprising noble metals and nitroxide compounds. The system uses an H-shaped two-chamber electrochemical electrolytic cell, the two chambers are separated by an anion exchange membrane, and a wire is connected with an electrochemical workstation to serve asThe power supply and the testing instrument are provided, M-CF is used as a working electrode and is fixed in an anode chamber, and electrolyte in the anode chamber is 0.1M Na 2 CO 3 A mixture of 1mM TEMPO and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, M-CF is subjected to an activation treatment. M-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 The product was then subjected to liquid chromatography.
The product distribution is shown in FIG. 4, and, first, the selective oxidation of glucose by the noble metal catalyst (M-CF) alone is weak, and glucaric acid is hardly obtained. Second, after the noble metal catalyst (M-CF) and the nitroxide compound are coupled, there is no significant improvement over the nitroxide compound alone system, so the coupling of the noble metal and the nitroxide compound does not allow for highly selective oxidation to glucaric acid.
Example 6 electrocatalytic System containing separation of transition Metal and nitroxide Compounds
An electrocatalytic system containing a transition metal (for example Ni) and a nitroxide compound (for example TEMPO) for separation. The system uses an H-type two-chamber electrochemical electrolytic cell, two chambers are separated by an anion exchange membrane, a lead is connected with an electrochemical workstation as a power supply and a testing instrument, M-CF is used as a working electrode and is fixed in an anode chamber, and electrolyte in the anode chamber is 0.1M Na 2 CO 3 A mixture of 0 or 1mM TEMPO and 100mM glucose; the reference electrode and the counter electrode are fixed in a cathode chamber, and the electrolyte in the cathode chamber is 0.1M Na 2 CO 3 Is a solution of (a) and (b). Before the formal reaction, M-CF is subjected to an activation treatment. M-CF is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and 0.1M Na 2 CO 3 The solution is electrolyte solution, and is activated by cyclic voltammetry with potential range of 0.7-1.7V (vs. RHE), cycle times of 50 times and scanning frequency of 50mV s -1 。
The product was subjected to liquid chromatography and the product distribution is shown in fig. 5. Firstly, only adding a transition metal catalyst before reacting for 60min, and gradually converting glucose into an intermediate product gluconic acid as can be seen from the figure; then, taking out the transition metal catalyst after 60min, and adding a nitroxide free radical compound, so that the gluconic acid gradually starts to be converted into glucuronic acid; finally, a transition metal catalyst is added after 120min, and the glucuronic acid gradually starts to be converted into glucaric acid.
The results prove that the transition metal catalyst can promote the oxidation reaction of aldehyde groups in glucose and glucuronic acid, the nitroxide free radical compound can accelerate the oxidation of C6 hydroxyl at the tail end position of glucuronic acid, and the two cooperate to accelerate the selective oxidation of aldehyde groups and hydroxyl, so that the occurrence of side reactions is reduced, and the glucaric acid can be prepared by high-selective oxidation.
Fig. 6 is SEM images of the carbon felt supported transition metal Ni LDH (a, b) and the pre-reaction (c) and post-reaction (d), and it can be seen that the morphology of the carbon felt supported transition metal catalyst is not greatly changed before and after the reaction, and the catalyst morphology is relatively stable.
FIG. 7 is a carbon felt (a), carbon felt supported transition metal precursor Ni (OH) 2 (b) XRD patterns of Ni-CF before reaction (c), after reaction (d) and after regeneration (e) show that the catalyst phase part is changed due to the reconstruction of the surface of the transition metal catalyst loaded by the carbon felt before and after reaction, and the catalyst crystal form is recovered after the catalyst is regenerated.
FIG. 8 is a cyclic voltammogram (CV plot, 10mV s sweep rate) of a TEMPO, carbon felt supported transition metal Ni-CF, ni-CF and TEMPO coupling system -1 ). From the CV plot, it can be seen that the oxidation capacity of the Ni-TEMPO coupling system is enhanced, possibly related to the promotion of TEMPO circulation by the production of trivalent Ni species NiOOH by the Ni oxidation process.
The invention couples the transition metal-based catalyst with the nitroxide free radical compound to construct a set of electrocatalytic system for preparing the polycarboxylic acid by oxidizing the biomass with high selectivity. Realize the selective electrooxidation of various alditol substances, including glucose, 5-hydroxymethylfurfural, xylose, cellulose, hemicellulose, erythrose, glycerol, glycolaldehyde and other compounds. The present invention uses glucose as a representative compound as a reactant of the system to obtain the glucaric acid with high yield. The system has the obvious advantages of mild reaction conditions, extremely high catalytic efficiency, universality in the aspect of aldehyde alcohol biomass molecular oxidation, environmental friendliness and the like.
Claims (3)
1. A method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances is characterized in that: the method comprises the steps of using a carbon felt loaded with transition metal as an anode, using a platinum sheet electrode as a cathode, separating two poles of an electrolytic cell by an anion membrane to form an electrocatalytic reactor, and preparing the polycarboxylic acid by electrocatalytically oxidizing alditol substances through direct current at low voltage in an electrolyte containing nitroxide free radical compounds or derivatives thereof, alditol substances and inorganic salts;
the transition metal comprises at least one of Fe, co, ni, cu, zn and Mn; the nitroxide radical or its derivative comprises 2, 6-tetramethyl piperidine 1-oxyl radical 4-oxo-2, 6-tetramethylpiperidine-1-oxyl, 4-amino-2, 6-tetramethylpiperidine-1-oxyl 4-cyano-2, 6-tetramethylpiperidine 1-oxyl radical, 4-hydroxy-2, 6-tetramethylpiperidine 1-oxyl radical at least one of 4-carboxyl-2, 6-tetramethyl piperidine 1-oxygen free radical and 4-acetamido-2, 6-tetramethyl piperidine 1-oxygen free radical; the alditol substances comprise at least one of glucose, 5-hydroxymethylfurfural, xylose, cellulose, hemicellulose, erythrose, glycerol and glycolaldehyde;
the preparation method of the transition metal-loaded carbon felt comprises the following steps: dissolving urea and nitrate in deionized water, adding absolute ethyl alcohol, stirring, carrying out ultrasound, then adding pretreated carbon felt, carrying out hydrothermal reaction, preserving heat for 12-24 hours at 150-200 ℃, taking out, washing with ethanol and water in sequence, and finally drying, calcining at 300-500 ℃; the molar ratio of the urea to the nitrate is 1:1-1:5;
the pretreated carbon felt treatment method comprises the following steps: sequentially carrying out ultrasonic treatment on a carbon felt under absolute ethyl alcohol and distilled water, washing to remove surface impurities, taking the carbon felt as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and NaOH solution as an electrolyte, carrying out oxidation treatment by adopting a chronopotentiometric method, and carrying out ultrasonic washing on the carbon felt with a large amount of distilled water to remove residual NaOH after the treatment is finished;
the transition metal-loaded carbon felt needs to be activated in a reaction system before being used, and the activation treatment comprises the following steps: the carbon felt loaded with transition metal is used as a working electrode, a platinum sheet is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, and Na 2 CO 3 The solution is electrolyte solution, and is subjected to cyclic voltammetry activation treatment, the potential range is 0.7-1.7V (vs. RHE), the cycle times are 50-100 times, and the scanning frequency is 50-100 mV s -1 。
2. A method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol according to claim 1, wherein the method comprises the steps of: the concentration of the alditol substances is 10-2000 mmol/L, and the molar ratio of the nitroxide free radical compound or the derivative thereof to the alditol substances is 1:10-1:1000.
3. A method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol according to claim 1, wherein the method comprises the steps of: the inorganic salt comprises at least one of potassium sulfate, sodium hydroxide, potassium hydroxide, sodium sulfate, sodium chloride, potassium chloride, sodium carbonate and sodium bicarbonate, and the concentration of the electrolyte is 0.1-1 mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210222136.1A CN114574881B (en) | 2022-03-09 | 2022-03-09 | Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210222136.1A CN114574881B (en) | 2022-03-09 | 2022-03-09 | Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114574881A CN114574881A (en) | 2022-06-03 |
| CN114574881B true CN114574881B (en) | 2024-04-09 |
Family
ID=81773612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210222136.1A Active CN114574881B (en) | 2022-03-09 | 2022-03-09 | Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114574881B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115369432A (en) * | 2022-08-23 | 2022-11-22 | 大连理工大学 | Method for preparing nitrile by coupling electro-catalysis of primary alcohol and ammonia substances |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436910A (en) * | 2013-08-02 | 2013-12-11 | 天津工业大学 | Preparation method of gluconic acid and glucaric acid |
| CN111472020A (en) * | 2019-06-04 | 2020-07-31 | 中山大学 | Method for preparing 2,5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural with hydrotalcite-based layered catalyst |
| WO2021195953A1 (en) * | 2020-03-31 | 2021-10-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 2,5-furandicarboxylic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9598780B2 (en) * | 2015-01-08 | 2017-03-21 | Wisconsin Alumni Research Foundation | Electrochemical and photoelectrochemical oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and 2,5-diformylfuran |
-
2022
- 2022-03-09 CN CN202210222136.1A patent/CN114574881B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436910A (en) * | 2013-08-02 | 2013-12-11 | 天津工业大学 | Preparation method of gluconic acid and glucaric acid |
| CN111472020A (en) * | 2019-06-04 | 2020-07-31 | 中山大学 | Method for preparing 2,5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural with hydrotalcite-based layered catalyst |
| WO2021195953A1 (en) * | 2020-03-31 | 2021-10-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 2,5-furandicarboxylic acid |
Non-Patent Citations (1)
| Title |
|---|
| Allison C.Cardiel et al..Stabilities, Regeneration Pathways, and Electrocatalytic Properties of Nitroxyl Radicals for the Electrochemical Oxidation of 5-Hydroxymethylfurfural.2019,11138−11149. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114574881A (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111437846B (en) | Porous CoO/CoP nanotube and preparation method and application thereof | |
| CN114574881B (en) | Method for preparing polycarboxylic acid by electrocatalytic oxidation of alditol substances | |
| WO2011120441A1 (en) | Paired electrosynthetic method for producing butanedioic acid and sulfuric acid | |
| CN110787820B (en) | Heteroatom nitrogen surface modification MoS2Preparation and application of nano material | |
| CN114836781B (en) | Preparation method and application of lamellar Cu-based N-doped graphene catalyst | |
| CN114086202B (en) | Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production | |
| CN113249743B (en) | Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof | |
| CN114717571A (en) | Anolyte and benzaldehyde and hydrogen coupling co-production system and application | |
| CN109331804B (en) | Graphene nanodisk and preparation method and application thereof | |
| CN116516392B (en) | CoSe nano-sheet electrocatalyst with cation vacancy and preparation method and application thereof | |
| CN114438525B (en) | Method for synthesizing furoic acid by electrochemical conversion of furfuraldehyde cathode | |
| CN113416977B (en) | KRu 4 O 8 Nanorod material, preparation method and application thereof | |
| CN112144073B (en) | Electrocatalytic reduction of CO under heteropolyacid ionic liquid-indium double-catalytic system2Method for preparing ethanolic acid | |
| CN114481170B (en) | Method for synthesizing furoic acid by furfural in linear paired electrochemical manner | |
| CN113969410B (en) | Method for synthesizing 2, 5-dihydroxymethyl furan by electrocatalytic hydrogenation of 5-hydroxymethylfurfural by adopting non-noble metal oxide | |
| CN112626553B (en) | Hollow carbon tube composite material and preparation method and application thereof | |
| CN114921808B (en) | Vanadium-doped iridium dioxide electrocatalyst, and preparation method and application thereof | |
| CN115537871A (en) | Preparation method and application of nickel hydroxide electrode material | |
| CN111905820B (en) | Preparation method of oxygen evolution electrocatalyst containing transition metal organic polymer | |
| CN116575063A (en) | Electrode material, electrolysis device and application thereof | |
| CN116590747A (en) | Ru/RuO 2 /Co 3 O 4 CC composite material, preparation method and application thereof | |
| CN116876032A (en) | Method for synthesizing organic acid ligand hybrid nickel cobalt hydroxide catalyst by one-step hydrothermal method and application | |
| CN118147680A (en) | Electrocatalytic system for continuously producing adipic acid by taking lignin phenol derivatives as raw materials and method for preparing adipic acid by using electrocatalytic system | |
| CN117488321A (en) | Electrocatalytic CO 2 Method for producing ethylene by reducing and coupling propionic acid oxidation | |
| CN117947433A (en) | Catalyst for electrochemical synthesis of terephthalic acid and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |