CN106040239B - A kind of high-dispersion nano metal simple-substance/carbon composite controllable method for preparing and its electro-catalysis application - Google Patents
A kind of high-dispersion nano metal simple-substance/carbon composite controllable method for preparing and its electro-catalysis application Download PDFInfo
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- CN106040239B CN106040239B CN201610358771.7A CN201610358771A CN106040239B CN 106040239 B CN106040239 B CN 106040239B CN 201610358771 A CN201610358771 A CN 201610358771A CN 106040239 B CN106040239 B CN 106040239B
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- mesoporous carbon
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000126 substance Substances 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 14
- 239000006185 dispersion Substances 0.000 title claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 238000002848 electrochemical method Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 239000003575 carbonaceous material Substances 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 231100000719 pollutant Toxicity 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims 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 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000010412 perfusion Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 235000015096 spirit Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 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 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005287 template synthesis Methods 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 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000001802 infusion Methods 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 230000008901 benefit Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000001925 catabolic effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QSQUFRGBXGXOHF-UHFFFAOYSA-N cobalt(III) nitrate Inorganic materials [Co].O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O QSQUFRGBXGXOHF-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 208000005135 methemoglobinemia Diseases 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Abstract
The present invention relates to a kind of high-dispersion nano metal simple-substance/carbon composite preparation method and its electro-catalysis applications, synthesize the order mesoporous carbon powder material with high-ratio surface；The oxidation processes material obtains mesoporous carbon of the surface with hydrophilic radical and high-ratio surface；Metal precursor is perfused by infusion process, and is translated into hydroxide with the method that ammonia is fumigated and is fixed in mesoporous confinement duct；In H2Lower high temperature reduction finally obtains high degree of dispersion nano metal simple substance/mesoporous carbon composite material.By taking Zero-valent Iron/mesoporous carbon as an example, using the composite material as working electrode, using three-electrode electro Chemical method, is restored by electro-catalysis and remove the nitrate in water body.The composite material that the present invention obtains, elemental metals nano particle is small, and is dispersed in the duct of carbon substrate, and the crystallization degree and load capacity of metal are easy to control in preparation process；High to the treatment effeciency of nitrate after electrode slice is made, the selectivity of nitrogen improves, and stability is good, the secondary pollutions such as non-metallic ion dissolution.
Description
Technical field
The present invention provides a kind of nanocomposite preparation methods that nitrate in removal water body is restored using electro-catalysis
And its application, belong to pollutant catabolic gene removal field, is related to a kind of mesoporous carbon-loaded high-content, polymolecularity metal simple-substance nanometer
The preparation method of granular materials.
Background technique
With the rapid development of economy, the use of a large amount of chemical nitrogen fertilizers, lives, the unreasonable place of industrial wastewater and sludge
Set, nitrate content increasingly increases in the surface water and groundwater of many countries and regions, have become one it is fairly common and
Serious environmental problem.The raising of nitrogen will cause water eutrophication and break out wawter bloom in natural water, while drinking water
The intake of excessive nitrate in source, can be converted into nitrite in human body, to induce methemoglobinemia, sternly
It will cause hypoxia death when weight.The World Health Organization provides NO in drinking water in water quality standard for drinking water3- N concentration is no more than
10 mg/L.Therefore, the water source for effectively controlling and handling high azotate pollution becomes the task of top priority.
The method of nitrate mainly has physics, chemistry and bioanalysis in removal water body at present.In contrast, physical method is gone
Except nitrate does not have selectivity, pollutant is only shifted or is concentrated there is no really degradation；The common anti-nitre of biology
Nitrate transformation is nitrogen by the reduction of microorganism by change method, but this method capacity of resisting impact load is poor, complex process,
Exist simultaneously secondary pollution problems；Chemical reduction method mainly includes metal simple-substance reduction method, catalysis reduction and electrochemical process.Gold
Belong to simple substance reduction method mainly using metal simple-substances such as iron, aluminium, zinc as reducing agent, has problems in that the product of reaction is difficult to turn
The secondary pollution for turning to harmless nitrogen, and metal ion being generated etc..And be catalyzed reduction using monometallic or bimetallic as
Catalyst restores nitrate, but usually requires to use hydrogen as reducing agent, and solubility is small under normal pressure for hydrogen, uses peace
Full property is bad.Electrochemical reducing is reducing agent using electronics, obtains the extensive concern of researcher in recent years.Usual electrochemistry
Often it is used in combination with noble metal catalyst, and the application for carrying out catalysis reduction is used in combination with base metal simple substance for electrochemical method
Still there is potentiality to be exploited.
Iron is a kind of metal cheap and easy to get.Nano zero valence iron is answered extensively because its particle size is small, reduction activation is strong
Research for pollutant removals all kinds of in water body.In conjunction with the advantage of nano zero valence iron and electrochemical method, while use is to nitre
Hydrochlorate, which carries out catalysis reduction, can cooperate with its removal ability of raising.However due to big specific surface and magnetism, nano zero valence iron is non-
It is often easy to reunite, greatly reduces its effective active position, and material release is had into certain nanometer in the environment in the process
Toxicity.Therefore nano zero valence iron is supported on certain carrier, thus can high degree of dispersion nano particle to prevent from reuniting, increase
Add its specific surface and active sites, and is capable of fixing metal and reduces secondary pollution.Ordered mesoporous material is a kind of aperture in 2~50 nm
Material have its unique advantage as novel nano material carrier.Especially ordered mesoporous carbon material has big ratio table
Area and pore volume, pore-size distribution is uniform and is continuously adjusted on nanoscale, and cellular structure is from one-dimensional to three-dimensional adjustable and advise
Then orderly, morphology controllable, skeleton structure are stablized, advantages of environment protection.Mesoporous carbon is highly stable in water body, mesopore orbit
It can be used as the confinement space of nano particle, load, dispersion and the nano-metal particle for fixing even particle size.In addition, carbon
Material is a kind of good conductive material.Nano zero-valence iron particle uniform load can be formed in the duct of mesoporous carbon
Particle sub-electrode.This is combined to the cathode of electrode, cooperates with simple substance catalytic reduction performance and chemical property, thus raising pair
The removal rate and selectivity of nitrate, while avoiding secondary pollution problem.
Using mesoporous carbon as the research of support dispersion nano zero valence iron it has been reported that but obtaining one kind by controlling synthesis and having
Little particle and evenly dispersed and high load capacity nano zero valence iron/meso-porous carbon material, being still one has the problem of challenge.
For angle prepared by material, nano zero valence iron usually (has the reagent such as NaBH of strong reducing power by liquid-phase reduction4), carbon heat
Reduction, vapour phase reduction (reducibility gas such as H2), pyrogenic metal predecessor Fe (CO)5The methods of obtain.For nano zero valence iron
Load, the method using vapour phase reduction is a preferable method of loading.In addition, iron predecessor is anti-during vapour phase reduction
It answers process to will cause a degree of predecessor Species migration and reunion, therefore improves there is still a need for the introducing of certain technology and disperse
Performance.
Summary of the invention
The purpose of the present invention is to provide a kind of polymolecularity, stability is good, nano metal simple substance/carbon of high reaction activity
By taking nano zero valence iron/mesoporous carbon as an example electrode slice is made in the composite material by composite material, in conjunction with electrocatalytic denitrification method, reduction
Remove the nitrate in water body.
Nano metal simple substance/mesoporous carbon composite material of preparation proposed by the invention is provided stable and can by mesoporous carbon
Conductive carrier has big specific surface area；Simultaneously because the confinement in mesoporous carbon duct acts on, elemental metals particle size is equal
One, crystallization degree can be controlled by maturing temperature and time, and tenor is adjustable between 1 ~ 70 wt%.
A kind of high-dispersion nano metal simple-substance/carbon composite controllable method for preparing proposed by the present invention, specific steps are such as
Under:
(1) synthesis has the order mesoporous carbon powder material of high-ratio surface；
(2) solution being configured by oxidant, the order mesoporous carbon powder material obtained with step (1) is mixed, 30~
Under 120 DEG C of water-baths, stir 0.5~24 hour；Cooling, filtering；It is dried in vacuo at 60 DEG C, obtains the mesoporous carbon materials of surface oxidation
Material；
(3) meso-porous carbon material for the surface oxidation for obtaining step (2) disperses in ethanol；It is simultaneously that metal precursor is molten
Solution is configured to the solution of 20 wt% in ethanol；Then both the above solution is mixed, stirring, metal precursor is made to be impregnated into Jie
In the carbon material duct of hole, until ethyl alcohol volatilization is dry in draught cupboard；The meso-porous carbon material for being filled with metal precursor that will be obtained
Be put into cuvette, cuvette is placed in the polytetrafluoroethylene (PTFE) bottle equipped with 14 wt% ammonia spirits, keep solid sample with
Ammonium hydroxide is not directly contacted with, and is handled 3 hours for 60 DEG C after sealing；It can dissolve impurity with water and ethanol washing, filtering removal sample surfaces,
Obtain loading the meso-porous carbon material of the metal hydroxides；
(4) meso-porous carbon material for the metal hydroxides that step (3) obtains is put into tube furnace, H2/N2High temperature under atmosphere
Roasting, obtains nano metal simple substance/mesoporous carbon composite material.
In the present invention, order mesoporous carbon powder material as described in step (1) are as follows: the FDU series of soft template method synthesis
The CMK's serial (CMK-3, CMK-5) of (FDU-14, FDU-15, FDU-16, FDU-18) or hard template synthesis etc. is a kind of or several
Kind or one of active carbon or carbon nanotube or several.
In the present invention, oxidant described in step (2) is one of nitric acid, hydrogen peroxide, potassium permanganate or ammonium persulfate
Or it is several, the concentration of the oxidant is the acidification of the M sulfuric acid of 0.5~2 M(0.5~2.0).
In the present invention, metal precursor described in step (3) is one kind of ferric nitrate, cobalt nitrate, nickel nitrate；Nano metal
The load capacity of simple substance can by change metal precursor additive amount or by it is secondary or three times perfusion control obtain.
In the present invention, after metal precursor is impregnated into the duct of meso-porous carbon material in step (3), ammonia fumigating need to be used
The hydroxide that steaming is translated into metal is fixed in the duct.
In the present invention, H used in step (4)2/N2It is the nitrogen atmosphere containing 10% hydrogen under atmosphere, high-temperature roasting temperature is
200~600 DEG C, calcining time is 0.5~4 h, controls H2/N2Gas flow rate be 25~200 mL/min, heating rate be 1 °/
min。
In the present invention, the nano metal simple substance/carbon composite specific surface area being prepared is 600~1200 cm3/
G, metal nanoparticle is single zero-valent state simple substance, and is dispersed in mesoporous carbon confinement duct, metal nanoparticle partial size
For 3~8 nm.
Application of the nano metal simple substance/carbon composite that preparation method of the present invention obtains in electro-catalysis reduction,
By taking Zero-valent Iron/carbon composite as an example, working electrode is made in nano zero valence iron/carbon composite, using three-electrode electro Chemical
Method restores the nitrate pollutants in water body by electro-catalysis.
In the present invention, the working electrode is according to Zero-valent Iron/carbon composite: carbon black: being dissolved in N- crassitude
The PVDF(10 g/L of ketone)=80 wt%:10 wt%:10 wt% ratio be uniformly mixed, be coated on nickel foam (cm of 1 cm × 1)
On, the drying 4~8 hours of 40~60 DEG C of baking oven, 120~140 DEG C drying 8~12 hours in vacuum drying oven, under 20 Mpa pressure
Compacting obtains；The dosage for being coated on the composite material on working electrode is 3~5 mg, and platinum electrode is used as to electrode, is saturated calomel
Electrode is reference electrode；Voltage -0.4~-4.0 V reacts 1~24 hour.
In the present invention, initial concentration containing nitrate is 20~500 mg/L in the water body, and electrolyte is sodium chloride, sulphur
One or more of sour sodium, hydrochloric acid or sodium hydroxide, pH value are 2~13.
The present invention, which has the advantages that, to be:
(1) the present invention provides a kind of preparation methods of nano metal simple substance/mesoporous carbon composite material.The preparation method is logical
It crosses using having high-ratio surface, the mesoporous carbon of duct three-dimensional communication passes through rear perfusion metal precursor and ammonia as supporting substrate
The method for changing again hydrogen reducing, it is adjustable compound to obtain high load amount, high degree of dispersion, granular size stable homogeneous, tenor
Material.
(2) this kind of applicating cooperation benefit of the invention using nano zero valence iron/carbon composite as the cathode of electrochemistry, provided
With the advantage of base metal simple substance catalysis reduction and electrochemical reduction, improves the removal to nitrate pollutants in water body and imitate
Rate.
(3) for above-mentioned composite material during electro-catalysis restores nitrate, reactivity is high, to the selectivity of nitrogen
Height, stability is good, not easily to fall off, reduces the generation of secondary pollution.
Detailed description of the invention
Fig. 1 nano zero valence iron/mesoporous carbon composite material transmission electron microscope (TEM) photo, is made by embodiment 2.
Fig. 2 nano zero valence iron/mesoporous carbon composite material electro-catalysis reduction removal nitrate recycling performance, uses reality
8 material of example is applied to obtain.
Specific embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
The preparation of phenolic resin and surface oxidation ordered mesoporous carbon material: first by 12.0 g phenol in 40~42 DEG C of water-baths
Middle melting, be added 2.52 g 20%(mass percentage concentrations) NaOH aqueous solution, stir 10 minutes, it is molten to add 20.4 g formaldehyde
Liquid (37 wt%), back flow reaction 1 hour, is cooled to room temperature at 70~75 DEG C.PH value of solution is adjusted to neutrality with the HCl of 0.6 M.
The solution system is placed in 45 DEG C of water-baths and is evaporated under reduced pressure 1~2 hour, obtain 14.1 g phenolic resin (molecular weight 200~
500).It is dissolved into 56.2 g dehydrated alcohols, centrifugation removal NaCl crystal is configured to the light brown that mass fraction is 20%
Phenolic resin performed polymer ethanol solution, it is spare.1.6 g nonionic surfactant polyethylene oxide-polypropylene oxide-is poly-
Ethylene oxide triblock copolymer (Pluronic F127) and 1.0 g, 0.2 M HCl are added in 8.0 g ethyl alcohol, at 40 DEG C
Lower stirring obtains clear solution in l hours.Then the phenolic resin of 20 wt% of 2.08 g tetraethyl orthosilicates and 5.0 g is added
Performed polymer ethanol solution, and continue stirring 2 hours.Uniformly mixed yellow solution is transferred in glass culture dish, room temperature
Lower placement is volatilized 8 hours, cooling through 100 DEG C of dryings.Obtained orange-yellow thin-film material is scraped from culture dish, is suitably ground
After mill, 900 DEG C are heated to 2 DEG C/min in a nitrogen atmosphere and is kept for 2 hours.Obtained black powder is immersed in excess
10 wt% HF solution in, be stirred overnight, remove silica component, be filtered, washed and dried it is dry after obtain high-ratio surface
Powder meso-porous carbon material.Then 1.0 M H are configured2SO41 M nitric acid solution of acidification mixes obtained meso-porous carbon material simultaneously
Stirring, stirring in water bath 6 hours at 30 DEG C, filtering.It is dried in vacuo at 60 DEG C, finally obtains the powder mesoporous carbon of surface oxidation
Material.
Embodiment 2
The preparation of the loaded mesoporous carbon material of Zero-valent Iron: the meso-porous carbon material of 0.6 g surface oxidation is dispersed with stirring in 8.0 g
In ethyl alcohol；Simultaneously by 0.9 g Fe (NO3)3·9H2O dissolution is configured to the solution that mass fraction is 20 wt% in ethanol, and adds
Enter 0.5 mL, 0.2 M HCl and inhibits Fe (NO3)3·9H2The hydrolysis of O.The solution dissolved is added to the alcoholic dispersion of carbon
System, continues to stir, until ethyl alcohol volatilization is dry in draught cupboard.Obtained composite material is put into cuvette, glass tube is set
In the polytetrafluoroethylene (PTFE) bottle equipped with 14 wt% ammonia spirits, sample is kept to be not directly contacted with ammonium hydroxide, 60 DEG C of processing 3 after sealing
Hour, it is cooling, it can dissolve impurity with water and ethanol washing, filtering removal sample surfaces, obtain load Fe (OH)3Mesoporous carbon materials
Material.The composite material is put into 60 DEG C of dryings of vacuum drying oven, places into tube furnace, pure H2/N2The lower 400 DEG C of roastings 2 of (1:10) atmosphere
Hour, finally obtain Zero-valent Iron/mesoporous carbon composite material (resulting materials transmission electron microscope is shown in Fig. 1).
Embodiment 3
The preparation of the loaded mesoporous carbon material of cobalt: preparation method such as embodiment 2, except that being added in material preparation process
1.0 g Co(NO3)3·9H2O dissolution is configured to the solution that mass fraction is 20 wt% in ethanol
Embodiment 4
Electro-catalytic process removes nitrate: working electrode is made in nano zero valence iron/mesoporous carbon composite material first.It will answer
Condensation material, carbon black and the PVDF(10 g/L for being dissolved in N-Methyl pyrrolidone) by the mass ratio of 8:1:1 it is thoroughly mixed into black
Pulpous state is coated in nickel foam (cm of 1 cm × 1), is put into the drying 5 hours of 40 DEG C of baking oven, places into vacuum drying oven and does for 120 DEG C
It dry 8 hours, is suppressed 2 minutes under 20 Mpa pressure, obtains working electrode piece.About 3 mg/cm of the material being coated on electrode2.Platinum
Electrode is used as to electrode, and saturated calomel electrode is reference electrode, using three-electrode method, handles the waste water containing nitrate.Water distribution
For 100 mg/L nitrate nitrogens, 0.02 mol/L sodium chloride.Electrochemistry denitration reaction is carried out under -1.3 V voltages, is reacted 24 hours
Afterwards, the NO in solution is detected3 -、NO2 -And NH4 +, removal rate, the N of nitrate can be calculated2Conversion ratio and unit mass are compound
The processing capacity (the results are shown in Table 1) of material.
The preparation of 5 nano zero valence irons of embodiment/carbon composite and using the composite material as electrode catalyst restore remove
The method of nitrate such as embodiment 1,2,4 in water except that in material preparation process hydrogen maturing temperature be 600 DEG C, roasting
It burns the time 1 hour.
Embodiment 6
The preparation of nano zero valence iron/carbon composite and using the composite material as electrode catalyst reduction go water removal in nitric acid
The method of salt such as embodiment 1,2,4 except that in material preparation process iron load capacity be embodiment 2 in one third,
That is 0.3 g Fe (NO3)3·9H2O dissolution is configured to the solution that mass fraction is 10 wt% in ethanol.
Embodiment 7
The preparation of nano zero valence iron/carbon composite and using the composite material as electrode catalyst reduction go water removal in nitric acid
The method of salt such as embodiment 1,2,4 is except that removing water distribution during nitrate is 50 mg/L nitrate nitrogens.
Embodiment 8
The preparation of nano zero valence iron/carbon composite and using the composite material as electrode catalyst reduction go water removal in nitric acid
The method of salt such as embodiment 1,2,4 reuses same working electrode piece, electrolysis 4 except that during removal nitrate
It is secondary with obtain be recycled performance；Water distribution is 50 mg/L nitrate nitrogen (see figure 2)s during removing nitrate.
Table 1 be prepared in embodiment 4-7 the removal of nano zero valence iron/carbon composite electrochemical reduction nitrate effect
Rate, N2Selectivity and its unit mass remove capacity.
Table 1
| Embodiment | Removal rate (%) | N2Selectivity (%) | It removes capacity (mg/g) |
| Embodiment 4 | 30.5 | 85 | 435 |
| Embodiment 5 | 33.5 | 82 | 340 |
| Embodiment 6 | 16.8 | 65 | 64 |
| Embodiment 7 | 29.5 | 75 | 235 |
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (7)
1. a kind of high-dispersion nano metal simple-substance/carbon composite controllable method for preparing, it is characterised in that specific step is as follows:
(1) synthesis has the order mesoporous carbon powder material of high-ratio surface；
(2) solution being configured by oxidant, the order mesoporous carbon powder material obtained with step (1) is mixed, and 30~120 DEG C
Under water-bath, stir 0.5~24 hour；Cooling, filtering；It is dried in vacuo at 60 DEG C, obtains the meso-porous carbon material of surface oxidation；
(3) meso-porous carbon material for the surface oxidation for obtaining step (2) disperses in ethanol；
(4) metal precursor dissolution is configured to the solution of 20 wt% in ethanol；
(5) solution for obtaining step (3) and step (4) is mixed, is stirred, and metal precursor is made to be impregnated into meso-porous carbon material duct
In, until ethyl alcohol volatilization is dry in draught cupboard, obtain the meso-porous carbon material for being filled with metal precursor；The metal precursor
It is one kind of ferric nitrate, cobalt nitrate, nickel nitrate；The load capacity of nano metal simple substance by change metal precursor additive amount or
Person by it is secondary or three times perfusion control obtain；
(6) meso-porous carbon material for being filled with metal precursor that step (5) obtains is put into cuvette, cuvette is placed in
In polytetrafluoroethylene (PTFE) bottle equipped with 14 wt% ammonia spirits, solid sample is kept to be not directly contacted with ammonium hydroxide, after sealing at 60 DEG C
Reason 3 hours；It can dissolve impurity with water and ethanol washing, filtering removal sample surfaces, obtain Jie for loading the metal hydroxides
Hole carbon material；
(7) meso-porous carbon material for the metal hydroxides that step (6) obtains is put into tube furnace, H2/N2High temperature roasts under atmosphere
It burns, obtains nano metal simple substance/mesoporous carbon composite material；H used2/N2It is the nitrogen atmosphere containing 10% hydrogen, high temperature roasting under atmosphere
Burning temperature is 200~600 DEG C, and calcining time is 0.5~4 h, controls H2/N2Gas flow rate is 25~200 mL/min, heating speed
Rate is 1 °/min.
2. preparation method according to claim 1, it is characterised in that: order mesoporous carbon dust material as described in step (1)
Material are as follows: the one or several kinds or active carbon or carbon of the CMK series of the FDU series or hard template synthesis of soft template method synthesis are received
One of mitron is several.
3. preparation method according to claim 1, it is characterised in that: oxidant described in step (2) is nitric acid, dioxygen
One of water, potassium permanganate or ammonium persulfate are several, and the concentration of the oxidant is 0.5~2 M.
4. preparation method according to claim 1, it is characterised in that: the nano metal simple substance/carbon composite wood being prepared
The specific surface area of material is 600~1200 m2 / g, metal nanoparticle is single zero-valent state simple substance, and is dispersed in mesoporous carbon
In confinement duct, metal nanoparticle partial size is 3~8 nm.
5. a kind of nano metal that preparation method as described in claim 1 obtains simple substance/carbon composite is in electro-catalysis reduction
Application, it is characterised in that: working electrode is made in Nanoscale Iron/carbon composite, using three-electrode electro Chemical method, passes through electricity
Nitrate pollutants in catalysis reduction water body.
6. application according to claim 5, it is characterised in that: the working electrode is according to Nanoscale Iron/carbon composite:
Carbon black: the ratio for being dissolved in the 10 wt%:10 wt%:10 of g/L PVDF=80 wt% of N-Methyl pyrrolidone is uniformly mixed, and is applied
It is distributed in the nickel foam of the cm of 1 cm × 1, the drying 4~8 hours of 40~60 DEG C of baking oven, 120~140 DEG C of dryings 8 in vacuum drying oven~
It 12 hours, is made in the pushing of 20 Mpa pressure；The dosage for being coated on the composite material on working electrode is 3~5 mg, platinum electricity
Pole is used as to electrode, and saturated calomel electrode is reference electrode；Voltage -0.4~-4.0 V reacts 1~24 hour.
7. application according to claim 6, it is characterised in that: in the water body initial concentration containing nitrate be 20~
500 mg/L, electrolyte are one or more of sodium chloride, sodium sulphate, hydrochloric acid or sodium hydroxide, and pH value is 2~13.
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| CN110280300A (en) * | 2019-06-13 | 2019-09-27 | 中国科学技术大学 | A kind of preparation method and application loading Mn oxide ordered mesoporous carbon composite material |
| CN110237847B (en) * | 2019-07-22 | 2021-07-23 | 清华大学 | Electrocatalyst, electrode, and preparation method and application thereof |
| CN111170308A (en) * | 2020-01-19 | 2020-05-19 | 贵州中医药大学 | Method for preparing spherical hydrophilic nano mesoporous carbon material by chitosan-F127 binary system |
| CN112452327B (en) * | 2020-11-25 | 2021-12-21 | 同济大学 | Iron-based double-layer mesoporous silicon-carbon microsphere nano composite material and preparation method and application thereof |
| CN113083308B (en) * | 2021-04-12 | 2021-11-05 | 中国矿业大学 | Application of nickel-based catalyst with high specific surface area and hydrophilic activated carbon as carrier in aspect of catalytic hydro-hydrolysis |
| CN113233551B (en) * | 2021-05-20 | 2022-07-01 | 燕山大学 | Preparation method of catalytic reduction nitrate electrode and resource utilization technology thereof |
| CN116040752A (en) * | 2022-10-18 | 2023-05-02 | 青岛农业大学 | Preparation method and application of biochar electrode |
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