CN116328771A - Preparation method for preparing carbon-loaded monoatomic material by microwave-assisted heating - Google Patents
Preparation method for preparing carbon-loaded monoatomic material by microwave-assisted heating Download PDFInfo
- Publication number
- CN116328771A CN116328771A CN202310297995.1A CN202310297995A CN116328771A CN 116328771 A CN116328771 A CN 116328771A CN 202310297995 A CN202310297995 A CN 202310297995A CN 116328771 A CN116328771 A CN 116328771A
- Authority
- CN
- China
- Prior art keywords
- chloride
- microwave
- carbon
- oxide
- carbonate
- 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.)
- Pending
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 120
- 239000002243 precursor Substances 0.000 claims abstract description 66
- 239000011592 zinc chloride Substances 0.000 claims abstract description 60
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 60
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 26
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000001103 potassium chloride Substances 0.000 claims abstract description 23
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 23
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 13
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims abstract description 13
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001942 caesium oxide Inorganic materials 0.000 claims abstract description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 13
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 13
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 13
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims abstract description 13
- 229940102127 rubidium chloride Drugs 0.000 claims abstract description 13
- 229910001952 rubidium oxide Inorganic materials 0.000 claims abstract description 13
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 13
- 239000002250 absorbent Substances 0.000 claims abstract description 12
- 230000002745 absorbent Effects 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013256 coordination polymer Substances 0.000 claims description 8
- 229920001795 coordination polymer Polymers 0.000 claims description 8
- 239000013310 covalent-organic framework Substances 0.000 claims description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- -1 metalloporphyrin Chemical compound 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 5
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000554 ionomer Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 4
- 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 description 4
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 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 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000001746 carotenes Chemical class 0.000 claims description 4
- 235000005473 carotenes Nutrition 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 235000001727 glucose Nutrition 0.000 claims description 4
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229920000831 ionic polymer Polymers 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 53
- 239000000203 mixture Substances 0.000 description 19
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910003298 Ni-Ni Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
-
- 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
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides application of an accelerator in preparing a carbon-loaded monoatomic material by a microwave heating method; the promoter comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate. The invention adopts a specific accelerator to prepare the carbon-carried monoatomic material by a microwave heating method, and further adds a microwave absorbent zinc chloride to fully pyrolyze an organic precursor with poor microwave absorption capability under microwaves to obtain the highly carbonized carbon-carried metal monoatomic material. The invention adopts zinc chloride as a microwave absorber to absorb microwave energy for heating, and the accelerator is used for enhancing the microwave absorbing capacity of the zinc chloride, so that the microwave heating temperature is greatly improved, the full pyrolysis of the organic precursor is realized, and the addition of the accelerator not only greatly enhances the microwave heating capacity of the organic precursor, but also has the advantages of low cost and easy removal after heating.
Description
Technical Field
The invention belongs to the technical field of preparation of carbon-supported monoatomic materials, relates to application of an accelerator in preparation of carbon-supported monoatomic materials by a microwave heating method and a preparation method of the carbon-supported monoatomic materials, and particularly relates to a preparation method of the carbon-supported monoatomic materials by microwave-assisted heating.
Background
Carbon-supported monoatomic materials have attracted great attention in the fields of catalysis, optoelectronics and the like due to their excellent conductivity, ultrahigh stability and abundant anchor sites. However, the conventional pyrolysis method for constructing a carbon-supported monoatomic material is not only time-consuming, but also results in high waste of energy and time because it requires long-time heating. The microwave heating has low energy consumption and short time consumption, and can effectively solve the problem of traditional heating.
However, the microwave-assisted heating reported so far is mainly focused on carbon materials because it can efficiently absorb the energy of microwaves. However, most organic precursors have poor microwave absorption capability, which greatly limits the further application of microwave-assisted heating in the preparation of carbon-supported monoatomic materials.
Therefore, how to find a more suitable way, further widen the raw materials for preparing the carbon-supported monoatomic material by microwave-assisted heating, solve the above problems in the prior art, and construct the carbon-supported monoatomic material from the direction of the organic precursor, still need to be explored, and are one of the focuses of attention of a great deal of researchers with prospective in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an application of an accelerator in preparing a carbon-supported monoatomic material by a microwave heating method and a preparation method of the carbon-supported monoatomic material, in particular a preparation method of the carbon-supported monoatomic material by microwave-assisted heating. The preparation method provided by the invention enhances the wave absorbing capacity of the raw materials, greatly improves the microwave heating temperature, and realizes the full pyrolysis of the organic precursor, so that the carbon-loaded monoatomic material can be prepared by taking the organic precursor as a carbon source, and the preparation method has the advantages of simple synthesis steps and mild conditions, is suitable for large-scale production popularization and application, and has good practical prospect.
The invention provides application of an accelerator in preparing a carbon-loaded monoatomic material by a microwave heating method;
the promoter comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
Preferably, the application is specifically the application of the accelerator and the zinc chloride in preparing the carbon-loaded monoatomic material by a microwave heating method;
the mass ratio of the zinc chloride to the accelerator is 1: (0.2-1.2);
the raw materials of the microwave heating method comprise organic precursors.
Preferably, the organic precursor includes an organic precursor containing a metal element;
the organic precursor comprises one or more of MOFs, COFs, metal-organic complexes, metal-organic coordination polymers and ionic polymers;
the zinc chloride is a microwave absorbent;
the raw materials of the microwave heating method also comprise a nitrogen source and/or a carbon source.
The invention provides a preparation method of a carbon-supported monoatomic material, which comprises the following steps:
1) Mixing an organic precursor, zinc chloride and an accelerator, heating by microwaves, and washing to obtain the carbon-loaded monoatomic material.
Preferably, the organic precursor includes an organic precursor containing a metal element;
the promoter comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate;
the mass ratio of the organic precursor to the zinc chloride is 1: (1.5-8);
the carbon-supported metal monoatomic material is a highly carbonized carbon-supported metal monoatomic material.
Preferably, the organic precursor comprises one or more of MOFs, COFs, metal-organic complexes, metal-organic coordination polymers, and ionic polymers;
the mass ratio of the organic precursor to the accelerator is 1: (0.2-8);
the mass ratio of the zinc chloride to the accelerator is 1: (0.2-1.2).
Preferably, the organic precursor comprises one or more of Ni-ZIF, ni-MET-6, metal phthalocyanine, metalloporphyrin, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and copper acetylacetonate;
the microwave heating is performed in an air atmosphere;
the zinc chloride is a microwave absorbent;
the metal monoatoms in the carbon-supported metal monoatomic material are connected to carbon through-N-bonds.
Preferably, the raw materials of the microwave heating method further comprise a nitrogen source and/or a carbon source;
the nitrogen source comprises one or more of melamine, dicyandiamide, urea, ammonium fluoride, ammonium chloride, ammonium bromide and ammonium bicarbonate;
the carbon source comprises one or more of ascorbic acid, sucrose, cyclodextrin, glucose, carotene, starch and polyvinylpyrrolidone;
the mass ratio of the organic precursor to the nitrogen source is 1 (2-10);
the mass ratio of the organic precursor to the carbon source is 1 (2-30).
Preferably, the heating power of the microwaves is 400-3000W;
the wave band of the microwave is 300-6000 MHz;
the microwave heating time is 1.5-10 minutes;
the microwave heating further comprises a grinding step and/or a washing step.
Preferably, the ultrasonic washing solution is one or more of water, hydrochloric acid solution, nitric acid solution and sulfuric acid solution;
the pH value of the ultrasonic washing solution is 1-7;
the ultrasonic washing time is 0.5-5 minutes;
the times of ultrasonic washing are 1-5 times.
The invention provides application of an accelerator in preparing a carbon-loaded monoatomic material by a microwave heating method; the promoter comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate. Compared with the prior art, the method adopts the specific accelerator to prepare the carbon-supported monoatomic material by a microwave heating method, and further adds the microwave absorbent zinc chloride to fully pyrolyze the organic precursor with poor microwave absorption capability under microwaves to obtain the highly carbonized carbon-supported metal monoatomic material.
According to the method for obtaining the carbon-supported metal monoatomic material by adding zinc chloride and the accelerator for auxiliary microwave heating, the zinc chloride is used as a microwave absorbent to absorb microwave energy for heating, the auxiliary agent is used for enhancing the microwave absorbing capacity of the zinc chloride, the microwave heating temperature is greatly increased, the full pyrolysis of an organic precursor is realized, and the accelerator is added into the zinc chloride to greatly enhance the microwave heating capacity of the zinc chloride, so that the problems of low graphitization degree, poor conductivity and weak single zinc chloride absorbing capacity of a carbon substrate after carbonization of the precursor when only zinc chloride is added are solved. And compared with the traditional carbon material used as a microwave absorbent, the combination of the zinc chloride and the accelerator has the advantages of low cost and easy removal after heating. Meanwhile, the preparation method has simple synthesis steps and mild conditions, is suitable for large-scale production popularization and application, and has good practical prospect.
Experimental results show that the microwave pyrolysis is insufficient when no accelerator is added, and the carbonization degree of the obtained material is very low. And after the accelerator is added, the material can be fully pyrolyzed to obtain the carbon-loaded monoatomic material with high graphitization degree.
Drawings
FIG. 1 is a schematic diagram of a synthetic route of a precursor Ni-ZIF-8;
FIG. 2 is a powder X-ray diffraction chart of the synthesized Ni-ZIF-8 of example 1 of the present invention;
FIG. 3 is Ni 1 -N-C-50 carbon supportSchematic of the synthetic route of the monoatomic catalyst;
FIG. 4 is a diagram of Ni synthesized in example 1 of the present invention 1 -N-C-50、Ni 1 -N-C-15 and Ni 1 -powder X-ray diffraction pattern of N-C-0;
FIG. 5 is a diagram of Ni synthesized in example 1 of the present invention 1 -N-C-50、Ni 1 -N-C-15 and Ni 1 -raman spectrum of N-C-0;
FIG. 6 is a diagram of Ni synthesized in example 1 of the present invention 1 -N-C-50 and Ni 1 N of-N-C-15 2 Sucking the attached drawings;
FIG. 7 is a diagram of Ni synthesized in example 1 of the present invention 1 -N-C-50 and Ni 1 -pore size distribution profile of N-C-15;
FIG. 8 is a diagram of Ni synthesized in example 1 of the present invention 1 -N-C-50 and Ni 1 -fourier transform of N-C-15 expands the X-ray absorbing fine structure.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The raw materials used in the present invention are not particularly limited in purity, and the present invention is preferably analytically pure or a purity which is conventional in the field of preparation of carbon-supported metal monoatomic materials.
All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
All processes of the present invention, the abbreviations of which are conventional in the art, are each well-defined in the art of their relevant use, and the skilled artisan will be able to understand the conventional process steps thereof based on the abbreviations.
The invention provides application of an accelerator in preparing a carbon-loaded monoatomic material by a microwave heating method;
the promoter comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
In the present invention, the promoter includes one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate, and may be lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, or cesium carbonate.
In the invention, the application is particularly preferably the application of the accelerator and the zinc chloride in preparing the carbon-loaded monoatomic material by a microwave heating method.
In the invention, the mass ratio of the zinc chloride to the accelerator is preferably 1: (0.2 to 1.2), more preferably 1: (0.4 to 1.0), more preferably 1: (0.6-0.8).
In the present invention, the raw material of the microwave heating method preferably includes an organic precursor, more preferably an organic precursor containing a metal element, more preferably one or more of MOFs, COFs, metal-organic complexes, metal-organic coordination polymers, ionomers, more preferably MOFs, COFs, metal-organic complexes, metal-organic coordination polymers, or ionomers.
In the present invention, the zinc chloride is preferably a microwave absorber.
In the present invention, the raw material for the microwave heating method preferably further includes a nitrogen source and/or a carbon source.
The invention provides a preparation method of a carbon-supported monoatomic material, which comprises the following steps:
1) Mixing an organic precursor, zinc chloride and an accelerator, heating by microwaves, and washing to obtain the carbon-loaded monoatomic material.
In the present invention, the promoter preferably includes one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate, more preferably lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, or cesium carbonate.
In the present invention, the mass ratio of the organic precursor to zinc chloride is preferably 1: (1.5 to 8), more preferably 1: (3-7), more preferably 1: (4-6).
In the present invention, the carbon-supported metal monoatomic material is preferably a highly carbonized carbon-supported metal monoatomic material.
In the present invention, the organic precursor preferably includes an organic precursor containing a metal element, more preferably one or more of MOFs, COFs, metal-organic complexes, metal-organic coordination polymers, ionomers, more preferably MOFs, COFs, metal-organic complexes, metal-organic coordination polymers, or ionomers. Specifically, the organic precursor preferably includes one or more of Ni-ZIF, ni-MET-6, metal phthalocyanine, metalloporphyrin, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, and copper acetylacetonate, more preferably Ni-ZIF-8, ni-MET-6 (Ni-Zn- (C) 2 N 3 H 2 ) 2 ) Metal phthalocyanine, metalloporphyrin, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate or copper acetylacetonate. Wherein when the organic precursor is one or more of metal phthalocyanine, metalloporphyrin, ferric acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and copper acetylacetonate, the raw material preferably further comprises a nitrogen source and/or a carbon source.
In the present invention, the nitrogen source preferably includes one or more of melamine, dicyandiamide, urea, ammonium fluoride, ammonium chloride, ammonium bromide and ammonium bicarbonate, more preferably melamine, dicyandiamide, urea, ammonium fluoride, ammonium chloride, ammonium bromide or ammonium bicarbonate.
In the present invention, the carbon source preferably includes one or more of ascorbic acid, sucrose, cyclodextrin, glucose, carotene, starch, and polyvinylpyrrolidone, more preferably ascorbic acid, sucrose, cyclodextrin, glucose, carotene, starch, or polyvinylpyrrolidone.
In the present invention, the mass ratio of the organic precursor to the nitrogen source is preferably 1 (2 to 10), more preferably 1 (3 to 9), still more preferably 1 (4 to 8), and still more preferably 1 (4 to 7).
In the present invention, the mass ratio of the organic precursor to the carbon source is preferably 1 (2 to 30), more preferably 1 (5 to 25), and still more preferably 1 (10 to 20).
In the present invention, the mass ratio of the organic precursor to the accelerator is preferably 1: (0.2 to 8), more preferably 1: (1 to 6), more preferably 1: (3-4).
In the invention, the mass ratio of the zinc chloride to the accelerator is preferably 1: (0.2 to 1.2), more preferably 1: (0.4 to 1.0), more preferably 1: (0.6-0.8).
In the present invention, the microwave heating is preferably performed under an air atmosphere.
In the present invention, the zinc chloride is preferably a microwave absorber.
In the present invention, the metal monoatoms in the carbon-supported metal monoatomic material are preferably bonded to carbon through an-N-linkage.
In the present invention, the heating power of the microwave is preferably 400 to 3000W, more preferably 600 to 2000W, and still more preferably 800 to 1600W.
In the present invention, the microwave band is preferably 300 to 6000MHz, more preferably 400 to 1000MHz.
In the present invention, the time of the microwave heating is preferably 1.5 to 10 minutes, more preferably 2 to 8 minutes, and still more preferably 3 to 5 minutes.
In the present invention, the microwave heating further preferably includes a grinding step and/or a washing step, more preferably a grinding step or a washing step.
In the present invention, the ultrasonic-washing solution is preferably one or more of water, hydrochloric acid solution, nitric acid solution and sulfuric acid solution, more preferably water, hydrochloric acid solution, nitric acid solution or sulfuric acid solution.
In the present invention, the pH of the ultrasonic washing solution is preferably 1 to 7, more preferably 2 to 4.
In the present invention, the time of the ultrasonic washing is preferably 0.5 to 5 minutes, more preferably 1 to 4 minutes, and still more preferably 2 to 3 minutes.
In the present invention, the number of times of ultrasonic washing is preferably 1 to 5 times, more preferably 2 to 4 times.
The invention is a complete and refined whole technical proposal, better ensures the structure and composition of the carbon-loaded single-atom material, further improves the wave absorbing capacity of the organic precursor and the stability and the high efficiency of the preparation process, and the preparation method of the carbon-loaded single-atom material specifically comprises the following steps:
by adding the microwave absorbent zinc chloride and the accelerator, the organic precursor with poor microwave absorption capability is fully pyrolyzed under the microwave to obtain the highly carbonized carbon-loaded metal monoatomic material.
Specifically, the promoter is lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate or cesium carbonate.
Specifically, the method for preparing the carbon-loaded monoatomic material by microwave-assisted heating comprises the following specific steps:
and (3) physically mixing the organic precursor with zinc chloride and the accelerator, placing the mixture into an open container, then carrying out microwave heating, taking out and grinding the obtained solid, then carrying out ultrasonic washing in a solution to remove the residual zinc and the accelerator, and finally centrifuging and drying to obtain the carbon-loaded nanomaterial.
Specifically, the mass ratio of the organic precursor to the zinc chloride is 1: (1.5-8).
Specifically, the mass ratio of the organic precursor to the accelerator is 1: (0.2-8).
Specifically, the mass ratio of the zinc chloride to the accelerator is 1: (0.2-1.2).
Specifically, the microwave heating power is 400-3000W.
Specifically, the microwave heating time is 1.5-10 minutes.
Specifically, the ultrasonic washing solution is water, hydrochloric acid solution, nitric acid solution, sulfuric acid solution or two-by-two combination thereof.
Specifically, the pH value of the ultrasonic washing solution is 1-7.
Specifically, the ultrasonic washing time is 0.5-5 minutes.
Specifically, the ultrasonic washing times are 1-5 times.
Further, the invention is realized by the following technical scheme:
and (3) physically mixing the organic precursor with zinc chloride and the accelerator, placing the mixture into an open container, then carrying out microwave heating, taking out and grinding the obtained solid, then carrying out ultrasonic washing in a solution to remove the residual zinc and the accelerator, and finally centrifuging and drying to obtain the carbon-loaded monoatomic material.
Specifically, the promoter is lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate or cesium carbonate; potassium chloride is most preferred.
Specifically, the mass ratio of the organic precursor to the zinc chloride is 1:1.5-8; the optimal mass ratio is 1:2.
Specifically, the mass ratio of the organic precursor to the accelerator is 1:0.2-8; the optimal mass ratio is 1:0.5.
Specifically, the mass ratio of the zinc chloride to the accelerator is 1:0.2-1.2; the optimal mass ratio is 1:0.5.
Specifically, the microwave heating power is 400-3000W; the optimum heating power is 800W.
Specifically, the microwave heating time is 1.5-10 minutes; the optimal microwave heating time is 3 minutes.
Specifically, the ultrasonic washing solution is water, hydrochloric acid solution, nitric acid solution, sulfuric acid solution or two-by-two combination thereof.
Specifically, the pH value of the ultrasonic washing solution is 1-7; the optimum pH is 1.
Specifically, the ultrasonic washing time is 0.5-5 minutes; the optimal time value is 1 minute.
Specifically, the ultrasonic washing times are 1-5 times; the optimal number of times is 2.
The invention provides the application of the accelerator in preparing the carbon-supported monoatomic material by the microwave heating method and the preparation method for preparing the carbon-supported monoatomic material by microwave-assisted heating. The invention adopts a specific accelerator to prepare the carbon-carried monoatomic material by a microwave heating method, and further adds a microwave absorbent zinc chloride to fully pyrolyze an organic precursor with poor microwave absorption capability under microwaves to obtain the highly carbonized carbon-carried metal monoatomic material.
According to the method for obtaining the carbon-supported metal monoatomic material by adding zinc chloride and the accelerator for auxiliary microwave heating, the zinc chloride is used as a microwave absorbent to absorb microwave energy for heating, the auxiliary agent is used for enhancing the microwave absorbing capacity of the zinc chloride, the microwave heating temperature is greatly increased, the full pyrolysis of an organic precursor is realized, and the accelerator is added into the zinc chloride to greatly enhance the microwave heating capacity of the zinc chloride, so that the problems of low graphitization degree, poor conductivity and weak single zinc chloride absorbing capacity of a carbon substrate after carbonization of the precursor when only zinc chloride is added are solved. And compared with the traditional carbon material used as a microwave absorbent, the combination of the zinc chloride and the accelerator has the advantages of low cost and easy removal after heating. Meanwhile, the preparation method has simple synthesis steps and mild conditions, is suitable for large-scale production popularization and application, and has good practical prospect.
Experimental results show that the microwave pyrolysis is insufficient when no accelerator is added, and the carbonization degree of the obtained material is very low. And after the accelerator is added, the material can be fully pyrolyzed to obtain the carbon-loaded monoatomic material with high graphitization degree.
For further explanation of the present invention, the application of the accelerator provided in the present invention in preparing a carbon-supported monoatomic material by a microwave heating method and a preparation method of a carbon-supported monoatomic material will be described in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Microwave-assisted heating synthesis of carbon-loaded single atom by taking Ni-ZIF-8 as precursor
(1) Synthesizing a precursor Ni-ZIF-8:
referring to FIG. 1, FIG. 1 is a schematic diagram of the synthesis route of a precursor Ni-ZIF-8.
Nickel nitrate hexahydrate (1.6 g) and zinc nitrate hexahydrate (0.8 g) were added to 60mL of methanol (solution A). 2-methylimidazole (3.76 g) was dissolved in 60mL of methanol (solution B). Solution B was then added to solution a and the mixture was stirred at room temperature for 12 hours. And washing with ethanol three times, centrifuging, and drying at 60deg.C for 12 hr to obtain Ni-ZIF-8.
The obtained Ni-ZIF-8 was subjected to XRD spectrum measurement, and the results are shown in FIG. 2.
Referring to FIG. 2, FIG. 2 is a powder X-ray diffraction chart of the synthesized Ni-ZIF-8 of example 1 of the present invention.
By comparing the theoretical spectrum of powder XRD with the XRD spectrum of the synthesized Ni-ZIF-8, the successful synthesis of the Ni-ZIF-8 with the established target by the method can be determined.
(2)Ni 1 -synthesis of N-C-50 carbon supported monoatomic catalyst:
referring to FIG. 3, FIG. 3 is Ni 1 -a schematic of the synthetic route of an N-C-50 carbon supported monoatomic catalyst.
120mg of Ni-ZIF-8 was ground with zinc chloride (240 mg) and potassium chloride (60 mg) by using an agate mortar, and the mixture was placed in a microwave tube and placed in a conical flask to be kept vertical. They are further placed in a household microwave oven at 800WMicrowave heating was performed for 3 minutes at power. The mixture obtained after heating was ultrasonically washed in 1M hydrochloric acid for 1 minute and centrifuged, and washing was repeated 1 more time to remove residual zinc chloride and potassium chloride. Finally drying the mixture at 90 ℃ for 12 hours to finally obtain Ni 1 -N-C-50。
(3) Comparative sample Ni 1 -synthesis of N-C-15 monoatomic catalyst:
120mg of Ni-ZIF-8 was ground with zinc chloride (240 mg) and potassium chloride (18 mg) by using an agate mortar, and the mixture was placed in a microwave tube and placed in a conical flask to be kept vertical. They were further placed in a household microwave oven and subjected to microwave heating at 800W for 3 minutes. The mixture obtained after heating was ultrasonically washed in 1M hydrochloric acid for 1 minute and centrifuged, and washing was repeated 1 more time to remove residual zinc chloride and potassium chloride. Finally drying the mixture at 90 ℃ for 12 hours to finally obtain Ni 1 -N-C-15。
(4) No accelerator Ni is added 1 -synthesis of N-C-0 control monoatomic catalyst:
120mg of Ni-ZIF-8 and zinc chloride (240 mg) were ground by using an agate mortar, and the mixture was placed in a microwave tube and placed in an Erlenmeyer flask to be kept upright. They were further placed in a household microwave oven and subjected to microwave heating at 800W for 3 minutes. The mixture obtained after heating was ultrasonically washed in 1M hydrochloric acid for 1 minute and centrifuged, and washing was repeated 1 more time to remove residual zinc chloride and potassium chloride. Finally drying the mixture at 90 ℃ for 12 hours to finally obtain Ni 1 -N-C-0。
For the Ni obtained 1 -N-C-50、Ni 1 -N-C-15、Ni 1 XRD spectra were run on-N-C-0 and the results are shown in FIG. 4.
Referring to FIG. 4, FIG. 4 shows Ni synthesized in example 1 of the present invention 1 -N-C-50、Ni 1 -N-C-15 and Ni 1 -powder X-ray diffraction pattern of N-C-0.
As shown in FIG. 4, ni 1 -N-C-0、Ni 1 -N-C-15 and Ni 1 The intensity of the C (002) and C (101) peaks in the XRD pattern of-N-C-50 increases progressively, which means as the accelerator is advancedAnd the carbonization degree of the material increases and the carbonization temperature increases. While no peaks of metal were found in XRD results.
For the Ni obtained 1 -N-C-50、Ni 1 -N-C-15、Ni 1 Raman spectroscopy was performed on-N-C-0 and the results are shown in fig. 3.
Referring to FIG. 5, FIG. 5 shows Ni synthesized in example 1 of the present invention 1 -N-C-50、Ni 1 -N-C-15 and Ni 1 -raman spectrum of N-C-0.
As shown in FIG. 5, ni 1 The absence of distinct D and G peaks for N-C-0 indicates that the microwave antipyretic material obtained in the absence of the addition of the accelerator has a very low degree of carbonization. While Ni 1 -N-C-50 and Ni 1 N-C-15 has distinct D and G peaks, indicating that the addition of the accelerator significantly increases the degree of carbonization of the material.
For the Ni obtained 1 -N-C-50、Ni 1 N-C-15 Nitrogen adsorption test was performed and the results are shown in FIGS. 6 and 7.
Referring to FIG. 6, FIG. 6 shows Ni synthesized in example 1 of the present invention 1 -N-C-50 and Ni 1 N of-N-C-15 2 The drawing is sucked.
Referring to FIG. 7, FIG. 7 shows Ni synthesized in example 1 of the present invention 1 -N-C-50 and Ni 1 -pore size distribution profile of N-C-15.
As shown in fig. 6 and 7, ni 1 -N-C-50 and Ni 1 N-C-15 has a large specific surface area and a mesoporous structure, indicating that the synthesis method is conducive to obtaining a large specific surface area and a mesoporous structure.
Referring to FIG. 8, FIG. 8 shows Ni synthesized in example 1 of the present invention 1 -N-C-50 and Ni 1 -fourier transform of N-C-15 expands the X-ray absorbing fine structure.
As shown in FIG. 8, ni 1 -N-C-50 and Ni 1 Ni in N-C-15 is N-coordinated and no metallic Ni-Ni bond is present, indicating the Ni obtained 1 -N-C-50 and Ni 1 -N-C-15 is a monoatomic catalyst.
Example 2
Microwave synthesis of carbon-loaded monoatomic material by taking Ni-MET-6 as precursor
0.4g of zinc chloride and 0.075g of nickel nitrate hexahydrate were dissolved in a solvent mixture consisting of 20mL of MF, 20mL of ethanol, 30mL of deionized water, and 10mL of ammonium hydroxide to form solution A. A total of 0.625mL of 1H-1,2, 3-triazole was added dropwise to solution A, immediately followed by the formation of a white product. The suspension was stirred for 2h. The white precipitate obtained was then collected by centrifugation after 3 washes with DMF and ethanol. Finally, the wet powder is dried at 100 ℃ for 24 hours to obtain the Ni-MET-6 precursor.
120mg of Ni-MET-6 precursor was ground with zinc chloride (240 mg) and potassium chloride (60 mg) by using an agate mortar, and then the mixture was put into a microwave tube, and then placed in a conical flask to be kept vertical. They were further placed in a household microwave oven and subjected to microwave heating at 800W for 3 minutes. The mixture obtained after heating was ultrasonically washed in 1M hydrochloric acid for 1 minute and centrifuged, and washing was repeated 1 more time to remove residual zinc chloride and potassium chloride. Finally, drying the mixture at 90 ℃ for 12 hours to finally obtain nickel monoatoms.
Example 3
Microwave synthesis of carbon-loaded single atom by taking nickel phthalocyanine as precursor
10mg of nickel phthalocyanine, 100mg of melamine and 125mg of ascorbic acid are ground and mixed uniformly, 240mg of zinc chloride and 60mg of potassium chloride are added and ground uniformly by using an agate mortar, and then the mixture is put into a microwave tube and placed into a conical flask so as to keep vertical. They were further placed in a household microwave oven and subjected to microwave heating at 800W for 3 minutes. The mixture obtained after heating was ultrasonically washed in 1M hydrochloric acid for 1 minute and centrifuged, and washing was repeated 1 more time to remove residual zinc chloride and potassium chloride. Finally, the mixture is dried at 90 ℃ for 12 hours to finally obtain nickel monoatoms.
The foregoing has outlined the detailed description of the method for preparing a carbon-loaded monoatomic material by microwave-assisted heating, wherein specific examples are provided herein to illustrate the principles and embodiments of the invention and are intended to facilitate an understanding of the method and its core ideas, including the best mode, of practicing the invention, including making and using any device or system, and performing any incorporated methods, by any person skilled in the art. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The application of the accelerator in preparing the carbon-loaded monoatomic material by a microwave heating method;
the promoter comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
2. The use according to claim 1, characterized in that the use is in particular of accelerators and zinc chloride in the preparation of carbon-loaded monoatomic materials by microwave heating;
the mass ratio of the zinc chloride to the accelerator is 1: (0.2-1.2);
the raw materials of the microwave heating method comprise organic precursors.
3. The use according to claim 2, wherein the organic precursor comprises an organic precursor comprising a metal element;
the organic precursor comprises one or more of MOFs, COFs, metal-organic complexes, metal-organic coordination polymers and ionic polymers;
the zinc chloride is a microwave absorbent;
the raw materials of the microwave heating method also comprise a nitrogen source and/or a carbon source.
4. The preparation method of the carbon-supported monoatomic material is characterized by comprising the following steps of:
1) Mixing an organic precursor, zinc chloride and an accelerator, heating by microwaves, and washing to obtain the carbon-loaded monoatomic material.
5. The method according to claim 4, wherein the organic precursor comprises an organic precursor containing a metal element;
the promoter comprises one or more of lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate;
the mass ratio of the organic precursor to the zinc chloride is 1: (1.5-8);
the carbon-supported metal monoatomic material is a highly carbonized carbon-supported metal monoatomic material.
6. The method of claim 1, wherein the organic precursor comprises one or more of MOFs, COFs, metal-organic complexes, metal-organic coordination polymers, ionomers;
the mass ratio of the organic precursor to the accelerator is 1: (0.2-8);
the mass ratio of the zinc chloride to the accelerator is 1: (0.2-1.2).
7. The method of claim 1, wherein the organic precursor comprises one or more of Ni-ZIF, ni-MET-6, metal phthalocyanine, metalloporphyrin, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, and copper acetylacetonate;
the microwave heating is performed in an air atmosphere;
the zinc chloride is a microwave absorbent;
the metal monoatoms in the carbon-supported metal monoatomic material are connected to carbon through-N-bonds.
8. The method according to claim 1, wherein the raw materials of the microwave heating method further comprise a nitrogen source and/or a carbon source;
the nitrogen source comprises one or more of melamine, dicyandiamide, urea, ammonium fluoride, ammonium chloride, ammonium bromide and ammonium bicarbonate;
the carbon source comprises one or more of ascorbic acid, sucrose, cyclodextrin, glucose, carotene, starch and polyvinylpyrrolidone;
the mass ratio of the organic precursor to the nitrogen source is 1 (2-10);
the mass ratio of the organic precursor to the carbon source is 1 (2-30).
9. The method according to claim 1, wherein the heating power of the microwave is 400 to 3000W;
the wave band of the microwave is 300-6000 MHz;
the microwave heating time is 1.5-10 minutes;
the microwave heating further comprises a grinding step and/or a washing step.
10. The method of claim 9, wherein the ultrasonically washed solution is one or more of water, hydrochloric acid solution, nitric acid solution, and sulfuric acid solution;
the pH value of the ultrasonic washing solution is 1-7;
the ultrasonic washing time is 0.5-5 minutes;
the times of ultrasonic washing are 1-5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310297995.1A CN116328771A (en) | 2023-03-23 | 2023-03-23 | Preparation method for preparing carbon-loaded monoatomic material by microwave-assisted heating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310297995.1A CN116328771A (en) | 2023-03-23 | 2023-03-23 | Preparation method for preparing carbon-loaded monoatomic material by microwave-assisted heating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116328771A true CN116328771A (en) | 2023-06-27 |
Family
ID=86885278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310297995.1A Pending CN116328771A (en) | 2023-03-23 | 2023-03-23 | Preparation method for preparing carbon-loaded monoatomic material by microwave-assisted heating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116328771A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431993A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing mesoporous carbon material for electrochemical capacitor by using rice hulls as raw materials |
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| WO2014031368A1 (en) * | 2012-08-21 | 2014-02-27 | Corning Incorporated | Microwave energy-assisted, chemical activation of carbon |
| CN106542509A (en) * | 2016-10-19 | 2017-03-29 | 张家港市东大工业技术研究院 | A kind of efficient method for preparing class Graphene carbonitride |
| CN106744882A (en) * | 2016-12-28 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of quick method for preparing Graphene of microwave radiation technology stirring |
| CN112808288A (en) * | 2019-11-18 | 2021-05-18 | 郑州大学 | Nitrogen-phosphorus or nitrogen-phosphorus-sulfur co-doped carbon-loaded metal monoatomic catalyst and microwave-assisted preparation method thereof |
| CN113353947A (en) * | 2021-06-15 | 2021-09-07 | 江苏大学 | Method for preparing high-activity titanium boride ceramic powder by low-temperature microwave carbothermic reduction |
| CN113952985A (en) * | 2021-07-07 | 2022-01-21 | 中国科学技术大学 | Method for efficiently preparing high-performance MOF-based non-noble metal monatomic composite material under assistance of microwaves, composite material and application |
| US20220029173A1 (en) * | 2020-07-22 | 2022-01-27 | Rutgers, The State University Of New Jersey | Carbon Nanomaterial Supported Single Atom Catalysts and Methods of Preparing Same |
| CN114335573A (en) * | 2021-11-22 | 2022-04-12 | 湖南大学 | Nitrogen-doped porous carbon polyhedron-loaded bimetallic monatomic oxygen reduction catalyst and microwave-assisted preparation method and application thereof |
| KR20220109837A (en) * | 2021-01-29 | 2022-08-05 | 아주대학교산학협력단 | Method for manufacturing activated porous carbon, activated hierarchical porous carbon and electrode for supercapacitor using the same |
-
2023
- 2023-03-23 CN CN202310297995.1A patent/CN116328771A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431993A (en) * | 2011-09-22 | 2012-05-02 | 安徽工业大学 | Method for preparing mesoporous carbon material for electrochemical capacitor by using rice hulls as raw materials |
| WO2014031368A1 (en) * | 2012-08-21 | 2014-02-27 | Corning Incorporated | Microwave energy-assisted, chemical activation of carbon |
| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| CN106542509A (en) * | 2016-10-19 | 2017-03-29 | 张家港市东大工业技术研究院 | A kind of efficient method for preparing class Graphene carbonitride |
| CN106744882A (en) * | 2016-12-28 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of quick method for preparing Graphene of microwave radiation technology stirring |
| CN112808288A (en) * | 2019-11-18 | 2021-05-18 | 郑州大学 | Nitrogen-phosphorus or nitrogen-phosphorus-sulfur co-doped carbon-loaded metal monoatomic catalyst and microwave-assisted preparation method thereof |
| US20220029173A1 (en) * | 2020-07-22 | 2022-01-27 | Rutgers, The State University Of New Jersey | Carbon Nanomaterial Supported Single Atom Catalysts and Methods of Preparing Same |
| KR20220109837A (en) * | 2021-01-29 | 2022-08-05 | 아주대학교산학협력단 | Method for manufacturing activated porous carbon, activated hierarchical porous carbon and electrode for supercapacitor using the same |
| CN113353947A (en) * | 2021-06-15 | 2021-09-07 | 江苏大学 | Method for preparing high-activity titanium boride ceramic powder by low-temperature microwave carbothermic reduction |
| CN113952985A (en) * | 2021-07-07 | 2022-01-21 | 中国科学技术大学 | Method for efficiently preparing high-performance MOF-based non-noble metal monatomic composite material under assistance of microwaves, composite material and application |
| CN114335573A (en) * | 2021-11-22 | 2022-04-12 | 湖南大学 | Nitrogen-doped porous carbon polyhedron-loaded bimetallic monatomic oxygen reduction catalyst and microwave-assisted preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| MING WEN ET AL.: "Microwave-Assisted Rapid Synthesis of MOF-Based Single-Atom Ni Catalyst for CO2 Electroreduction at Ampere-Level Current", 《ANGEW. CHEM. INT. ED.》, vol. 63, 31 January 2024 (2024-01-31), pages 202318338 * |
| XINLONG XU ET AL.: "Solid phase microwave-assisted fabrication of Fe-doped ZIF-8 for single-atom Fe-N-C electrocatalysts on oxygen reduction", 《JOURNAL OF ENERGY CHEMISTRY》, vol. 54, 25 June 2020 (2020-06-25), pages 579 - 586, XP086433018, DOI: 10.1016/j.jechem.2020.06.046 * |
| 彭景东: "微波-熔融盐法快速制备生物炭及其吸附水中Pb(Ⅱ)研究", 万方学术, 23 November 2022 (2022-11-23) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109078649A (en) | A kind of transition metal-nitrogen-doped carbon based composites and preparation method thereof | |
| CN108479777B (en) | Preparation method and application of attapulgite composite photocatalyst | |
| CN113275041B (en) | Preparation of COF-316/CAT-1 composite material and photocatalytic carbon dioxide reduction | |
| CN110124723A (en) | ZnO/g-C3N4Composite photo-catalyst and its preparation method and application | |
| CN111151285B (en) | Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof | |
| CN112973750A (en) | Carbon quantum dot coated metal monoatomic-carbon nitride composite material and preparation method thereof | |
| CN112705207A (en) | Preparation method of adjustable metal monoatomic doped porous carbon and application of adjustable metal monoatomic doped porous carbon in microwave catalysis | |
| CN107651708A (en) | A kind of method that microwave hydrothermal prepares 1T@2H MoS2 | |
| CN114554819B (en) | Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof | |
| CN111944482A (en) | Preparation method of echinoid carbon nanotube-coated Co particle composite wave-absorbing material | |
| CN114195197B (en) | Magnetic porous carbon compound and preparation method and application thereof | |
| CN113769763B (en) | CdS-Au nano-catalyst and preparation method and application thereof | |
| CN102627834A (en) | Preparation method of chitosan modification barium ferrite filling multi-walled carbon nanotube/poly 3-methylthiophene composite wave-absorbing material | |
| CN102139911A (en) | Reaction device and method for preparing nano zinc oxide | |
| Yang et al. | 2D/2D Ti3C2/Bi4O5Br2 nanosheet heterojunction with enhanced visible light photocatalytic activity for NO removal | |
| CN114471711A (en) | Polythiophene-carbon nitride composite photocatalyst and preparation method and application thereof | |
| CN116328771A (en) | Preparation method for preparing carbon-loaded monoatomic material by microwave-assisted heating | |
| CN108940325A (en) | A kind of binary composite semiconductor light-catalyst materials A g2CrO4/ BiOI and its preparation and application | |
| CN106564952B (en) | A kind of method that carbohydrate organic carbon reduction prepares class graphene molybdenum disulfide-graphene composite material | |
| CN114367312B (en) | Ag + -Ag 0 Graphite-phase-doped carbon nitride coupled cobalt oxime molecule composite photocatalyst and preparation method and application thereof | |
| Wang et al. | Solar thermal-activated photocatalysis for hydrogen production and aqueous triethanolamine polymerization | |
| Khan et al. | Mesoporous Prussian Blue as the highly effective and selective catalyst for CO2 conversion into cyclic carbonates under mild conditions | |
| CN110743583A (en) | 0D/2D iron phosphide/cadmium sulfide composite photocatalyst and preparation method and application thereof | |
| CN113694963B (en) | Cobalt-embedded nitrogen-rich porous carbon material/self-assembled nano porphyrin composite photocatalyst, and preparation method and application thereof | |
| CN110629245B (en) | Nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photoelectric reduction of CO2Method of producing a composite material |
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 |