CN110496619A - CuH catalyst, CuH derivative catalyst, preparation method and application - Google Patents
CuH catalyst, CuH derivative catalyst, preparation method and application Download PDFInfo
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- CN110496619A CN110496619A CN201910851306.0A CN201910851306A CN110496619A CN 110496619 A CN110496619 A CN 110496619A CN 201910851306 A CN201910851306 A CN 201910851306A CN 110496619 A CN110496619 A CN 110496619A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 175
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 238000009795 derivation Methods 0.000 claims abstract description 70
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910000085 borane Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 230000005518 electrochemistry Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims description 76
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 9
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 238000001548 drop coating Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 claims description 3
- ZDQWVKDDJDIVAL-UHFFFAOYSA-N catecholborane Chemical compound C1=CC=C2O[B]OC2=C1 ZDQWVKDDJDIVAL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 3
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 claims description 3
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- -1 borane dimethylsulfide ether complexes Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- KHYAFFAGZNCWPT-UHFFFAOYSA-N boron;n,n-diethylaniline Chemical compound [B].CCN(CC)C1=CC=CC=C1 KHYAFFAGZNCWPT-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000002269 spontaneous effect Effects 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/72—Copper
-
- B01J35/33—
-
- B01J35/40—
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Abstract
The present invention provides a kind of CuH catalyst, CuH derivative catalyst, preparation method and application; with borane complex etc. for reducing agent; CuH catalyst is prepared using liquid chemical method; the CuH catalyst that particle diameter distribution is uniform, crystal phase is purer can be prepared under -20 DEG C~80 DEG C, condition of normal pressure; preparation method is simple, and is suitble to large-scale production；The CuH catalyst of preparation has coarse active surface, in air or oxygen can spontaneous derivation be the different Cu base crystal phase catalyst of series, process is simple, without the regulation Cu base catalyst crystalline phases structure such as many and diverse surface plasma processing and heat treatment；The Cu obtained by CuH catalyst derivation2O/CuO multiphase catalyst shows excellent electrochemistry CO2Reducing property, C2H4Selectivity, can be realized technical grade current density electrolysis and catalytic stability at more carbon products selectivity；Cu base catalyst electro-catalysis CO can be achieved in the present invention2Reduction preparation C2H4Equal C2+The industrial applications of chemicals.
Description
Technical field
The invention belongs to industrial electro catalytic field, it is related to a kind of CuH catalyst, CuH derivative catalyst, preparation method and answers
With.
Background technique
Electrochemistry CO2Reduction can utilize renewable and more than needed electric power resource by CO2It is converted into the fuel and chemistry of high value
Product have become a kind of potential energy conversion and storing technology, while future is expected to realize zero-emission carbon cycle, effectively slow
Greenhouse effects are solved, are had important practical significance.Wherein, C2H4As a kind of CO2Electrochemical reduction product, production industry are
The core of petrochemical industry, in recent years, electrochemistry CO2Reduction preparation C2H4A kind of technology as clean and effective attracts attention.
Cu base catalyst as it is currently the only being capable of electro-catalysis CO2Also original production C2H4Catalyst, but presently, there are preparations
Method is complicated, is not suitable for large-scale production, and that there are selectivity of product is poor, catalytic activity is low and catalytic stability is poor etc. many asks
Topic.Although improving CO to a certain extent by the methods of scale topography regulation, state of oxidation regulation2Also original production C2H4's
Selectivity, but still it is not able to achieve C stable under technical grade electric current2H4Production.
Therefore, develop a kind of novel Cu base catalyst, with provide preparation method is simple, be suitble to large-scale production and preparation,
Stable, efficient catalyst, to be catalyzed reduction CO2, improve product C2H4Selectivity, realize electrochemistry CO2Restore C processed2H4
Equal C2+The industrialization and scale application of chemicals, are necessary.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of CuH catalyst, CuH are derivative
Catalyst, preparation method and application, it is above-mentioned a series of existing for Cu base catalyst in the prior art for solving the problems, such as.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation method of CuH catalyst, including with
Lower step:
Mantoquita presoma and borane complex are provided, and are dissolved in organic solvent respectively；
The mantoquita presoma and borane complex are reacted under certain condition, generate reaction product；
The reaction product is separated, purified and dried, CuH catalyst is obtained.
Optionally, the mantoquita presoma is selected from copper chloride (CuCl2), stannous chloride (CuCl), copper bromide (CuBr2), iodine
Change copper (CuI), copper nitrate (Cu (NO3)2), copper acetate (Cu (Ac)2), copper sulphate (CuSO4), acetylacetone copper (Cu (acac)2)
In any one or more.
Optionally, the borane complex is selected from borine tert-butylamine, borine tetrahydrofuran complex, borane dimethylsulf iotade
Complex compound, boranepyridine complex compound, catecholborane, frequently which liquor-saturated borine, 2- picoline borine, N, N- diethylaniline boron
Alkane, boron triethyl, any one or more in diethyl (3- pyridine) base borine.
Optionally, the organic solvent is selected from ethyl alcohol, n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl
Sulfoxide, tetrahydrofuran, methanol, benzene, chloroform, any one or more in carbon tetrachloride.
Optionally, the range of the molar ratio of the mantoquita presoma and the borane complex includes 0.25~20,
Wherein, the range of the molar concentration of the mantoquita presoma includes 1mmol/L~1mol/L.
Optionally, the range for generating the reaction temperature of the reaction product includes -20 DEG C~80 DEG C.
Optionally, the reaction condition for generating the reaction product includes one of ultrasound, stirring, standing or a variety of.
Optionally, the reaction atmosphere for generating the reaction product includes one of argon gas, nitrogen and air or a variety of.
Optionally, the step of separation includes using one of suction filtration, centrifugation or a variety of steps for carrying out solid-liquor separation
Suddenly.
Optionally, the step of purification includes the steps that being purified using multiple cleaning solvent dispensing laundry, wherein
The cleaning solvent includes ethyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, tetrahydrofuran, first
Alcohol, benzene, chloroform, any one or more in carbon tetrachloride.
Optionally, the step of the drying includes using one of vacuum, argon gas and nitrogen or a variety of environmental dryings,
In, when dry using vacuum environment, the range of vacuum degree includes 0kPa~100kPa.
The present invention provides a kind of CuH catalyst, and the CuH catalyst prepares the CuH catalyst using any of the above-described
Method prepares.
The present invention provides a kind of preparation method of CuH derivation catalyst, comprising the following steps:
The CuH catalyst is provided；
The CuH catalyst is exposed in air or oxygen, in -20 DEG C~80 DEG C release H2To generate Cu, formed
CuH/Cu multiphase, completely release H2Cu crystal phase is formed afterwards；
Cu crystal phase surface aoxidizes, and forms Cu/Cu2O multiphase continues oxidation and generates Cu2O crystal phase, further
Oxidation forms Cu2O/CuO multiphase.
The present invention provides a kind of CuH derivation catalyst, and the CuH derivation catalyst prepares the CuH derivation using above-mentioned
The method of catalyst prepares.
The present invention provides a kind of application of CuH derivation catalyst, and the CuH derivation catalyst is using described in above-mentioned preparation
The method of CuH derivation catalyst prepares, and the CuH derivation catalyst is applied to electrochemistry CO2Reduction preparation C2+Chemistry
Product.
Optionally, the electrolytic cell includes flow cell channel, and the CuH derivation catalyst is applied to technical grade current density
Electrochemistry CO2Reduction preparation C2+Chemicals, wherein range >=500mAcm of the technical grade current density-2, C2H4Choosing
Selecting property >=50%, more carbon product selectivity >=80%.
Optionally, gas-diffusion electrode use three-decker, wherein middle layer be with 10wt.%~40wt.%PTFE at
The carbon paper of reason is that support is used as gas diffusion layers, and the CuH derivation described in the side drop coating of the middle layer or spraying or spin coating is urged
Agent brushes PTFE hydrophobic layer or adherency PTFE polymer film as Catalytic Layer, in the other side of the middle layer.
As described above, CuH catalyst of the invention, CuH derive catalyst, preparation method and application, with borane complex
For reducing agent, CuH catalyst is prepared using liquid chemical method, particle diameter distribution can be prepared under -20 DEG C~80 DEG C, condition of normal pressure
The CuH catalyst uniform, crystal phase is purer, preparation method is simple, and is suitble to large-scale production；The CuH catalyst of preparation has thick
Rough active surface, in air or oxygen can spontaneous derivation be the different Cu base crystal phase catalyst of series, process is simple, nothing
Need the regulation Cu base catalyst crystalline phases structures such as many and diverse surface plasma processing and heat treatment；It is obtained by CuH catalyst derivation
Cu2O/CuO multiphase catalyst can show fabulous CO when using flow cell channel electrolysis2Reduction activation
Energy, C2H4Selectivity, can be realized 500mAcm at more carbon products selectivity-2Above technical grade current density electrolysis, while energy
Excellent catalytic stability is enough kept, current top standard is reached, is expected to realize Cu base catalyst electro-catalysis CO2Reduction preparation
C2H4Equal C2+The industrial applications of chemicals.
Detailed description of the invention
Fig. 1 is shown as preparing the process flow chart of CuH catalyst in the present invention.
Fig. 2 is shown as preparing the process flow chart of CuH derivation catalyst in the present invention.
Fig. 3 is shown as the SEM figure of the CuH catalyst prepared in example 1.
Fig. 4 is shown as the enlargement ratio SEM figure of the CuH catalyst prepared in example 1.
Fig. 5 is shown as the XRD spectra of the CuH catalyst prepared in example 1 and CuH derivation catalyst.
The side the Cu K X-ray near side (ns) that Fig. 6 is shown as the CuH derivation catalyst prepared in example 1 absorbs XANES spectrogram.
Fig. 7 is shown as the side the Cu K Fourier transformation distal edge fine structure of the CuH derivation catalyst prepared in example 1
EXAFS spectrogram.
Fig. 8 is shown as in example 1 increasing CuCl2The SEM figure of prepared CuH catalyst after one times of amount.
Fig. 9 is shown as the Cu obtained in example 1 by the CuH catalyst derivation prepared2The Cu of O/CuO multiphase catalyst
2p XPS spectrum figure.
Figure 10 is shown as the Cu obtained in example 1 by the CuH catalyst derivation prepared2O/CuO multiphase catalyst
Auger Auger spectrogram.
Figure 11 is shown as the Cu obtained in example 2 by the CuH catalyst derivation prepared2O/CuO multiphase catalyst exists
The faradic efficiency figure of more carbon products is obtained under different KOH concentration of electrolyte and different current densities.
Figure 12 is shown as the Cu obtained in example 2 by the CuH catalyst derivation prepared2O/CuO multiphase catalyst and
Performance comparison figure of the substrate carbon paper material in 3M KOH electrolyte.
Figure 13 is shown as the Cu obtained in example 2 by the CuH catalyst derivation prepared2O/CuO multiphase catalyst exists
In 3M KOH electrolyte and 500mAcm-2Stability test result spectrogram.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Please refer to Fig. 1~Figure 13.It should be noted that diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, only shown in schema then with related component in the present invention rather than package count when according to actual implementation
Mesh, shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can arbitrarily change for one kind, and its
Assembly layout kenel may also be increasingly complex.
Such as Fig. 1, the present embodiment provides a kind of preparation method of CuH catalyst, the present embodiment is reduction with borane complex
Agent, using liquid chemical method prepare CuH catalyst, can under -20 DEG C~80 DEG C, condition of normal pressure, prepare particle diameter distribution it is uniform,
The purer CuH catalyst of crystal phase, preparation method is simple, and is suitble to large-scale production.
As an example, the mantoquita presoma can be selected from copper chloride (CuCl2), stannous chloride (CuCl), copper bromide
(CuBr2), cupric iodide (CuI), copper nitrate (Cu (NO3)2), copper acetate (Cu (Ac)2), copper sulphate (CuSO4), acetylacetone copper
(Cu(acac)2) in any one or more, the mantoquita presoma is selected according to specific needs.
As an example, the borane complex can be selected from borine tert-butylamine, borine tetrahydrofuran complex, borine diformazan
Thioether complex compound, boranepyridine complex compound, catecholborane, frequently which liquor-saturated borine, 2- picoline borine, N, N- diethylaniline
Borine, boron triethyl, any one or more in diethyl (3- pyridine) base borine, can specifically be selected as needed.
As an example, the organic solvent is selected from ethyl alcohol, n,N-Dimethylformamide, n,N-dimethylacetamide, diformazan
Base sulfoxide, tetrahydrofuran, methanol, benzene, chloroform, any one or more in carbon tetrachloride.
As an example, the range of the molar ratio of the mantoquita presoma and the borane complex include 0.25~
20, such as 0.25,5,10,15,20, wherein the range of the molar concentration of the mantoquita presoma includes 1mmol/L~1mol/
L, such as 1mmol/L, 500mmol/L, 1mol/L.
As an example, generate the reaction temperature of the reaction product range include -20 DEG C~80 DEG C, such as -20 DEG C, 0 DEG C,
25 DEG C, 40 DEG C, 80 DEG C etc..
As an example, the reaction condition for generating the reaction product includes one of ultrasound, stirring, standing or a variety of；
The reaction atmosphere for generating the reaction product includes one of argon gas, nitrogen and air or a variety of.
As an example, the step of separation includes using one of suction filtration, centrifugation or a variety of progress solid-liquor separations
Step；The step of purification, includes the steps that being purified using multiple cleaning solvent dispensing laundry, wherein the washing is molten
Agent includes ethyl alcohol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, tetrahydrofuran, methanol, benzene, chlorine
Imitative, any one or more in carbon tetrachloride；The step of the drying include using one of vacuum, argon gas and nitrogen or
A variety of environmental dryings, wherein when dry using vacuum environment, the range of vacuum degree includes 0kPa~100kPa.
The present embodiment also provides a kind of CuH catalyst, and the CuH catalyst is prepared using any of the above-described method.This
Embodiment can prepare the CuH catalyst with coarse active surface, so that the CuH catalyst can in air or oxygen
Spontaneous derivation is the different Cu base crystal phase catalyst of series, and process is simple, at many and diverse surface plasma processing and heat
The regulation Cu base catalyst crystalline phases structure such as reason.
Such as Fig. 2, the present embodiment provides a kind of preparation method of CuH derivation catalyst, the present embodiment is by the CuH for preparing
Catalyst in air or oxygen can spontaneous derivation be the different Cu base crystal phase catalyst of series, preparation method is simple, and its
The Cu of middle acquisition2O/CuO multiphase catalyst shows excellent electrochemistry CO2Reducing property, using flow cell channel electricity
Xie Shi can show fabulous CO2Reduction activation, C2H4Selectivity, can be realized 500mAcm at more carbon products selectivity-2With
On technical grade current density electrolysis, while being able to maintain excellent catalytic stability, reach current top standard, be expected to reality
Existing Cu base catalyst electro-catalysis CO2Reduction preparation C2H4Equal C2+The industrial applications of chemicals.
The present embodiment also provides a kind of CuH derivation catalyst, and the CuH derivation catalyst is catalyzed using the CuH derivation
The preparation method of agent prepares, wherein the CuH derivation catalyst may include be exposed to by the CuH catalyst air or
In oxygen, in -20 DEG C~80 DEG C release H2The Cu generated afterwards is formed by CuH/Cu multiphase；Or it is mixed by the CuH/Cu
Crystal phase discharges H completely2The Cu crystal phase formed afterwards；Or it is aoxidized by Cu crystal phase surface, the Cu/Cu of formation2O multiphase；
Or the Cu/Cu by being formed2O multiphase continues the Cu that oxidation generates2O crystal phase；Or the Cu by generating2O crystal phase, into
One step aoxidizes the Cu to be formed2One of O/CuO multiphase is a variety of.With the Cu in the present embodiment2O/CuO multiphase
As an example, but being not limited to this.
The present embodiment also provides a kind of application of CuH derivation catalyst, and the CuH derivation catalyst includes that above-mentioned CuH spreads out
Change catalyst, and the CuH derivation catalyst is applied to electrochemistry CO2Reduction preparation C2H4Equal C2+Chemicals.In the present embodiment,
The Cu obtained by the CuH catalyst derivation2O/CuO multiphase catalyst can be realized greater than 500mAcm-2Technical grade electricity
Current density electrolysis, while being able to maintain excellent C2H4Selectivity, more carbon product selectivity and catalytic stability, reach current
Top standard is expected to realize Cu base catalyst electro-catalysis CO2Reduction preparation C2H4Equal C2+The industrial applications of chemicals.
As an example, the electrolytic cell includes flow cell channel, it is close that the CuH derivation catalyst is applied to technical grade electric current
The electrochemistry CO of degree2Reduction preparation C2+Chemicals, wherein range >=500mAcm of the technical grade current density-2, C2H4's
Selectivity >=50%, more carbon product selectivity >=80%.
As an example, gas-diffusion electrode uses three-decker, middle layer is to be handled with 10wt.%~40wt.%PTFE
Carbon paper be support be used as gas diffusion layers, the CuH derivation described in the side drop coating of the middle layer or spraying or spin coating catalysis
Agent brushes PTFE hydrophobic layer or adherency PTFE polymer film as Catalytic Layer, in the other side of the middle layer.
Below by way of specific embodiment, to be further detailed:
Embodiment 1
Prepare CuH catalyst and CuH derivation catalyst, the specific steps are as follows:
It accurately weighs 10.871g borine tert-butylamine (86.97g/mol) to be placed in 50mL beaker, it is molten that ethyl alcohol is then added
It solves and is settled in 50mL volumetric flask, obtain the borine tert-butylamine solution of 2.5M.
Accurately weigh the anhydrous CuCl of 134.5mg2(134.5g/mol) is added in 500mL beaker, then measures 200mL ethyl alcohol
It is added, is placed in 25 DEG C of thermostatic ultrasonic dissolutions in 100W Ultrasound Instrument, forms the CuCl of dissolution2Solution.
The CuCl of dissolution is added in borine tert-butylamine solution described in quantitative 2.5mL2In solution, thermostatic ultrasonic is kept
React 2h.
Suspension after above-mentioned reaction is subjected to suction filtration separation, and with 300mL ethyl alcohol dispensing laundry obtained solid in three times.
Products therefrom is then placed in normal-temperature vacuum drying box dry 2h, CuH catalyst can be obtained.Water should be avoided in the process
It is added, strict control reaction and drying temperature.
The CuH catalyst of preparation is placed in and is stored at room temperature, spontaneous derivation is carried out, finally can get stable Cu2O/CuO
Multiphase catalyst.
Such as above-mentioned steps, other parameters are constant, by the CuCl of addition2The amount amount of doubling be 269mg, repeat it is above-mentioned
CuH catalyst is prepared in step.
Related physical characterization is carried out to resulting CuH derivation catalyst after initial resulting CuH catalyst and derivation, such as
Under:
Fig. 3 is the SEM figure of the CuH catalyst of preparation, and as seen from the figure, the partial size of the CuH catalyst prepared is more equal
One, average particle diameter size is in 190nm or so.
Fig. 4 is the expansion multiplying power SEM figure of the CuH catalyst of preparation, as seen from the figure, using borane complex as reducing agent, is adopted
Rough degree with the CuH catalyst of liquid chemical method preparation is larger, therefore, so that CuH catalyst is with coarse
Active surface, at room temperature can spontaneous derivation be the different Cu base crystal phase catalyst of series, process is simple, without many and diverse table
The regulation Cu base catalyst crystalline phases structure such as surface plasma processing and heat treatment.
Fig. 5 be preparation CuH derivation catalyst XRD diagram, as seen from the figure, by the CuH catalyst storage prepared in
At room temperature, can spontaneous derivation at any time at room temperature, final preparation, which is formed, has Cu2The CuH derivation of O/CuO multiphase is urged
Agent.
Fig. 6 be preparation CuH catalyst at room temperature, store one day, the side the Cu K X-ray of CuH derivation catalyst
Near side (ns) absorbs spectrogram (XANES), and wherein near edge structure illustrates that the CuH derivation catalyst is between zeroth order Cu and monovalence Cu
Mixed valence.
Fig. 7 is the side the Cu K Fourier transformation distal edge fine structure spectrogram (EXAFS) of the CuH derivation catalyst of preparation, figure
There are Cu-O and Cu-Cu keys for spectrum display CuH derivation catalyst, disclose the presence of oxidation state and metallic state, wherein Cu-Cu peak intensity
Much smaller than Cu foil Cu-Cu key peak intensity, illustrate that Cu is the low co-ordination state of high activity in the CuH derivation catalyst.
Fig. 8 is with increasing CuCl under the conditions of Fig. 32The SEM figure of prepared CuH catalyst after one times of amount, as seen from the figure, system
The partial size of the standby CuH catalyst obtained is more uniform, and average particle diameter size is in 390nm or so, compared with Fig. 3, illustrates, prepares
The particle size of the CuH catalyst particle ruler of CuH catalyst that increases with the increase of the amount of mantoquita presoma, thus prepare
It is very little to be regulated and controled by regulating and controlling the amount of mantoquita presoma.
Fig. 9 is the Cu obtained by the CuH catalyst derivation prepared2The Cu of O/CuO multiphase catalyst (being determined by XRD)
2p XPS spectrum figure, diagram shows that there are divalent Cu and low price Cu, but the spectrogram can not determine the specific valence state of low price copper.
Figure 10 is the Cu obtained by the CuH catalyst derivation prepared2The Auger (Auger) of O/CuO multiphase catalyst
Spectrogram, main peak is at 570.3eV combination energy, corresponding monovalence Cu, and spectrogram does not show the presence of zeroth order Cu, therefore, in conjunction with Cu
The result of 2p XPS spectrum figure illustrates the Cu that XRD is determined jointly2O/CuO multiphase catalyst is divalent and monovalence mixed valence.
Embodiment 2
Accurately weigh the Cu obtained in 20mg embodiment 1 by CuH catalyst derivation2O/CuO multiphase catalyst, liquid relief
Rifle quantitatively pipettes 0.96mL ethyl alcohol and 0.04mL Nafion solution (5wt.%), is placed in the Ultrasound Instrument of 100W, ultrasonic disperse
60min.Take drop coating mode by the CuH derivation catalyst drop coating in gas-diffusion electrode substrate, naturally dry formation is urged
Change layer, catalysis effective area is 1cm2, catalyst loading 1mgcm-2.Wherein, gas-diffusion electrode substrate middle layer use with
The carbon paper of 20wt.%PTFE processing is support, as gas diffusion layers, the CuH derivation described in the side drop coating of the middle layer
Catalyst brushes PTFE hydrophobic layer or adherency PTFE polymer film as the Catalytic Layer, in the other side of the middle layer.It adopts
With flow cell channel, two Room of anode and cathode is separated using AT-1 anion-exchange membrane (HephasEnergyCo., Ltd.), air chamber
Room import is passed through high-purity CO2Gas uses mass flowmenter control gas flow rate for 20sccm, and gas chamber's outlet access is online
Gas-chromatography, so as to subsequent gas-phase product composition analysis.Anode and cathode electrolyte chamber is pumped into electrolysis by peristaltic pump circulation respectively
Liquid, coutroi velocity 5mlmin-1.Then constant current test is carried out, and analyzes gas-phase product composition.
Figure 11 is the Cu obtained by the CuH catalyst derivation prepared2O/CuO multiphase catalyst is electrolysed in different KOH
Under liquid concentration and different current densities, the faradic efficiency figure of more carbon products.Wherein, as concentration of electrolyte increases, more carbon are produced
Object selectively increases, C2H4Selectivity up to 50%.In 2M KOH electrolyte, ampere grade current electroanalysis, C can be realized2H4Method
Draw efficiency 40% or more, more carbon product faradic efficiencies show high catalytic activity and selectivity 80% or more.
Figure 12 is the Cu obtained by the CuH catalyst derivation prepared2O/CuO multiphase catalyst and substrate carbon paper material
Performance comparison figure in 3M KOH electrolyte.Wherein, even if in the case where more exceeding potential condition, substrate carbon paper material almost without
Catalytic activity, only a small amount of CH4It generates, illustrates base material to the high activity and CO of working electrode2Reduction selectivity does not have tribute
It offers.
Figure 13 is the Cu obtained by the CuH catalyst derivation prepared2O/CuO multiphase catalyst is electrolysed in 3M KOH
In liquid and 500mAcm-2Stability test result spectrogram.Wherein, the Cu that the CuH catalyst derivation of preparation obtains2O/CuO mixing
Crystal phase catalyst can be stable operation 5 hours or more, maintain C2H445% or more, hydrogen faradic efficiency exists faradic efficiency
5% hereinafter, show good application prospect.
In conclusion CuH catalyst of the invention, CuH derive catalyst, preparation method and application, with borane complex
For reducing agent, CuH catalyst is prepared using liquid chemical method, particle diameter distribution can be prepared under -20 DEG C~80 DEG C, condition of normal pressure
The CuH catalyst uniform, crystal phase is purer, preparation method is simple, and is suitble to large-scale production；The CuH catalyst of preparation has thick
Rough active surface, in air or oxygen can spontaneous derivation be the different Cu base crystal phase catalyst of series, process is simple, nothing
Need the regulation Cu base catalyst crystalline phases structures such as many and diverse surface plasma processing and heat treatment；It is obtained by CuH catalyst derivation
Cu2O/CuO multiphase catalyst can show fabulous CO when using flow cell channel electrolysis2Reduction activation
Energy, C2H4Selectivity, can be realized 500mAcm at more carbon products selectivity-2Above technical grade current density electrolysis, while energy
Excellent catalytic stability is enough kept, current top standard is reached, is expected to realize Cu base catalyst electro-catalysis CO2Reduction preparation
C2H4Equal C2+The industrial applications of chemicals.So the present invention effectively overcomes various shortcoming in the prior art and has height
Value of industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (17)
1. a kind of preparation method of CuH catalyst, which comprises the following steps:
Mantoquita presoma and borane complex are provided, and are dissolved in organic solvent respectively；
The mantoquita presoma and borane complex are reacted under certain condition, generate reaction product；
The reaction product is separated, purified and dried, CuH catalyst is obtained.
2. the preparation method of CuH catalyst according to claim 1, it is characterised in that: the mantoquita presoma is selected from chlorine
Change copper (CuCl2), stannous chloride (CuCl), copper bromide (CuBr2), cupric iodide (CuI), copper nitrate (Cu (NO3)2), copper acetate
(Cu(Ac)2), copper sulphate (CuSO4), acetylacetone copper (Cu (acac)2) in any one or more.
3. the preparation method of CuH catalyst according to claim 1, it is characterised in that: the borane complex is selected from boron
Alkane tert-butylamine, borine tetrahydrofuran complex, borane dimethylsulfide ether complexes, boranepyridine complex compound, catecholborane, frequency
Which liquor-saturated borine, 2- picoline borine, N, N- diethylaniline borane, boron triethyl, in diethyl (3- pyridine) base borine
Any one or more.
4. the preparation method of CuH catalyst according to claim 1, it is characterised in that: the organic solvent be selected from ethyl alcohol,
N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, tetrahydrofuran, methanol, benzene, chloroform, in carbon tetrachloride
Any one or more.
5. the preparation method of CuH catalyst according to claim 1, it is characterised in that: the mantoquita presoma with it is described
The range of the molar ratio of borane complex includes 0.25~20, wherein the range of the molar concentration of the mantoquita presoma
Including 1mmol/L~1mol/L.
6. the preparation method of CuH catalyst according to claim 1, it is characterised in that: generate the anti-of the reaction product
The range for answering temperature includes -20 DEG C~80 DEG C.
7. the preparation method of CuH catalyst according to claim 1, it is characterised in that: generate the anti-of the reaction product
Answering condition includes one of ultrasound, stirring, standing or a variety of.
8. the preparation method of CuH catalyst according to claim 1, it is characterised in that: generate the anti-of the reaction product
Answering atmosphere includes one of argon gas, nitrogen and air or a variety of.
9. the preparation method of CuH catalyst according to claim 1, it is characterised in that: include adopting the step of the separation
With one of suction filtration, centrifugation or a variety of the step of carrying out solid-liquor separation.
10. the preparation method of CuH catalyst according to claim 1, it is characterised in that: include adopting the step of the purification
The step of being purified with multiple cleaning solvent dispensing laundry, wherein the cleaning solvent includes ethyl alcohol, N, N- dimethyl formyl
Amine, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, tetrahydrofuran, methanol, benzene, chloroform, in carbon tetrachloride any one or it is more
Kind.
11. the preparation method of CuH catalyst according to claim 1, it is characterised in that: the step of the drying includes adopting
With one of vacuum, argon gas and nitrogen or a variety of environmental dryings, wherein when dry using vacuum environment, the model of vacuum degree
It encloses including 0kPa~100kPa.
12. a kind of CuH catalyst, it is characterised in that: the CuH catalyst is using the preparation of any one of claim 1~11
It obtains.
13. a kind of preparation method of CuH derivation catalyst, which comprises the following steps:
The CuH catalyst prepared by any one of claim 1~11 is provided；
The CuH catalyst is exposed in air or oxygen, in -20 DEG C~80 DEG C release H2To generate Cu, it is mixed to form CuH/Cu
Synthetic phase, completely release H2Cu crystal phase is formed afterwards；
Cu crystal phase surface aoxidizes, and forms Cu/Cu2O multiphase continues oxidation and generates Cu2O crystal phase further aoxidizes
Form Cu2O/CuO multiphase.
14. a kind of CuH derivation catalyst, it is characterised in that: the CuH derivation catalyst is prepared using the method for claim 13
It obtains.
15. a kind of application of CuH derivation catalyst, it is characterised in that: the CuH derivation catalyst uses the side of claim 13
Method prepares, and the CuH derivation catalyst is applied to electrochemistry CO2Reduction preparation C2+Chemicals.
16. the application of CuH derivation catalyst according to claim 15, it is characterised in that: the electrolytic cell includes flowing
Electrolytic cell, the CuH derivation catalyst are applied to the electrochemistry CO of technical grade current density2Reduction preparation C2+Chemicals, wherein
Range >=500mAcm of the technical grade current density-2, C2H4Selectivity >=50%, more carbon products selectivity >=80%.
17. the application of CuH derivation catalyst according to claim 16, it is characterised in that: gas-diffusion electrode uses three
Layer structure, wherein it is support as gas diffusion layers that middle layer, which is using the carbon paper that 10wt.%~40wt.%PTFE is handled, in institute
CuH derivation catalyst described in the side drop coating or spraying or spin coating of middle layer is stated as Catalytic Layer, in the another of the middle layer
Side brush applies PTFE hydrophobic layer or adherency PTFE polymer film.
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| CN113862715A (en) * | 2021-07-28 | 2021-12-31 | 王荔 | Multivalent copper nano material, preparation method thereof and application of multivalent copper nano material as electrocatalyst in carbon capture technology |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994015988A1 (en) * | 1992-12-31 | 1994-07-21 | Shell Oil Company | Copper hydrides as co-catalysts for olefin polymerization |
| CN101797495A (en) * | 2010-03-25 | 2010-08-11 | 中国科学技术大学 | Organic dye adsorbent namely gold doped cuprous oxide and preparation method thereof |
| DE102008064682A1 (en) * | 2008-10-06 | 2010-12-16 | Alexander Dr. Yakushev | Anionic borane polymer, as well as its use and preparation |
| CN102655889A (en) * | 2009-12-18 | 2012-09-05 | 艾斯特勒科技公司 | Medical device for short time use with quickly releasable antibacterial agent |
| CN104230778A (en) * | 2014-07-14 | 2014-12-24 | 大连大学 | Method for synthesizing beta-alkyloxoacyl-gamma-alkyl-N-alkyl-gamma-butyrolactam |
| CN108495836A (en) * | 2016-01-28 | 2018-09-04 | 伊士曼化工公司 | N-butanal single stage is converted to 2- ethyl hexanals |
| CN109999806A (en) * | 2019-04-02 | 2019-07-12 | 河南师范大学 | It is a kind of for being catalyzed the preparation method of the monometallic nanometer copper catalyst of ammonia borane hydrolysis dehydrogenation |
-
2019
- 2019-09-10 CN CN201910851306.0A patent/CN110496619B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994015988A1 (en) * | 1992-12-31 | 1994-07-21 | Shell Oil Company | Copper hydrides as co-catalysts for olefin polymerization |
| DE102008064682A1 (en) * | 2008-10-06 | 2010-12-16 | Alexander Dr. Yakushev | Anionic borane polymer, as well as its use and preparation |
| CN102655889A (en) * | 2009-12-18 | 2012-09-05 | 艾斯特勒科技公司 | Medical device for short time use with quickly releasable antibacterial agent |
| CN101797495A (en) * | 2010-03-25 | 2010-08-11 | 中国科学技术大学 | Organic dye adsorbent namely gold doped cuprous oxide and preparation method thereof |
| CN104230778A (en) * | 2014-07-14 | 2014-12-24 | 大连大学 | Method for synthesizing beta-alkyloxoacyl-gamma-alkyl-N-alkyl-gamma-butyrolactam |
| CN108495836A (en) * | 2016-01-28 | 2018-09-04 | 伊士曼化工公司 | N-butanal single stage is converted to 2- ethyl hexanals |
| CN109999806A (en) * | 2019-04-02 | 2019-07-12 | 河南师范大学 | It is a kind of for being catalyzed the preparation method of the monometallic nanometer copper catalyst of ammonia borane hydrolysis dehydrogenation |
Non-Patent Citations (11)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113862715A (en) * | 2021-07-28 | 2021-12-31 | 王荔 | Multivalent copper nano material, preparation method thereof and application of multivalent copper nano material as electrocatalyst in carbon capture technology |
| CN113862715B (en) * | 2021-07-28 | 2023-10-03 | 王荔 | Multivalent copper nanomaterial, preparation method thereof and application of multivalent copper nanomaterial serving as electrocatalyst in carbon capture technology |
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