CN116926376A - Cadmium bismuth alloy and preparation method and application thereof - Google Patents
Cadmium bismuth alloy and preparation method and application thereof Download PDFInfo
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- CN116926376A CN116926376A CN202310751358.7A CN202310751358A CN116926376A CN 116926376 A CN116926376 A CN 116926376A CN 202310751358 A CN202310751358 A CN 202310751358A CN 116926376 A CN116926376 A CN 116926376A
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- 229910001152 Bi alloy Inorganic materials 0.000 title claims abstract description 49
- YAMPQRWRFJYHJN-UHFFFAOYSA-N [Cd].[Bi] Chemical compound [Cd].[Bi] YAMPQRWRFJYHJN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006722 reduction reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 26
- 150000001621 bismuth Chemical class 0.000 claims abstract description 26
- 150000001661 cadmium Chemical class 0.000 claims abstract description 25
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 14
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001451 bismuth ion Inorganic materials 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 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
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B3/26—Reduction of carbon dioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a cadmium bismuth alloy and a preparation method and application thereof. The invention provides a cadmium-bismuth alloy, which comprises cadmium and bismuth; the cadmium accounts for 1-10 mol percent of the cadmium-bismuth alloy. The catalyst for generating formate by electro-catalytic reduction of carbon dioxide by using the cadmium bismuth alloy can greatly improve the selectivity of formate. The invention also provides a preparation method of the cadmium bismuth alloy, which comprises the following steps: uniformly dispersing bismuth salt in a first solvent to obtain bismuth salt dispersion liquid; dissolving cadmium salt in a second solvent to obtain a cadmium salt solution; and mixing the bismuth salt dispersion liquid and the cadmium salt solution, and then dripping the mixture into a reducing agent solution to perform a reduction reaction to obtain the cadmium-bismuth alloy. The preparation method provided by the invention has simple steps, is easy to operate, and can be used for industrial production.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a cadmium bismuth alloy and a preparation method and application thereof.
Background
Electrocatalytic carbon dioxide reduction to produce high value products is an effective strategy for reducing carbon emissions and achieving carbon neutralization, formate as a carbon dioxide reduction product has higher economic value and wider industrial application, and liquid formate is easy to separate from the reaction gases. In the process of preparing formate by electrocatalytic carbon dioxide reduction, a catalyst is needed, and most of the existing catalysts are copper-based catalysts, tin-based catalysts or bismuth-based catalysts; the bismuth-based catalyst has higher selectivity for preparing formate through catalytic reduction than tin-based catalyst and copper-based catalyst, but the selectivity of the pure bismuth metal catalyst is only 85.5%, and the selectivity of the existing catalyst for preparing formate through catalytic reduction of carbon dioxide needs to be further improved.
Disclosure of Invention
In view of the above, the invention provides a cadmium-bismuth alloy, a preparation method and application thereof, and the cadmium-bismuth alloy provided by the invention can be used as a catalyst to remarkably improve the selectivity of electrocatalytic carbon dioxide reduction formate.
In order to solve the technical problems, the invention provides a cadmium-bismuth alloy, which comprises cadmium and bismuth; the cadmium accounts for 1-10 mol percent of the cadmium-bismuth alloy.
Preferably, the cadmium accounts for 3-10% of the molar percentage of the cadmium-bismuth alloy.
The invention also provides a preparation method of the cadmium bismuth alloy, which comprises the following steps:
dispersing bismuth salt in a first solvent to obtain bismuth salt dispersion;
dissolving cadmium salt in a second solvent to obtain a cadmium salt solution;
and mixing the bismuth salt dispersion solution and the cadmium salt solution, and then dripping the mixture into a reducing agent solution to perform a reduction reaction to obtain the cadmium-bismuth alloy.
Preferably, the reducing agent solution comprises an aqueous sodium borohydride solution or an aqueous potassium borohydride solution.
Preferably, the bismuth salt comprises bismuth sulfate, bismuth chloride or bismuth nitrate.
Preferably, the cadmium salt includes cadmium sulfate, cadmium chloride, or cadmium nitrate.
Preferably, the temperature of the reduction reaction is-1 ℃;
the time of the reduction reaction is 0.4-0.6 h.
Preferably, the reduction reaction further comprises: and washing the product after the reduction reaction with water and acetone in sequence.
The invention also provides an application of the cadmium bismuth alloy prepared by the technical scheme or the preparation method of the technical scheme as a catalyst.
Preferably, the catalyst is a catalyst for electrocatalytic reduction of carbon dioxide to formate.
The invention provides a cadmium-bismuth alloy, which comprises cadmium and bismuth; the cadmium accounts for 1-10 mol percent of the cadmium-bismuth alloy. The invention improves the catalytic performance of the cadmium-bismuth alloy by limiting the mole percentage content of cadmium in the cadmium-bismuth alloy within the range when the cadmium-bismuth alloy is used as a catalyst; the cadmium bismuth alloy is used as a catalyst for generating formate through electrocatalytic carbon dioxide reduction, so that the selectivity of formate can be greatly improved.
The invention also provides a preparation method of the cadmium bismuth alloy, which comprises the following steps: dispersing bismuth salt in a first solvent to obtain bismuth salt dispersion; dissolving cadmium salt in a second solvent to obtain a cadmium salt solution; and mixing the bismuth salt dispersion liquid and the cadmium salt solution, and then dripping the mixture into a reducing agent solution to perform a reduction reaction to obtain the cadmium-bismuth alloy. The preparation method provided by the invention has simple steps, is easy to operate, and can be used for industrial production.
Detailed Description
The invention provides a cadmium-bismuth alloy, which comprises cadmium and bismuth; the cadmium accounts for 1-10% of the mole percentage of the cadmium-bismuth alloy, preferably 3-10%, and more preferably 3-5%.
The invention limits the mole percent of cadmium in the cadmium-bismuth alloy to the above range, which is beneficial to achieving uniform atomic dispersion level. In the present invention, cadmium is distributed in the cadmium bismuth alloy in the form of monoatoms or clusters.
The invention introduces a small amount of Cd metal into Bi metal to realize that the catalyst material can perform electrocatalytic CO to a large extent 2 High selectivity for formate preparation.
The invention also provides a preparation method of the cadmium bismuth alloy, which comprises the following steps:
dispersing bismuth salt in a first solvent to obtain bismuth salt dispersion;
dissolving cadmium salt in a second solvent to obtain a cadmium salt solution;
and mixing the bismuth salt solution and the cadmium salt solution, and then dripping the mixture into a reducing agent solution to perform a reduction reaction to obtain the cadmium-bismuth alloy.
All materials are commercially available products conventionally in the present invention unless otherwise specified.
The bismuth salt is dispersed in a first solvent to obtain bismuth salt dispersion liquid. In the present invention, the bismuth salt preferably includes bismuth sulfate, bismuth chloride or bismuth nitrate, more preferably bismuth chloride. In the present invention, the first solvent is preferably ethanol or acetone, more preferably ethanol. In the present invention, the ethanol is preferably absolute ethanol. In the present invention, the molar concentration of bismuth element in the bismuth salt dispersion is preferably 0.3mol/L to 0.5mol/L, more preferably 0.4mol/L. In the present invention, the dispersion is preferably performed under ultrasonic conditions, and the power of the ultrasonic wave is preferably 30 to 40KHz, more preferably 35 to 40KHz; the time of the ultrasonic wave is preferably 8 to 12 minutes, more preferably 10 minutes.
The invention dissolves cadmium salt in the second solvent to obtain cadmium salt solution. In the present invention, the second solvent is preferably water or ethanol, more preferably water. In the present invention, the cadmium salt preferably includes cadmium sulfate, cadmium chloride or cadmium nitrate, more preferably cadmium chloride. In the present invention, the molar concentration of the cadmium element in the cadmium salt solution is preferably 0.01 to 0.3mol/L, more preferably 0.06 to 0.08mol/L. The invention has no special requirement on the dissolution, so long as the dissolution is complete.
After bismuth salt dispersion liquid and cadmium salt solution are obtained, the bismuth salt dispersion liquid and the cadmium salt solution are mixed and then added into a reducing agent solution in a dropwise manner, and a reduction reaction is carried out to obtain the cadmium bismuth alloy. In the present invention, the mixing is preferably performed under ultrasonic conditions; the power of the ultrasonic wave is preferably 30-40 KHz, more preferably 35-40 KHz; the time of the ultrasonic wave is preferably 8 to 12 minutes, more preferably 10 minutes.
In the present invention, the reducing agent solution preferably includes an aqueous sodium borohydride solution or an aqueous potassium borohydride solution, more preferably an aqueous sodium borohydride solution. In the present invention, the molar concentration of the sodium borohydride aqueous solution is preferably 4.8 to 5.2mol/L, more preferably 5mol/L. In the present invention, the volume ratio of the bismuth salt dispersion liquid to the cadmium salt solution is preferably 6:1 to 4:1, more preferably 5:1. In the present invention, the volume ratio of the bismuth salt dispersion liquid and the reducing agent solution is preferably 5:3 to 5:2, more preferably 5:2. The invention preferably controls the proportion of cadmium and bismuth in the cadmium-bismuth alloy by controlling the content of bismuth ions and cadmium ions in the mixed solution obtained by mixing. In the present invention, the rate of the dropping is preferably dropping dropwise.
The invention has no special requirement on the mixing, so long as the mixing can be uniform.
In the present invention, the temperature of the reduction reaction is preferably-1 to 1 ℃, more preferably 0 ℃; the time of the reduction reaction is preferably 0.4 to 0.6 hours, more preferably 0.5 hours. The temperature of the reduction reaction is preferably provided by means of an ice bath.
The invention can reduce cadmium ions and bismuth ions to form the cadmium-bismuth alloy through reduction reaction.
In the present invention, the reduction reaction preferably further comprises: carrying out solid-liquid separation on the system after the reduction reaction; and (3) sequentially washing the solid obtained by solid-liquid separation with water and acetone. In the present invention, the solid-liquid separation is preferably centrifugation. The invention has no special requirements on the centrifugation, as long as the solid and the liquid can be separated. In the present invention, the water for washing is preferably deionized water. In the present invention, the water washing serves to remove water-soluble compounds from the remaining reactants; the acetone wash serves to remove compounds dissolved in acetone from the remaining reactants.
The invention also provides an application of the cadmium bismuth alloy prepared by the technical scheme or the preparation method of the technical scheme as a catalyst. In the present invention, the catalyst is preferably a catalyst that electrocatalytic reduction of carbon dioxide to formate. The method for preparing formate by electrocatalytic carbon dioxide reduction has no special requirement, and can be carried out in a conventional mode in the field.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Dispersing 630mg of bismuth chloride in 5mL of ethanol, and performing ultrasonic treatment for 10min under the condition of 40KHz to obtain bismuth chloride dispersion;
4.6mg of cadmium chloride 2/5 hydrate is dissolved in 1mL of water to obtain a cadmium chloride solution;
adding 1mL of cadmium salt solution into 5mL of bismuth salt dispersion liquid, carrying out ultrasonic treatment under the condition of 40KHz for 10min, uniformly mixing, dropwise adding the mixed solution into 2mL of 5mol/L sodium borohydride aqueous solution under the condition of ice bath, reducing for 0.5h, centrifuging a system after reduction reaction, sequentially washing the centrifuged solid with water and acetone to obtain a cadmium bismuth alloy (Cd) with 1mol percent of cadmium 1 Bi 99 )。
Example 2
A cadmium bismuth alloy (Cd) having a cadmium mole percent of 3% was prepared as in example 1 3 Bi 97 ) Except that 14.1mg of cadmium chloride 2/5 hydrate was dissolved in 1mL of water to obtain a cadmium chloride solution.
Example 3
A cadmium bismuth alloy (Cd) having a cadmium mole percent of 5% was prepared as in example 1 5 Bi 95 ) Except that 24mg of cadmium chloride 2/5 hydrate was weighed and dissolved in 1mL of water to obtain a cadmium chloride solution.
Example 4
A cadmium bismuth alloy (Cd) having a cadmium mole percent of 10% was prepared as in example 1 10 Bi 90 ) Except that 50.7mg of cadmium chloride 2/5 hydrate was dissolved in 1mL of water to obtain a cadmium chloride solution.
Comparative example 1
Pure bismuth metal was used as a comparative example.
Comparative example 2
Pure cadmium metal was used as a comparative example.
Comparative example 3
A cadmium bismuth alloy (Cd) having a cadmium mole percent of 30% was prepared as in example 1 30 Bi 70 ) Except that 195.7mg of cadmium chloride 2/5 hydrate was dissolved in 1mL of water to obtain a cadmium chloride solution.
The alloys of examples 1 to 4 and comparative examples 1 to 3 were examined for catalytic performance as catalysts as follows. Description of electrocatalytic apparatus and reaction conditions: the catalyst electrocatalytic CO 2 The reduction to formate is carried out at normal temperature and pressure. In the form of CO 2 The electrocatalytic reduction reaction is carried out for the reaction gas in an H-type electrolytic cell system. The proton exchange membrane is used for separating the cathode and the anode of the electrolytic cell, wherein the cathode compartment uses 15mL of 0.5mol/LKHCO 3 As electrolyte, the anode compartment used 10mL of 0.1mol/L H 2 SO 4 Is electrolyte and CO is continuously introduced into the cathode compartment during the reaction 2 And carrying out catalytic reduction reaction.
Using a three electrode system, 1mg of catalyst was supported on 1cm by applying a potential through an electrochemical workstation (CHI 660E) 2 The carbon paper of (2) is used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, a metal platinum mesh is used as a counter electrode, the reaction current is measured, and the current density is calculated. Wherein E is used RHE ＝E Ag/AgCl +0.197+ph×0.059 converts all potentials to reversible hydrogen electrode potentials.
The formate concentration was measured using a nuclear magnetic resonance spectrometer, and the faraday efficiency of formate was calculated to measure the selectivity of formate product, as shown in formula 1:
wherein C is Formate salt The concentration of formate, V is the volume of electrolyte in the cathode chamber, I is current, and t is reaction time.
The results of the catalytic properties of the alloys of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1.
Table 1 catalytic properties of the alloys provided in examples 1 to 4 and comparative examples 1 to 3
As can be seen from the data in Table 1, the introduction of a small amount of cadmium metal increases the selectivity of the bismuth-based catalyst for preparing formate compared to the pure bismuth metal catalyst, and the Faraday efficiency of formate is higher than 90% in the range of 1-10% of doped cadmium molar content. Demonstrated cadmium incorporation for CO 2 The electrocatalytic preparation of formate has a promoting effect. When the molar content of cadmium accounts for 3 percent of the alloy, the Faraday efficiency of formate is 99 percent, and the selectivity performance is optimal. Meanwhile, the bismuth-based catalyst containing cadmium metal is higher than-16 mAcm in formate bias current density -2 . Under the condition that the applied voltage is close, the current density performance of the cadmium bismuth alloy is equal to or even higher than that of the existing literature, and the fact that the alloy material provided by the invention can realize high-selectivity formate synthesis under the condition of lower voltage and can reduce the energy consumption of electrochemical reduction is also demonstrated.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A cadmium bismuth alloy comprising cadmium and bismuth; the cadmium accounts for 1-10 mol percent of the cadmium-bismuth alloy.
2. The cadmium-bismuth alloy according to claim 1, wherein the cadmium accounts for 3-10% of the molar percentage of the cadmium-bismuth alloy.
3. The method for preparing the cadmium bismuth alloy according to claim 1 or 2, comprising the steps of:
dispersing bismuth salt in a first solvent to obtain bismuth salt dispersion;
dissolving cadmium salt in a second solvent to obtain a cadmium salt solution;
and mixing the bismuth salt dispersion solution and the cadmium salt solution, and then dripping the mixture into a reducing agent solution to perform a reduction reaction to obtain the cadmium-bismuth alloy.
4. A method of preparation according to claim 3, wherein the reducing agent solution comprises an aqueous sodium borohydride solution or an aqueous potassium borohydride solution.
5. A method of preparation according to claim 3, wherein the bismuth salt comprises bismuth sulphate, bismuth chloride or bismuth nitrate.
6. The method of claim 3, wherein the cadmium salt comprises cadmium sulfate, cadmium chloride, or cadmium nitrate.
7. The method according to claim 3, wherein the temperature of the reduction reaction is-1 to 1 ℃;
the time of the reduction reaction is 0.4-0.6 h.
8. The method according to claim 3, wherein the reduction reaction is followed by: and washing the product after the reduction reaction with water and acetone in sequence.
9. The use of the cadmium bismuth alloy according to claim 1 or 2 or the cadmium bismuth alloy prepared by the preparation method according to any one of claims 3 to 8 as a catalyst.
10. Use according to claim 9, characterized in that the catalyst is a catalyst for the electrocatalytic reduction of carbon dioxide to formate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310751358.7A CN116926376A (en) | 2023-06-25 | 2023-06-25 | Cadmium bismuth alloy and preparation method and application thereof |
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