CN110538650B - Cerium oxide supported bismuth nano catalyst and preparation method and application thereof - Google Patents
Cerium oxide supported bismuth nano catalyst and preparation method and application thereof Download PDFInfo
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- CN110538650B CN110538650B CN201910836526.6A CN201910836526A CN110538650B CN 110538650 B CN110538650 B CN 110538650B CN 201910836526 A CN201910836526 A CN 201910836526A CN 110538650 B CN110538650 B CN 110538650B
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 114
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 67
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019253 formic acid Nutrition 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 96
- 238000003756 stirring Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000011261 inert gas Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- 238000006722 reduction reaction Methods 0.000 description 26
- 239000011734 sodium Substances 0.000 description 17
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000004321 preservation Methods 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 239000007832 Na2SO4 Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001075 voltammogram Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XEZOSAFGGJNNMY-UHFFFAOYSA-N [O-2].[Ce+3].[Bi+3].[O-2].[O-2] Chemical compound [O-2].[Ce+3].[Bi+3].[O-2].[O-2] XEZOSAFGGJNNMY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Abstract
The invention discloses a cerium oxide supported bismuth nano catalyst and a preparation method and application thereof, belonging to the fields of catalyst technology and energy sustainable development. Firstly, preparing a carrier cerium oxide at room temperature by a one-step reduction method; then, the carrier cerium oxide is mixed with Bi (NO)3)3·5H2And O, mixing, centrifuging, drying, calcining and the like to obtain the cerium oxide supported bismuth nano catalyst. The cerium oxide loaded bismuth nano-catalyst makes full use of a large number of defects in cerium oxide, and is combined with bismuth nano-particles, so that the number of active sites can be increased, and the activity of the catalyst can be remarkably improved. In particular, in the electrochemical reduction of CO2In formic acid production, the cerium oxide supported bismuth nano catalyst has excellent catalytic activity and excellent stability.
Description
Technical Field
The invention relates to the field of catalyst technology and energy sustainable development, in particular to a cerium oxide supported bismuth nano catalyst and a preparation method and application thereof.
Background
With increasing energy demand, there is a dramatic increase in CO in the atmosphere2The climate warming and ecological problems caused by the content become serious challenges for the sustainable development of human beings. Thus, for CO2The method can be effectively utilized and converted into green resources, and has extremely important significance. In which the CO is reduced electrocatalytically2And renewable electric energy (solar energy, wind energy and the like) can be effectively utilized, so that the device is widely concerned by researchers. In a large number of CO2Among the reduction products, formic acid, which is a product having a higher added value, can be applied not only to the pharmaceutical, leather, and textile industries but also to the hydrogen carrier of fuel cells, and thus formic acid is considered to be an extremely attractive CO2And (4) reducing the product. In addition, the synthesis of formic acid by traditional methods is complex and not environmentally friendly, and therefore, CO is reduced by electrocatalysis2Formic acid production is a very promising process.
At present, although some catalysts are used for the electro-reduction of CO2High selectivity and high Faraday Efficiency (FE) are obtained in the production of formic acid, but the FE of the formic acid is sensitive to external current density, so that the generation rate of the formic acid is limited. Usually at a higher current density (>60mA/cm2) Then, FE of formic acid is greatly reduced by the hydrogen evolution reaction. Therefore, there is an urgent need to develop a highly selective and highly active high performance electro-reduction CO2Catalyst for producing formic acid to ensure CO is promoted2The reduction rate of the formic acid can keep higher FE of formic acid.
Disclosure of Invention
The invention aims to provide a cerium oxide supported bismuth nano catalyst, and a preparation method and application thereof, so as to solve the problems in the background technology.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a preparation method of a cerium oxide supported bismuth nano catalyst comprises the following steps:
s01, putting the carrier cerium oxide into water, and uniformly stirring to obtain a solution C;
s02, adding Bi (NO) to the solution C3)3·5H2O, stirring uniformly to obtain a solution D; the Bi (NO)3)3·5H2The adding mass of O is 2-5 times of the mass of the carrier cerium oxide;
s03, mixing Na2CO3Slowly adding the solution into the solution D, and uniformly stirring to obtain a solution E;
s04, sequentially carrying out centrifugation, water washing, alcohol washing and vacuum drying treatment on the solution E to obtain a precursor;
s05, placing the precursor in inert gas/H2Calcining the mixture in the mixed gas to obtain the cerium oxide supported bismuth nano catalyst.
In a preferable embodiment of the present invention, in step S03, Na is added2CO3The mass of solute in the solution is 0.8-1.2 times of the mass of the carrier cerium oxide.
In another preferred embodiment of the present invention, in step S04, the temperature of vacuum drying is 35 to 50 ℃.
In another preferred embodiment of the present invention, in step S05, the inert gas/H2H in the mixed gas2The volume concentration of the catalyst is 8-12%, the calcining temperature is 100-200 ℃, and the calcining time is 0.5-2 h.
In another preferred embodiment of the present invention, the preparation method of the carrier cerium oxide comprises the following steps:
s11, adding Ce (NO)3)3·6H2Dissolving O in water to obtain a solution A;
s12, adding NaBH to the solution A4Stirring uniformly to obtain a solution B; the NaBH4Is Ce (NO) in mass3)3·6H20.1-0.4 times of the mass of O;
and S13, sequentially carrying out centrifugation, water washing, alcohol washing and drying on the solution B to obtain the carrier cerium oxide.
In another preferred embodiment of the present invention, in step S13, the drying temperature is 50-70 ℃.
The embodiment of the invention also provides a cerium oxide supported bismuth nano catalyst prepared by the preparation method.
The embodiment of the invention also provides application of the cerium oxide supported bismuth nano catalyst in electrocatalytic reduction of CO2Application in formic acid production.
In another preferred embodiment of the present invention, the electrocatalytic reduction of CO is performed2The method for producing formic acid comprises the following steps: dispersing the cerium oxide supported bismuth nano catalyst and the conductive carbon black in a water/ethanol mixed solution, and then adding a perfluorosulfonic acid type polymer for mixing to obtain a dispersion liquid; then, the dispersion was dropped on a carbon cloth to form a working electrode, Ag/AgCl and Pt meshes were used as a reference electrode and a counter electrode, respectively, and Na was added2SO4The solution is used as electrolyte; then, the electrolysis voltage of-1.4 to-1.9 Vvs. Ag/AgCl is applied to CO2And carrying out electrolytic reduction to obtain formic acid.
According to another preferable scheme adopted by the embodiment of the invention, the mass of the cerium oxide supported bismuth nano catalyst and the conductive carbon black is (4-6): 1; the volume ratio of water to ethanol in the water/ethanol mixed solution is (0.8-1.2) to 1; the mass volume ratio of the cerium oxide supported bismuth nano catalyst to the perfluorosulfonic acid polymer is 1 (8-12) in terms of mg/mu L; the Na is2SO4The molar concentration of the solution is 0.1-0.3M.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
(1) the preparation method of the cerium oxide supported bismuth nano catalyst provided by the embodiment of the invention adopts a one-step reduction method, can prepare the carrier cerium oxide at room temperature, and has the advantages of short synthesis time, simple and convenient operation and the like. In addition, the embodiment of the invention adopts the amorphous cerium oxide as the carrier, can fully utilize a large number of defects in the cerium oxide to combine with the bismuth nanoparticles, thereby increasing the number of active sites and obviously improving the activity of the catalyst.
(2) The synthesized carrier cerium oxide supported bismuth nano catalyst has high selectivity, and the catalyst is used in sodium sulfate electrolyte at normal temperature and normal temperatureReduction of CO2Electrochemical reduction, excellent catalytic activity for the formation of formic acid and excellent stability.
Drawings
FIG. 1 shows CeO obtained in comparative example 1xAnd Bi/CeO obtained in example 1xX-ray diffraction pattern of the catalyst.
FIG. 2 shows Bi/CeO obtained in example 1xThe catalyst is respectively in inert gas and CO2Saturated Na2SO4Linear voltammogram in the electrolyte.
FIG. 3 shows the pure bismuth catalyst prepared in comparative example 2 in inert gas and CO respectively2Saturated Na2SO4Linear voltammogram in the electrolyte.
FIG. 4 shows Bi/CeO obtained in example 1xCatalyst CO at normal temperature and pressure2Na in the atmosphere2SO4Current-time curves at different electrolysis voltages in the electrolyte.
FIG. 5 shows the pure Bi catalyst prepared in comparative example 2 under normal temperature and pressure CO2Na in the atmosphere2SO4Current-time curves at different voltages in the electrolyte.
FIG. 6 shows Bi/CeO obtained in example 1xCatalyst, pure Bi catalyst obtained in comparative example 2, and Bi/CeO obtained in comparative example 32The faradaic efficiency of formic acid of the catalyst under different electrolytic voltages at normal temperature and normal pressure is compared with a curve.
FIG. 7 shows Bi/CeO obtained in example 1xCatalyst, pure Bi catalyst obtained in comparative example 2, and Bi/CeO obtained in comparative example 32The production rate of formic acid of catalyst under different electrolytic voltages of normal temperature and pressure compares the curve chart.
FIG. 8 shows Bi/CeO obtained in example 1xCatalyst CO at normal temperature and pressure2Na in the atmosphere2SO4Long term stability profile at-1.7V vs. ag/AgCl in the electrolyte.
FIG. 9 shows a cerium oxide supported bismuth nanocatalyst (Bi/CeO) prepared in comparative example 32) Respectively in inert gas and CO2Saturated Na2SO4Linear voltammogram in the electrolyte.
FIG. 10 shows Bi/CeO in comparative example 32Catalyst CO at normal temperature and pressure2Na in the atmosphere2SO4Current-time curves at different voltages in the electrolyte.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a cerium oxide supported bismuth nano catalyst and a preparation method thereof, and particularly the preparation method of the cerium oxide supported bismuth nano catalyst comprises the following steps:
(1) 1.5g of Ce (NO)3)3·6H2Dissolving O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) to solution A was added 400mg of NaBH4Stirring uniformly, and carrying out reduction reaction for 40min to obtain a solution B;
(3) sequentially centrifuging, washing with water and alcohol, and drying at 60 deg.C to obtain cerium oxide (CeO) as carrierx)；
(4) Placing 400mg of carrier cerium oxide in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution C, wherein the ultrasonic frequency is 40 kHz;
(5) to solution C was added 1.5g of Bi (NO)3)3·5H2O, uniformly stirring by using ultrasonic waves to obtain a solution D, wherein the ultrasonic frequency is 40 kHz;
(6) 400mg of Na2CO3Dissolving in ultrapure water, and stirring with ultrasonic wave to obtain Na2CO3Solution, wherein the ultrasonic frequency is 40 kHz; then adding Na2CO3Slowly dripping the solution into the solution D, and uniformly stirring to obtain a solution E; wherein, the stirring is carried out at room temperature, and the stirring time is 90 min;
(7) sequentially carrying out centrifugation, water washing and alcohol washing on the solution E, and then placing the solution E at the temperature of 40 ℃ for vacuum drying treatment to obtain a precursor;
(8) placing the precursor in inert gas/H2Calcining in mixed gas to obtain the cerium oxide supported bismuth nano catalyst (Bi/CeO)x). Wherein, inert gas/H2H in the mixed gas2The volume concentration of the catalyst is 10 percent, the calcining temperature is 150 ℃, the calcining (heat preservation) time is 1h, and the inert gas can be argon (Ar).
Example 2
The embodiment provides a cerium oxide supported bismuth nano catalyst and a preparation method thereof, and particularly the preparation method of the cerium oxide supported bismuth nano catalyst comprises the following steps:
(1) 1g of Ce (NO)3)3·6H2Dissolving O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) to solution A was added 100mg of NaBH4Uniformly stirring, and carrying out reduction reaction for 10min to obtain a solution B;
(3) sequentially centrifuging, washing with water and alcohol, and drying at 50 deg.C to obtain cerium oxide (CeO) as carrierx)；
(4) Putting 100mg of carrier cerium oxide into ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution C;
(5) to solution C was added 0.5g of Bi (NO)3)3·5H2O, uniformly stirring by utilizing ultrasonic waves to obtain a solution D;
(6) 120mg of Na2CO3Dissolving in ultrapure water, and stirring with ultrasonic wave to obtain Na2CO3A solution; then adding Na2CO3Slowly dripping the solution into the solution D, and uniformly stirring to obtain a solution E; wherein the stirring is carried out at room temperature for 3 hours0min；
(7) Sequentially carrying out centrifugation, water washing and alcohol washing on the solution E, and then carrying out vacuum drying treatment at the temperature of 35 ℃ to obtain a precursor;
(8) placing the precursor in inert gas/H2Calcining the mixture in the mixed gas to obtain the cerium oxide supported bismuth nano catalyst. Wherein, inert gas/H2H in the mixed gas2The volume concentration of the catalyst is 8 percent, the calcining temperature is 100 ℃, the calcining (heat preservation) time is 0.5h, and the inert gas can be argon (Ar).
Example 3
The embodiment provides a cerium oxide supported bismuth nano catalyst and a preparation method thereof, and particularly the preparation method of the cerium oxide supported bismuth nano catalyst comprises the following steps:
(1) 2g of Ce (NO)3)3·6H2Dissolving O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) add 800mg of NaBH to solution A4Uniformly stirring, and carrying out reduction reaction for 60min to obtain a solution B;
(3) sequentially centrifuging, washing with water and alcohol, and drying at 70 deg.C to obtain cerium oxide (CeO) as carrierx)；
(4) Placing 800mg of carrier cerium oxide in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution C;
(5) to solution C was added 1.6g of Bi (NO)3)3·5H2O, uniformly stirring by utilizing ultrasonic waves to obtain a solution D;
(6) 640mg of Na2CO3Dissolving in ultrapure water, and stirring with ultrasonic wave to obtain Na2CO3A solution; then adding Na2CO3Slowly dripping the solution into the solution D, and uniformly stirring to obtain a solution E; wherein, the stirring is carried out at room temperature, and the stirring time is 120 min;
(7) sequentially carrying out centrifugation, water washing and alcohol washing on the solution E, and then placing the solution E at the temperature of 50 ℃ for vacuum drying treatment to obtain a precursor;
(8) placing the precursor in inert gas/H2Calcining the mixture in the mixed gas to obtain the cerium oxide supported bismuth nano catalyst. Wherein, inert gas/H2H in the mixed gas2The volume concentration of the catalyst is 12 percent, the calcining temperature is 200 ℃, the calcining (heat preservation) time is 2 hours, and the inert gas can be argon (Ar).
Example 4
This example provides a method for electrocatalytic reduction of CO using the cerium oxide supported bismuth nanocatalyst prepared in example 12Application in formic acid production. In particular, the electrocatalytic reduction of CO2The method for producing formic acid comprises the following steps: after dispersing the cerium oxide-supported bismuth nanocatalyst prepared in example 1 and conductive carbon black (commercially available XC-72 carbon black) in a water/ethanol mixed solution, a perfluorosulfonic acid type polymer (commercially available Nafion) was added and mixed to obtain a dispersion liquid; then, the dispersion was dropped on a carbon cloth to form a working electrode, Ag/AgCl and Pt meshes were used as a reference electrode and a counter electrode, respectively, and Na was added2SO4The solution is used as electrolyte; then, the electrolysis voltage of the CO is adjusted to-1.4 to-1.9V vs. Ag/AgCl2And carrying out electrolytic reduction to obtain formic acid. Wherein the mass ratio of the cerium oxide supported bismuth nano catalyst to the conductive carbon black is 5: 1; the volume ratio of water to ethanol in the water/ethanol mixed solution is 1: 1; the mass-volume ratio of the cerium oxide supported bismuth nano catalyst to the perfluorosulfonic acid polymer is 1:10 in terms of mg/mu L; the Na is2SO4The molar concentration of the solution was 0.3M. The prepared formic acid can be detected by liquid-phase nuclear magnetic resonance, specifically, 1mL of electrolyzed electrolyte is added with 200 mu L D2O (containing 0.1 mu L DMSO) is shaken up, and the content of the formic acid can be detected by liquid-phase nuclear magnetic resonance.
Example 5
This example provides a method for electrocatalytic reduction of CO using the cerium oxide supported bismuth nanocatalyst prepared in example 12Application in formic acid production. In particular, the electrocatalytic reduction of CO2The method for producing formic acid comprises the following steps: the cerium oxide prepared in example 1 was loaded with bismuth sodiumDispersing a rice catalyst and conductive carbon black (commercial XC-72 carbon black) in a water/ethanol mixed solution, and then adding a perfluorosulfonic acid polymer (commercial Nafion) for mixing to obtain a dispersion liquid; then, the dispersion was dropped on a carbon cloth to form a working electrode, Ag/AgCl and Pt meshes were used as a reference electrode and a counter electrode, respectively, and Na was added2SO4The solution is used as electrolyte; then, the electrolysis voltage of the CO is adjusted to-1.4 to-1.9V vs. Ag/AgCl2And carrying out electrolytic reduction to obtain formic acid. Wherein the mass ratio of the cerium oxide supported bismuth nano catalyst to the conductive carbon black is 4: 1; the volume ratio of water to ethanol in the water/ethanol mixed solution is 0.8: 1; the mass-volume ratio of the cerium oxide supported bismuth nano catalyst to the perfluorosulfonic acid polymer is 1:8 in terms of mg/mu L; the Na is2SO4The molar concentration of the solution was 0.1M.
Example 6
This example provides a method for electrocatalytic reduction of CO using the cerium oxide supported bismuth nanocatalyst prepared in example 12Application in formic acid production. In particular, the electrocatalytic reduction of CO2The method for producing formic acid comprises the following steps: after dispersing the cerium oxide-supported bismuth nanocatalyst prepared in example 1 and conductive carbon black (commercially available XC-72 carbon black) in a water/ethanol mixed solution, a perfluorosulfonic acid type polymer (commercially available Nafion) was added and mixed to obtain a dispersion liquid; then, the dispersion was dropped on a carbon cloth to form a working electrode, Ag/AgCl and Pt meshes were used as a reference electrode and a counter electrode, respectively, and Na was added2SO4The solution is used as electrolyte; then, the electrolysis voltage of the CO is adjusted to-1.4 to-1.9V vs. Ag/AgCl2And carrying out electrolytic reduction to obtain formic acid. Wherein the mass ratio of the cerium oxide supported bismuth nano catalyst to the conductive carbon black is 6: 1; the volume ratio of water to ethanol in the water/ethanol mixed solution is 1.2: 1; the mass-volume ratio of the cerium oxide supported bismuth nano catalyst to the perfluorosulfonic acid polymer is 1:12 in terms of mg/mu L; the Na is2SO4The molar concentration of the solution was 0.3M.
Comparative example 1
This comparative example provides a carrier cerium oxide (CeO)x) The product isThe preparation method of the carrier cerium oxide comprises the following steps:
(1) 1.5g of Ce (NO)3)3·6H2Dissolving O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) to solution A was added 400mg of NaBH4Stirring uniformly, and carrying out reduction reaction for 40min to obtain a solution B;
(3) sequentially centrifuging, washing with water and alcohol, and drying at 60 deg.C to obtain cerium oxide (CeO) as carrierx)。
The carrier cerium oxide (CeO) prepared in comparative example 1 was subjected to X-ray powder diffractionx) And the cerium oxide supported bismuth nanocatalyst (Bi/CeO) prepared in example 1x) The crystallinity of (2) was examined, and the examination results are shown in FIG. 1. Wherein, the carrier cerium oxide is of a low-crystallinity structure, and the bismuth-loaded cerium oxide bismuth nano-catalyst obtained after bismuth loading still maintains weaker crystallinity.
Comparative example 2
This comparative example provides a pure bismuth catalyst (pure Bi) prepared by a method comprising the steps of:
(1) 1.5g of Bi (NO)3)3·5H2Dissolving O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution F;
(2) 400mg of Na2CO3Dissolving in ultrapure water, and stirring with ultrasonic wave to obtain Na2CO3A solution; then adding Na2CO3Slowly dripping the solution into the solution F, and uniformly stirring to obtain a solution G; wherein, the stirring is carried out at room temperature, and the stirring time is 90 min;
(3) sequentially carrying out centrifugation, water washing and alcohol washing on the solution G, and then carrying out vacuum drying treatment at the temperature of 40 ℃ to obtain a precursor;
(4) placing the precursor in inert gas/H2Calcining the bismuth in the mixed gas to obtain the pure bismuth catalyst (pureBi). Wherein, inert gas/H2H in the mixed gas2Is 10% by volume, calcinedThe temperature of (2) is 150 ℃, the time of calcination (heat preservation) is 1h, and the inert gas can be argon (Ar).
Comparative example 3
This comparative example provides a ceria-supported bismuth nanocatalyst (Bi/CeO)2) The preparation method of the catalyst comprises the following steps:
(1) 1g of Ce (NO)3)3·6H2Dissolving O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution H, wherein the ultrasonic frequency is 40 kHz;
(2) slowly adding the solution H into a NaOH solution, and uniformly stirring to obtain a solution I; wherein the concentration of the NaOH solution is 6mol/L, and the stirring is carried out at room temperature for 30 min;
(3) transferring the solution I to a high-temperature high-pressure reaction kettle, and carrying out hydrothermal reaction to obtain a solution J; wherein the heat preservation temperature is 100 ℃, and the heat preservation time is 24 hours;
(4) sequentially centrifuging, washing with water, washing with alcohol, and drying at 40 deg.C to obtain carrier cerium dioxide (CeO)2)；
(5) 400mg of CeO2Placing the solution in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution K;
(6) to solution K was added 1.5g of Bi (NO)3)3·5H2O, uniformly stirring by utilizing ultrasonic waves to obtain a solution L;
(7) 400mg of Na2CO3Dissolving in ultrapure water, and stirring with ultrasonic wave to obtain Na2CO3A solution; then adding Na2CO3Slowly dripping the solution into the solution L, and uniformly stirring to obtain a solution M; wherein, the stirring is carried out at room temperature, and the stirring time is 90 min;
(8) sequentially carrying out centrifugation, water washing and alcohol washing on the solution M, and then carrying out vacuum drying treatment at the temperature of 40 ℃ to obtain a precursor;
(9) placing the precursor in inert gas/H2Calcining in mixed gas to obtain the cerium dioxide loaded bismuth nano catalyst (Bi/CeO)2). Wherein, inert gas/H2H in the mixed gas2The volume concentration of the catalyst is 10 percent, the calcining temperature is 150 ℃, the calcining (heat preservation) time is 1h, and the inert gas can be argon (Ar).
In addition, electrocatalytic reduction of CO as provided in example 42Method for producing formic acid using the pure bismuth catalyst (pure Bi) obtained in comparative example 2 and the cerium oxide-supported bismuth nanocatalyst (Bi/CeO) obtained in comparative example 32) Bismuth nano-catalyst pair CO loaded instead of cerium oxide2And carrying out electrolytic reduction to obtain the formic acid.
Referring to the attached fig. 2, 3 and 9, fig. 2 shows the cerium oxide supported bismuth nano-catalyst prepared in example 1 respectively in inert gas and CO2Saturated Na2SO4Linear voltammograms in the electrolyte; FIG. 3 shows the pure bismuth catalyst prepared in comparative example 2 in inert gas and CO respectively2Saturated Na2SO4Linear voltammograms in the electrolyte; FIG. 9 shows Bi/CeO obtained in comparative example 32The catalyst is respectively in inert gas and CO2Saturated Na2SO4Linear voltammogram in the electrolyte. As can be seen from the figure, the cerium oxide supported bismuth nanocatalyst prepared in example 1 has CO pairing2Has stronger reducing effect.
Referring to FIGS. 4, 5 and 10, FIG. 4 shows a cerium oxide supported bismuth nanocatalyst (Bi/CeO) prepared in example 1x) CO at normal temperature and pressure2Na in the atmosphere2SO4Current density-Time curves at different electrolytic voltages in the electrolyte; FIG. 5 shows CO at room temperature and pressure for pure Bi catalyst in comparative example 22Na in the atmosphere2SO4Current-time curves at different voltages in the electrolyte; FIG. 10 shows Bi/CeO in comparative example 32Catalyst CO at normal temperature and pressure2Na in the atmosphere2SO4Current-time curves at different voltages in the electrolyte; the results of the current-time (I-t) curves show that at each electrolysis voltage (Potential), Bi/CeO was obtained in comparison to pure Bi catalyst obtained in comparative example 2 and Bi/CeO obtained in comparative example 32Catalyst, Bi/CeO from example 1xCatalysisThe agents all show greater current with obvious advantages for CO2Has stronger reducing effect.
Referring to FIGS. 6-7, FIG. 6 shows Bi/CeO obtained in example 1xCatalyst, pure Bi catalyst obtained in comparative example 2, and Bi/CeO obtained in comparative example 32The Faraday Efficiency (FE) comparison results of the catalyst under normal temperature and normal pressure and different electrolysis voltages of formic acid; FIG. 7 shows Bi/CeO obtained in example 1xCatalyst, pure Bi catalyst obtained in comparative example 2, and Bi/CeO obtained in comparative example 32The results of the comparison of the production rates (production rates) of formic acid at different electrolysis voltages of the catalyst at normal temperature and pressure. It can be seen that, at each electrolysis voltage (Potential), Bi/CeO was obtained in comparison with pure Bi catalyst obtained in comparative example 2 and Bi/CeO obtained in comparative example 32Catalyst, Bi/CeO from example 1xThe catalyst not only has extremely high production rate, but also can keep higher Faraday efficiency. Wherein, at-1.7 Vvs. Ag/AgCl, the electrocatalytic reduction of CO of example 42The Faraday Efficiency (FE) of the formic acid is 98 percent and reaches the highest, and the production rate of the formic acid reaches 1800 mu mol.h-1·cm-2(ii) a Electrocatalytic reduction of CO from example 4 at-1.8V vs. Ag/AgCl2The production rate of formic acid is 2600 mu mol.h-1·cm-2The maximum value is reached, the FE of formic acid is 92%. Therefore, the catalytic activity of the cerium oxide supported bismuth nano catalyst provided by the embodiment of the invention is far higher than that of the S-In reported at present2O3derived In (production rate: 1449. mu. mol. h)-1·cm-2And FE: 93%), sn (s)/Au needles (production rate: 957. mu. mol. h-1·cm-2，FE：93％)、porous SnO2(production rate: 811. mu. mol. h)-1·cm-2And FE: 87%), Pd nano inert gas gels (production rate: 398 mu mol.h-1·cm-2And FE: 97%), and the like.
Further, referring to FIG. 8, Bi/CeO obtained in example 1xCatalyst CO at normal temperature and pressure2Na in the atmosphere2SO4at-1.7V vs. Ag/AgCl in the electrolyteLong term stability curve; it can be known that the current is kept stable within 37h of the electrocatalysis process, and the FE of the formic acid can be kept at about 97% within 34h, so that the stability is excellent.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. The preparation method of the cerium oxide supported bismuth nano catalyst is characterized by comprising the following steps of:
s01, putting the carrier cerium oxide into water, and uniformly stirring to obtain a solution C;
s02, adding Bi (NO) to the solution C3)3·5H2O, stirring uniformly to obtain a solution D; the Bi (NO)3)3·5H2The adding mass of O is 2-5 times of the mass of the carrier cerium oxide;
s03, mixing Na2CO3Slowly adding the solution into the solution D, and uniformly stirring to obtain a solution E;
s04, sequentially carrying out centrifugation, water washing, alcohol washing and vacuum drying treatment on the solution E to obtain a precursor;
s05, placing the precursor in inert gas/H2Calcining the mixed gas to obtain a cerium oxide supported bismuth nano catalyst;
the preparation method of the carrier cerium oxide comprises the following steps:
s11, adding Ce (NO)3)3·6H2Dissolving O in water to obtain a solution A;
s12, adding NaBH to the solution A4Stirring uniformly to obtain a solution B; the NaBH4Is Ce (NO) in mass3)3·6H20.1-0.4 times of the mass of O;
and S13, sequentially carrying out centrifugation, water washing, alcohol washing and drying on the solution B to obtain the carrier cerium oxide.
2. The method of claim 1, wherein in step S03, Na is added2CO3The mass of solute in the solution is 0.8-1.2 times of the mass of the carrier cerium oxide.
3. The method of claim 1, wherein in step S04, the temperature for vacuum drying is 35-50 ℃.
4. The method of claim 1, wherein in step S05, the inert gas/H is used as the carrier gas2H in the mixed gas2The volume concentration of the catalyst is 8-12%, the calcining temperature is 100-200 ℃, and the calcining time is 0.5-2 h.
5. The method of claim 1, wherein the drying temperature in step S13 is 50-70 ℃.
6. A cerium oxide-supported bismuth nanocatalyst prepared by the preparation method according to any one of claims 1 to 5.
7. The use of the cerium oxide supported bismuth nano-catalyst according to claim 6 in electrocatalytic reduction of CO2Application in formic acid production.
8. The application of the cerium oxide supported bismuth nano-catalyst as claimed in claim 7, wherein the electrocatalytic reduction of CO is performed2The method for producing formic acid comprises the following steps: dispersing the cerium oxide supported bismuth nano catalyst and the conductive carbon black in a water/ethanol mixed solution, and then adding a perfluorosulfonic acid type polymer for mixing to obtain a dispersion liquid; then, the dispersion liquid is dripped onto carbon cloth to form a working electrodeAg/AgCl and Pt meshes are respectively used as a reference electrode and a counter electrode, and Na is added2SO4The solution is used as electrolyte; then, the electrolysis voltage of Ag/AgCl is applied to CO under the voltage of-1.9 to-1.4V vs2And carrying out electrolytic reduction to obtain formic acid.
9. The application of the cerium oxide supported bismuth nano catalyst as claimed in claim 8, wherein the mass of the cerium oxide supported bismuth nano catalyst and the conductive carbon black is (4-6): 1; the volume ratio of water to ethanol in the water/ethanol mixed solution is (0.8-1.2) to 1; the mass volume ratio of the cerium oxide supported bismuth nano catalyst to the perfluorosulfonic acid polymer is 1 (8-12) according to mg/mu L; the Na is2SO4The molar concentration of the solution is 0.1-0.3M.
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