CN110538650A - 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
- Publication number
- CN110538650A CN110538650A CN201910836526.6A CN201910836526A CN110538650A CN 110538650 A CN110538650 A CN 110538650A CN 201910836526 A CN201910836526 A CN 201910836526A CN 110538650 A CN110538650 A CN 110538650A
- Authority
- CN
- China
- Prior art keywords
- cerium oxide
- solution
- catalyst
- bismuth nano
- supported bismuth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 95
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 68
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 80
- 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
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000005119 centrifugation Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 100
- 238000003756 stirring Methods 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 28
- 239000011261 inert gas Substances 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 235000017550 sodium carbonate Nutrition 0.000 claims description 19
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 10
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 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
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 40
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007547 defect 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 27
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 15
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 description 13
- 235000011152 sodium sulphate Nutrition 0.000 description 13
- 239000007832 Na2SO4 Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000004321 preservation Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000001075 voltammogram Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- -1 CO2 saturated Na2SO4 Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 230000007774 longterm Effects 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
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 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
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000446 fuel 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
- 239000008188 pellet Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000010792 warming Methods 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
- B01J23/16—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 (NO3) 3.5H 2O, and the steps of centrifugation, drying, calcination and the like are carried out 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 CO2 to produce formic acid, 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 the increasing demand for energy, the climate warming and ecological problems caused by the rapidly increasing CO2 content in the atmosphere become a serious challenge for human sustainable development. Therefore, it is of great importance to effectively utilize CO2 and convert it into a green resource. Among them, the electrocatalytic reduction of CO2 can effectively utilize renewable electric energy (solar energy, wind energy, etc.), and thus has received much attention from researchers. Among the numerous CO2 reduction products, formic acid, which is a higher value-added product, can be applied not only to the pharmaceutical, leather, and textile industries but also to the hydrogen carrier of fuel cells, and thus is considered to be an extremely attractive CO2 reduction product. In addition, the synthesis of formic acid by conventional methods is complex and not environmentally friendly, and therefore, the production of formic acid by electrocatalytic reduction of CO2 is a very promising method.
Currently, although some catalysts achieve higher selectivity in the electro-reduction of CO2 to produce formic acid and obtain higher Faradaic Efficiency (FE), the FE of formic acid is sensitive to external current density, which results in a limitation of the formic acid production rate. Generally, at higher current densities (>60mA/cm2), the FE of formic acid is greatly reduced by the hydrogen evolution reaction. Therefore, at present, a high-selectivity and high-activity catalyst for electrically reducing CO2 to produce formic acid is urgently needed to be developed, so that the rate of reducing CO2 to produce formic acid is increased, and meanwhile, high FE of formic acid can be maintained.
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 (NO3) 3.5H 2O into the solution C, and uniformly stirring to obtain a solution D; the added mass of the Bi (NO3) 3.5H 2O is 2-5 times of the mass of the carrier cerium oxide;
s03, slowly adding the Na2CO3 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;
And S05, placing the precursor in an inert gas/H2 mixed gas for calcining to obtain the cerium oxide supported bismuth nano catalyst.
In a preferable embodiment of the present invention, in step S03, the mass of the solute in the Na2CO3 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 adopted in the embodiment of the invention, in the step S05, the volume concentration of H2 in the inert gas/H2 mixed gas is 8-12%, the calcination temperature is 100-200 ℃, and the calcination time is 0.5-2H.
In another preferred embodiment of the present invention, the preparation method of the carrier cerium oxide comprises the following steps:
S11, dissolving Ce (NO3)3 & 6H2O in water to obtain a solution A;
s12, adding NaBH4 into the solution A, and uniformly stirring to obtain a solution B; the added mass of NaBH4 is 0.1-0.4 times of the mass of Ce (NO3) 3.6H 2O;
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 production of formic acid by electrocatalytic reduction of CO 2.
In another preferred scheme adopted by the embodiment of the invention, the method for producing formic acid by electrocatalytic reduction of CO2 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, dropwise adding the dispersion liquid onto carbon cloth to form a working electrode, respectively taking Ag/AgCl and a Pt net as a reference electrode and a counter electrode, and taking NaSO4 solution as electrolyte; then, CO2 is subjected to electrolytic reduction under the electrolytic voltage of-1.4 to-1.9V vs. Ag/AgCl 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 molar concentration of the NaSO4 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, is used for CO2 electrochemical reduction at normal temperature and normal pressure in sodium sulfate electrolyte, and has excellent catalytic activity and excellent stability for formic acid generation.
drawings
FIG. 1 is an X-ray diffraction pattern of CeOx prepared in comparative example 1 and a Bi/CeOx catalyst prepared in example 1.
FIG. 2 is a linear voltammogram of the Bi/CeOx catalyst prepared in example 1 in an inert gas and a Na2SO4 electrolyte saturated with CO2, respectively.
Fig. 3 is a linear voltammogram of the pure bismuth catalyst prepared in comparative example 2 in an inert gas and a Na2SO4 electrolyte saturated with CO2, respectively.
FIG. 4 is a graph of current versus time at different electrolytic voltages in Na2SO4 electrolyte under an atmosphere of CO2 at normal temperature and pressure for the Bi/CeOx catalyst prepared in example 1.
FIG. 5 is a graph of current versus time at different voltages in Na2SO4 electrolyte under an atmosphere of CO2 at room temperature and pressure for the pure Bi catalyst prepared in comparative example 2.
FIG. 6 is a graph showing the comparison of the Faraday efficiencies of formic acid at different electrolysis voltages at room temperature and pressure for the Bi/CeOx catalyst obtained in example 1, the pure Bi catalyst obtained in comparative example 2, and the Bi/CeO2 catalyst obtained in comparative example 3.
FIG. 7 is a graph showing the comparison of the production rates of formic acid at different electrolysis voltages at room temperature and pressure for the Bi/CeOx catalyst obtained in example 1, the pure Bi catalyst obtained in comparative example 2, and the Bi/CeO2 catalyst obtained in comparative example 3.
FIG. 8 is a graph showing the long term stability of the Bi/CeOx catalyst prepared in example 1 at-1.7V vs. Ag/AgCl in Na2SO4 electrolyte under an atmosphere of CO2 at normal temperature and pressure.
fig. 9 is a linear voltammogram of the ceria-supported bismuth nanocatalyst (Bi/CeO2) prepared in comparative example 3 in an inert gas and a CO2 saturated Na2SO4 electrolyte, respectively.
FIG. 10 is a graph of current versus time for different voltages in Na2SO4 electrolyte under an atmosphere of CO2 at room temperature and pressure for a Bi/CeO2 catalyst in comparative example 3.
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) dissolving 1.5g of Ce (NO3) 3.6H 2O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) adding 400mg of NaBH4 into the solution A, uniformly stirring, and carrying out reduction reaction for 40min to obtain a solution B;
(3) Sequentially carrying out centrifugation, water washing and alcohol washing on the solution B, and then drying at the temperature of 60 ℃ to obtain a carrier cerium oxide (CeOx);
(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) Adding 1.5g of Bi (NO3) 3.5H 2O into the solution C, and uniformly stirring by using ultrasonic waves to obtain a solution D, wherein the ultrasonic frequency is 40 kHz;
(6) Dissolving 400mg of Na2CO3 in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a Na2CO3 solution, wherein the ultrasonic frequency is 40 kHz; then slowly dropwise adding the Na2CO3 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) And (3) putting the precursor into an inert gas/H2 mixed gas for calcining to obtain the cerium oxide supported bismuth nano catalyst (Bi/CeOx). Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 10%, 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) Dissolving 1g of Ce (NO3) 3.6H 2O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) Adding 100mg of NaBH4 into the solution A, uniformly stirring, and carrying out reduction reaction for 10min to obtain a solution B;
(3) Sequentially carrying out centrifugation, water washing and alcohol washing on the solution B, and then drying at the temperature of 50 ℃ to obtain a carrier cerium oxide (CeOx);
(4) Putting 100mg of carrier cerium oxide into ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution C;
(5) adding 0.5g of Bi (NO3) 3.5H 2O into the solution C, and uniformly stirring by ultrasonic waves to obtain a solution D;
(6) Dissolving 120mg of Na2CO3 in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a Na2CO3 solution; then slowly dropwise adding the Na2CO3 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 30 min;
(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) And (3) putting the precursor into an inert gas/H2 mixed gas for calcining to obtain the cerium oxide supported bismuth nano catalyst. Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 8%, 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) dissolving 2g of Ce (NO3) 3.6H 2O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) Adding 800mg of NaBH4 into the solution A, uniformly stirring, and carrying out reduction reaction for 60min to obtain a solution B;
(3) sequentially carrying out centrifugation, water washing and alcohol washing on the solution B, and then drying at the temperature of 70 ℃ to obtain a carrier cerium oxide (CeOx);
(4) Placing 800mg of carrier cerium oxide in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution C;
(5) adding 1.6g of Bi (NO3) 3.5H 2O into the solution C, and uniformly stirring by ultrasonic waves to obtain a solution D;
(6) Dissolving 640mg of Na2CO3 in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a Na2CO3 solution; then slowly dropwise adding the Na2CO3 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) and (3) putting the precursor into an inert gas/H2 mixed gas for calcining to obtain the cerium oxide supported bismuth nano catalyst. Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 12%, the calcining temperature is 200 ℃, the calcining (heat preservation) time is 2H, and the inert gas can be argon (Ar).
example 4
the embodiment provides an application of the cerium oxide supported bismuth nano-catalyst prepared in the embodiment 1 in the production of formic acid by electrocatalytic reduction of CO 2. Specifically, the method for producing formic acid by electrocatalytic reduction of CO2 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, dropwise adding the dispersion liquid onto carbon cloth to form a working electrode, respectively taking Ag/AgCl and a Pt net as a reference electrode and a counter electrode, and taking NaSO4 solution as electrolyte; then, CO2 was subjected to electrolytic reduction at an electrolytic voltage of-1.4 to-1.9 Vvs. Ag/AgCl 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 molar concentration of the NaSO4 solution was 0.3M. The prepared formic acid can be detected by liquid-phase nuclear magnetic resonance, and specifically, the content of the formic acid can be detected by liquid-phase nuclear magnetic resonance by adding 200 mu L D2O (containing 0.1 mu L DMSO) into 1mL of electrolyzed electrolyte and shaking up.
example 5
the embodiment provides an application of the cerium oxide supported bismuth nano-catalyst prepared in the embodiment 1 in the production of formic acid by electrocatalytic reduction of CO 2. Specifically, the method for producing formic acid by electrocatalytic reduction of CO2 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, dropwise adding the dispersion liquid onto carbon cloth to form a working electrode, respectively taking Ag/AgCl and a Pt net as a reference electrode and a counter electrode, and taking NaSO4 solution as electrolyte; then, CO2 is subjected to electrolytic reduction under the electrolytic voltage of-1.4 to-1.9V vs. Ag/AgCl 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 molar concentration of the NaSO4 solution was 0.1M.
Example 6
The embodiment provides an application of the cerium oxide supported bismuth nano-catalyst prepared in the embodiment 1 in the production of formic acid by electrocatalytic reduction of CO 2. Specifically, the method for producing formic acid by electrocatalytic reduction of CO2 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, dropwise adding the dispersion liquid onto carbon cloth to form a working electrode, respectively taking Ag/AgCl and a Pt net as a reference electrode and a counter electrode, and taking NaSO4 solution as electrolyte; then, CO2 is subjected to electrolytic reduction under the electrolytic voltage of-1.4 to-1.9V vs. Ag/AgCl 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 molar concentration of the NaSO4 solution was 0.3M.
comparative example 1
The comparative example provides a carrier cerium oxide (CeOx), which is prepared by a method comprising the steps of:
(1) Dissolving 1.5g of Ce (NO3) 3.6H 2O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution A;
(2) Adding 400mg of NaBH4 into the solution A, uniformly stirring, and carrying out reduction reaction for 40min to obtain a solution B;
(3) and (3) sequentially carrying out centrifugation, water washing and alcohol washing on the solution B, and then drying at the temperature of 60 ℃ to obtain the carrier cerium oxide (CeOx).
the crystallinity of the cerium oxide supported bismuth nanocatalyst (Bi/CeOx) prepared in comparative example 1 and the cerium oxide supported bismuth nanocatalyst (CeOx) prepared in example 1 was measured by X-ray powder diffraction, and the 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) dissolving 1.5g of Bi (NO3) 3.5H 2O in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution F;
(2) dissolving 400mg of Na2CO3 in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a Na2CO3 solution; then slowly dropwise adding the Na2CO3 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) And (3) putting the precursor into an inert gas/H2 mixed gas for calcining to obtain the pure bismuth catalyst (pure Bi). Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 10%, the calcining temperature is 150 ℃, the calcining (heat preservation) time is 1H, and the inert gas can be argon (Ar).
Comparative example 3
This comparative example provides a ceria-supported bismuth nanocatalyst (Bi/CeO2) prepared by a method comprising the steps of:
(1) dissolving 1g of Ce (NO3) 3.6H 2O 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 carrying out centrifugation, water washing and alcohol washing on the solution J, and then drying at the temperature of 40 ℃ to obtain a carrier cerium dioxide (CeO 2);
(5) Placing 400mg of CeO2 in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a solution K;
(6) Adding 1.5g of Bi (NO3) 3.5H 2O into the solution K, and uniformly stirring by using ultrasonic waves to obtain a solution L;
(7) dissolving 400mg of Na2CO3 in ultrapure water, and uniformly stirring by using ultrasonic waves to obtain a Na2CO3 solution; then slowly dropwise adding the Na2CO3 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) and (3) putting the precursor into an inert gas/H2 mixed gas for calcining to obtain the cerium dioxide supported bismuth nano catalyst (Bi/CeO 2). Wherein, the volume concentration of H2 in the inert gas/H2 mixed gas is 10%, the calcining temperature is 150 ℃, the calcining (heat preservation) time is 1H, and the inert gas can be argon (Ar).
in addition, according to the method for producing formic acid by electrocatalytic reduction of CO2 provided in example 4, CO2 was subjected to electrolytic reduction to produce formic acid by using the pure bismuth catalyst (pure Bi) obtained in comparative example 2 and the ceria-supported bismuth nanocatalyst (Bi/CeO2) obtained in comparative example 3, respectively, instead of the ceria-supported bismuth nanocatalyst.
Referring to fig. 2, 3 and 9, fig. 2 is a linear voltammogram of the cerium oxide supported bismuth nanocatalyst prepared in example 1 in an inert gas and a Na2SO4 electrolyte saturated with CO2, respectively; FIG. 3 is a linear voltammogram of the pure bismuth catalyst prepared in comparative example 2 in an inert gas and a Na2SO4 electrolyte saturated with CO2, respectively; FIG. 9 is a linear voltammogram of the Bi/CeO2 catalyst prepared in comparative example 3 in an inert gas and a CO2 saturated Na2SO4 electrolyte, respectively. As can be seen from the figure, the cerium oxide supported bismuth nanocatalyst prepared in example 1 has stronger reducing effect on CO 2.
Referring to fig. 4, 5 and 10, fig. 4 is a Current density-Time (Time) curve of the cerium oxide supported bismuth nano catalyst (Bi/CeOx) prepared in example 1 under the atmosphere of CO2 at normal temperature and pressure in Na2SO4 electrolyte at different electrolytic voltages; FIG. 5 is a current-time curve of the pure Bi catalyst in comparative example 2 under different voltages in Na2SO4 electrolyte under an atmosphere of CO2 at normal temperature and pressure; FIG. 10 is a graph of current versus time at different voltages in a Na2SO4 electrolyte under an atmosphere of CO2 at normal temperature and pressure for a Bi/CeO2 catalyst in comparative example 3; the current-time (I-t) curve results show that the Bi/CeOx catalyst prepared in example 1 exhibited a greater current at each electrolysis voltage (Potential) than the pure Bi catalyst prepared in comparative example 2 and the Bi/CeO2 catalyst prepared in comparative example 3, with a distinct advantage of greater reduction of CO 2.
Referring to FIGS. 6 to 7, FIG. 6 shows the results of comparing the Faraday Efficiencies (FE) of the Bi/CeOx catalyst obtained in example 1, the pure Bi catalyst obtained in comparative example 2, and the Bi/CeO2 catalyst obtained in comparative example 3 with formic acid at different electrolysis voltages at normal temperature and pressure; FIG. 7 is a comparison of the production rates (Product rates) of formic acid at different electrolysis voltages at room temperature and pressure for the Bi/CeOx catalyst obtained in example 1, the pure Bi catalyst obtained in comparative example 2, and the Bi/CeO2 catalyst obtained in comparative example 3. It can be seen that the Bi/CeOx catalyst prepared in example 1 not only has an extremely high production rate but also maintains a high faraday efficiency at each electrolysis voltage (Potential) relative to the pure Bi catalyst obtained in comparative example 2 and the Bi/CeO2 catalyst prepared in comparative example 3. Wherein, at-1.7V vs. Ag/AgCl, the Faraday Efficiency (FE) of the electro-catalytic reduction of CO2 to produce formic acid of example 4 is 98%, which reaches the highest, and the production rate of formic acid reaches 1800 mu mol.h < -1. cm < -2 >; the production rate of formic acid from the electrocatalytic reduction of CO2 of example 4 was 2600. mu. mol. h-1. cm-2 at-1.8V vs. Ag/AgCl, reaching a maximum with a FE of formic acid of 92%. From this, it can be seen that the catalytic activity of the cerium oxide supported bismuth nano-catalyst provided by the embodiment of the present invention is much higher than that of the catalysts reported so far, such as S-In2O3derived In (production rate: 1449. mu. mol. h-1. cm-2, 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-2, FE: 87%), Pd nano inert gas pellets (production rate: 398. mu. mol. h-1. cm-2, FE: 97%).
referring to FIG. 8, the long term stability curve of the Bi/CeOx catalyst prepared in example 1 at-1.7V vs. Ag/AgCl in Na2SO4 electrolyte under the atmosphere of CO2 at normal temperature and pressure; 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 (10)
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 (NO3) 3.5H 2O into the solution C, and uniformly stirring to obtain a solution D; the added mass of the Bi (NO3) 3.5H 2O is 2-5 times of the mass of the carrier cerium oxide;
S03, slowly adding the Na2CO3 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;
And S05, placing the precursor in an inert gas/H2 mixed gas for calcining to obtain the cerium oxide supported bismuth nano catalyst.
2. the method of claim 1, wherein in step S03, the solute in the Na2CO3 solution is 0.8-1.2 times 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 as claimed in claim 1, wherein in step S05, the volume concentration of H2 in the inert gas/H2 mixed gas is 8-12%, the calcination temperature is 100-200 ℃, and the calcination time is 0.5-2H.
5. the method for preparing the cerium oxide supported bismuth nano-catalyst according to claim 1, wherein the method for preparing the supported cerium oxide comprises the following steps:
s11, dissolving Ce (NO3)3 & 6H2O in water to obtain a solution A;
s12, adding NaBH4 into the solution A, and uniformly stirring to obtain a solution B; the added mass of NaBH4 is 0.1-0.4 times of the mass of Ce (NO3) 3.6H 2O;
And S13, sequentially carrying out centrifugation, water washing, alcohol washing and drying on the solution B to obtain the carrier cerium oxide.
6. the method according to claim 5, wherein the drying temperature in step S13 is 50-70 ℃.
7. A cerium oxide-supported bismuth nanocatalyst prepared by the preparation method according to any one of claims 1 to 6.
8. use of the cerium oxide-supported bismuth nanocatalyst of claim 7 in the electrocatalytic reduction of CO2 to produce formic acid.
9. The application of the cerium oxide supported bismuth nano-catalyst as claimed in claim 8, wherein the method for producing formic acid by electrocatalytic reduction of CO2 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, dropwise adding the dispersion liquid onto carbon cloth to form a working electrode, respectively taking Ag/AgCl and a Pt net as a reference electrode and a counter electrode, and taking NaSO4 solution as electrolyte; then, CO2 is subjected to electrolytic reduction under the electrolytic voltage of-1.4 to-1.9V vs. Ag/AgCl to obtain formic acid.
10. the application of the cerium oxide supported bismuth nano catalyst as claimed in claim 9, 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) in terms of mg/mu L; the molar concentration of the NaSO4 solution is 0.1-0.3M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910836526.6A CN110538650B (en) | 2019-09-05 | 2019-09-05 | Cerium oxide supported bismuth nano catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910836526.6A CN110538650B (en) | 2019-09-05 | 2019-09-05 | Cerium oxide supported bismuth nano catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110538650A true CN110538650A (en) | 2019-12-06 |
| CN110538650B CN110538650B (en) | 2020-08-14 |
Family
ID=68712539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910836526.6A Active CN110538650B (en) | 2019-09-05 | 2019-09-05 | Cerium oxide supported bismuth nano catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110538650B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111564641A (en) * | 2020-05-25 | 2020-08-21 | 中自环保科技股份有限公司 | Preparation method of catalyst layer in membrane electrode |
| CN113463119A (en) * | 2021-06-15 | 2021-10-01 | 华东理工大学 | Bismuth-based-silver-based composite material and preparation method and application thereof |
| CN113755878A (en) * | 2021-08-31 | 2021-12-07 | 北京大学深圳研究生院 | Preparation method and application of bismuth-based catalyst |
| CN114717583A (en) * | 2022-04-19 | 2022-07-08 | 浙江师范大学 | Preparation method and application of bismuth nanosheet supported palladium bimetallic catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150057149A1 (en) * | 2013-08-23 | 2015-02-26 | Basf Corporation | Catalysts for Oxidation of Carbon Monoxide and/or Volatile Organic Compounds |
| CN109482172A (en) * | 2018-12-29 | 2019-03-19 | 陕西师范大学 | A kind of degradation NOxBi/CeO2Composite photo-catalyst and preparation method thereof |
-
2019
- 2019-09-05 CN CN201910836526.6A patent/CN110538650B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150057149A1 (en) * | 2013-08-23 | 2015-02-26 | Basf Corporation | Catalysts for Oxidation of Carbon Monoxide and/or Volatile Organic Compounds |
| CN109482172A (en) * | 2018-12-29 | 2019-03-19 | 陕西师范大学 | A kind of degradation NOxBi/CeO2Composite photo-catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ADHIDESH S.KUMAWAT ET AL.: ""Comparative study of carbon supported Pb,Bi and Sn catalysts for electroreduction of carbon dioxide in alkaline medium"", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| CONGYI WU ET AL.: ""Highly efficient hydrogenation of carbon dioxide to methyl formate over supported gold catalysts"", 《GREEN CHEMISTRY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111564641A (en) * | 2020-05-25 | 2020-08-21 | 中自环保科技股份有限公司 | Preparation method of catalyst layer in membrane electrode |
| CN113463119A (en) * | 2021-06-15 | 2021-10-01 | 华东理工大学 | Bismuth-based-silver-based composite material and preparation method and application thereof |
| CN113463119B (en) * | 2021-06-15 | 2022-09-09 | 华东理工大学 | Bismuth-based-silver-based composite material and preparation method and application thereof |
| CN113755878A (en) * | 2021-08-31 | 2021-12-07 | 北京大学深圳研究生院 | Preparation method and application of bismuth-based catalyst |
| CN114717583A (en) * | 2022-04-19 | 2022-07-08 | 浙江师范大学 | Preparation method and application of bismuth nanosheet supported palladium bimetallic catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110538650B (en) | 2020-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110538650A (en) | Cerium oxide supported bismuth nano catalyst and preparation method and application thereof | |
| CN110947374A (en) | Hydroxyl metal oxide nano catalyst and preparation method thereof | |
| CN111672514A (en) | Bifunctional electrocatalytic material and preparation method and application thereof | |
| CN109772336A (en) | A kind of porous double-metal hydroxide catalyst and its preparation method and application for the oxidation of electro-catalysis alcohols selectivity | |
| CN111495394A (en) | Carbon cloth loaded CoS2/MoS2Heterojunction composite material and preparation method and application thereof | |
| CN111001414A (en) | Structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and preparation method thereof | |
| CN109371419B (en) | V-doped Ni with self-assembled short rods into dendritic shape3S2/NF electrode material and preparation method thereof | |
| CN111883785B (en) | Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof | |
| CN111054343A (en) | Electrocatalytic oxygen evolution material and preparation method thereof | |
| CN111041508A (en) | Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof | |
| CN111777102A (en) | Metal oxide-based bifunctional water decomposition nano material and preparation method thereof | |
| CN112522731B (en) | Preparation method of lanthanum-copper nano composite catalyst applied to efficient carbon dioxide reduction reaction for generating ethylene | |
| CN113235125A (en) | Nickel-based NiCo2O4Electrocatalyst and its use in electrocatalytic oxidation of glycerol | |
| CN114452994A (en) | W-shaped steel plate18O49CoO/NF self-supporting electrocatalytic material and preparation method thereof | |
| CN116657186A (en) | Heterogeneous catalytic electrode for seawater full-electrolysis hydrogen production and preparation method and application thereof | |
| CN113981468B (en) | Multi-dimensional nickel-cobalt-based sulfide heterojunction electrocatalytic composite material and preparation method thereof | |
| CN114774977B (en) | Sulfur-doped nickel hydroxide-cerium dioxide composite nanorod array electrocatalyst, preparation method and application thereof | |
| CN111992219B (en) | Novel nickel-iron electrolyzed water oxygen production catalyst and preparation method thereof | |
| CN113151841A (en) | Preparation method of CoO @ carbon nanotube film with HER/OER (HER/OER) dual-functional catalytic activity | |
| CN114892203B (en) | Method for synthesizing carbon monoxide by electrochemical catalytic conversion of carbon dioxide | |
| CN113755888B (en) | Novel Co@CoP2CF full-water electrolytic catalyst | |
| CN115652357B (en) | Sulfur-doped yttrium ruthenate, preparation method thereof and oxygen evolution reaction electrode | |
| LU504052B1 (en) | Preparation and application of non-copper-based electrocatalyst for electrocatalysis of carbon dioxide to methane | |
| CN115029713B (en) | Preparation method of nickel-based MOF self-reconfigurable heterojunction for electrolytic water-oxygen evolution reaction, obtained product and application | |
| CN115094465B (en) | Mo-doped Co loaded by carbon cloth9S8Nanometer array composite material and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |