CN117821995A - Method for rapidly synthesizing heterostructure electrocatalyst by using Joule heat and application - Google Patents
Method for rapidly synthesizing heterostructure electrocatalyst by using Joule heat and application Download PDFInfo
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- CN117821995A CN117821995A CN202410253254.8A CN202410253254A CN117821995A CN 117821995 A CN117821995 A CN 117821995A CN 202410253254 A CN202410253254 A CN 202410253254A CN 117821995 A CN117821995 A CN 117821995A
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000004744 fabric Substances 0.000 claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 78
- 238000010438 heat treatment Methods 0.000 claims abstract description 74
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 4
- -1 rare earth metal ions Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 43
- 239000010949 copper Substances 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001994 activation Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000007725 thermal activation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Abstract
The invention discloses a method for rapidly synthesizing a heterostructure electrocatalyst by Joule heat and application thereof, comprising the following steps: (1) Carrying out Joule heat activation on the carbon cloth in vacuum or inert atmosphere to obtain an activated carbon cloth substrate; (2) Dipping the activated carbon cloth substrate in a precursor solution or dripping the precursor solution on the activated carbon cloth substrate to obtain a load carbon cloth; the precursor solution contains transition metal ions and/or rare earth metal ions; (3) And carrying out joule heating on the loaded carbon cloth in vacuum or inert atmosphere to obtain the metal simple substance/metal oxide heterostructure electrocatalyst. The method has the advantages of low raw material cost, simple and efficient synthesis process and contribution to batch realization. The metal simple substance/metal oxide electrocatalyst synthesized by the method has a heterostructure and excellent electrocatalytic activity.
Description
Technical Field
The application belongs to the technical field of catalyst preparation, and particularly relates to a method for rapidly synthesizing a heterostructure electrocatalyst by using joule heat and application of the heterostructure electrocatalyst.
Background
CO in the atmosphere 2 Is converted into important C1 and C2 chemicals (such as two-electron products of carbon monoxide, formic acid, and the like, multi-electron products of methane, ethylene, ethanol, and the like) by an electrocatalytic mode, and is used for reducing CO 2 An effective technical means for serious ecological problems caused by emission. However, electrocatalytic CO 2 The problems of high reaction overpotential, poor product selectivity, low stability and the like exist, so the design and preparation of the high-efficiency and low-cost electrocatalyst are the problems to be solved urgently. The existing effective electrocatalyst still takes noble metal as the main material, has extremely high cost, and needs a low-cost high-activity electrocatalyst to replace the noble metal electrocatalyst.
Disclosure of Invention
The purpose of the application is to provide a method for rapidly synthesizing a heterostructure electrocatalyst by using joule heat and application of the heterostructure electrocatalyst.
The application utilizes the joule heating method to rapidly synthesize the heterostructure electrocatalyst, applies an electric field to the carbon cloth loaded with the precursor, and rapidly synthesizes the heterostructure of the metal simple substance/metal oxide on the carbon cloth. The precursor solution is prepared from the salt solution of the transition metal and/or the rare earth metal, and compared with the noble metal, the precursor solution has excellent stability and high activity, and simultaneously has lower cost.
In one aspect, the present application provides a method for joule-heated rapid synthesis of a heterostructure electrocatalyst comprising:
(1) Carrying out Joule heat activation on the carbon cloth in vacuum or inert atmosphere to obtain an activated carbon cloth substrate;
(2) Dipping the activated carbon cloth substrate in a precursor solution or dripping the precursor solution on the activated carbon cloth substrate to obtain a load carbon cloth; the precursor solution contains transition metal ions and/or rare earth metal ions;
(3) And carrying out joule heating on the loaded carbon cloth in vacuum or inert atmosphere to obtain the metal simple substance/metal oxide heterostructure electrocatalyst.
In the step (1), the carbon cloth is subjected to Joule heat activation, and the catalytic activation of the carbon cloth substrate and the adhesiveness to a precursor can be improved at a high temperature. In the step (3), the carried carbon cloth is subjected to Joule heating, and the transient high temperature promotes the transition metal ion carbon in the precursor to be reduced into a metal simple substance, and the aggregation of the catalyst can be avoided due to the rapid pyrolysis of the precursor, so that the highly dispersed nano-scale heterostructure electrocatalyst can be obtained in extremely short treatment time. The obtained heterostructure electrocatalyst material fully utilizes the synergistic effect of metal simple substances and metal oxides to rearrange the surface charges of the catalyst, and efficient catalytic active sites are formed at the heterogeneous interfaces, so that the reaction kinetics of the catalyst can be improved.
In some specific embodiments, in the step (1), heating power for performing joule heat activation on the carbon cloth is 30-70W, constant voltage is 6-10V, heating time is 5-60 s, heating times are 2-4 times, and cooling is performed for 1-10 s after each heating, and then the next heating is performed.
In some embodiments, in step (2), the total concentration of metal ions in the precursor solution is from 0.05mol/L to 0.2mol/L.
In some embodiments, in step (2), the precursor solution is a salt solution of one or more of cerium, copper, silver.
Further, the precursor solution is nitrate solution of one or more of cerium, copper and silver.
In some specific embodiments, in the step (3), the heating power for joule heating the load carbon cloth is 30-70W, the voltage is 7-9V, the heating time is 5-60 s each time, the heating times are 2-4 times, and the temperature is reduced for 1-10 s each time and then the next heating is performed.
Further, the voltage for joule heating the load carbon cloth in the step (3) is 7V-8V or 8V-9V.
In some embodiments, before step (2), further comprising: dipping the activated carbon cloth substrate in a first precursor solution or dripping the first precursor solution on the activated carbon cloth substrate, and then carrying out Joule heating on the activated carbon cloth substrate in vacuum or inert atmosphere to obtain the Ti 0-loaded carbon cloth substrate 2 Is characterized by comprising an activated carbon cloth substrate; wherein the first precursor solution is a mixed solution of tetrabutyl titanate and isopropanol.
Further, the first precursor solution uses isopropanol, benzene, ethanol, methanol or diethyl ether as a solvent.
In another aspect, the present application also provides the use of the above-synthesized heterostructure electrocatalyst as CO 2 Use in electrocatalysts.
Compared with the prior art, the application has the following characteristics and beneficial effects:
1. the method has the advantages of low raw material cost, simple and efficient synthesis process, greatly shortened synthesis time, high heat utilization rate and contribution to batch realization.
2. The synthesized metal simple substance/metal oxide electrocatalyst has a heterostructure, and based on the synergistic effect of the metal simple substance and the metal oxide, the electric charges on the metal surface are promoted to be rearranged, and then different catalytic active sites are formed at the heterogeneous interface, so that the electrocatalytic activity of the electrocatalyst is promoted.
3. The method can avoid agglomeration of the electrocatalyst particles due to rapid pyrolysis of the precursor, and the synthesized electrocatalyst has excellent dispersibility and is beneficial to promoting improvement of the electrocatalytic activity.
Drawings
FIG. 1 is an XRD spectrum of a comparative sample;
FIG. 2 is an XRD spectrum of the sample of example 1;
FIG. 3 is an SEM image of a comparative sample;
FIG. 4 is an SEM image of a sample of example 1;
FIG. 5 is N 2 CO and CO 2 TiO under atmosphere 2 Reduction of CO by CC electrocatalyst 2 Cyclic voltammograms of (2);
FIG. 6 is a graph of linear sweep voltammograms for comparative and example electrocatalyst samples.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present application more apparent, the present application will be described in further detail with reference to examples and comparative examples.
Unless otherwise indicated, all solutions mentioned below refer to aqueous solutions.
Comparative example
The sample prepared in this comparative example was TiO 2 The procedure for the CC electrocatalyst is as follows:
step 1: cleaning the carbon cloth:
firstly, taking 3cm multiplied by 1cm carbon cloth, adding 200ml acetone, and ultrasonically cleaning for 30min; then placing carbon in 100ml of nitric acid solution, and ultrasonically cleaning for 15min; then placing carbon in deionized water for ultrasonic cleaning for 10min; finally, the carbon is arranged in absolute ethyl alcohol and ultrasonically cleaned for 10min. The cleaned carbon cloth is put into a vacuum drying oven and dried at 60 ℃.
Step 2: joule heat activation is carried out on the carbon cloth to obtain an activated carbon cloth substrate:
arranging carbon in vacuum, connecting two sides of carbon cloth through a copper electrode clamp, applying direct current according to constant voltage of 8V and power of 45W, and carrying out Joule heating on the carbon cloth to obtain the activated carbon cloth substrate. Heating for 60s each time for 3 times, cooling for 1s after heating, and heating for the next time. In the present application, the heating time is the energization time.
Step 3: tiO preparation by Joule heat 2 CC electrocatalyst:
(1) The following steps are carried out according to 17: mixing tetrabutyl titanate and isopropanol in a mass ratio of 33 to obtain a precursor solution, wherein the volume of the precursor solution is 200mL; dipping the activated carbon cloth substrate in the precursor solution and keeping stirring for 12 hours until the activated carbon cloth substrate is loaded with the precursor to obtain the loaded carbon cloth;
(2) Putting the loaded carbon cloth into a blast drying oven, and drying at 60 ℃;
(3) Arranging load carbon in vacuum, connecting two sides of load carbon cloth through copper electrode clamps, applying direct current according to 35W power and 7V constant voltage, and joule heating the load carbon cloth to obtain TiO 2 CC electrocatalyst. In order to improve the catalytic performance, the loaded carbon cloth is subjected to Joule heating for a plurality of times, the energizing time of each heating is 30s, the heating is performed for 3 times, and the temperature is reduced for 1s after the heating is completed, and then the next heating is performed.
XRD and SEM tests were performed on the samples of this comparative example, and the obtained XRD patterns and SEM patterns are shown in fig. 1 and 3, respectively. As can be seen from FIG. 1, tiO in the sample 2 Rutile phase, PDF card number 86-0147.
Example 1
The sample prepared in this example was Cu-CeO 2 The procedure for the CC electrocatalyst is as follows:
step 1: cleaning the carbon cloth:
firstly, taking 3cm multiplied by 1cm carbon cloth, adding 200ml acetone, and ultrasonically cleaning for 30min; then placing carbon in 100ml of nitric acid solution, and ultrasonically cleaning for 15min; then placing carbon in deionized water for ultrasonic cleaning for 10min; finally, the carbon is arranged in absolute ethyl alcohol and ultrasonically cleaned for 10min. The cleaned carbon cloth is put into a vacuum drying oven and dried at 60 ℃.
Step 2: joule heat activation is carried out on the carbon cloth to obtain an activated carbon cloth substrate:
3cm multiplied by 1cm carbon is arranged in vacuum, two sides of the carbon cloth are connected through a copper electrode clamp, direct current is applied according to constant voltage of 8V with power of 45W, and joule heating is carried out on the carbon cloth, so that an activated carbon cloth substrate is obtained. Heating for 60s each time for 3 times, cooling for 1s after heating, and heating for the next time.
Step 3: preparation of Cu-CeO by Joule heat 2 CC electrocatalysisThe preparation method comprises the following steps:
(1) Preparing 50mL of precursor solution, wherein the precursor solution is a mixed aqueous solution of cerium nitrate and copper nitrate, the molar ratio of the cerium nitrate to the copper nitrate is 1:2, and the total metal ion concentration in the precursor solution is 0.1mol/L; dipping the activated carbon cloth substrate in the precursor solution and keeping stirring for 12 hours until the activated carbon cloth substrate is loaded with the precursor to obtain the loaded carbon cloth;
(2) Putting the loaded carbon cloth into a blast drying oven, and drying at 60 ℃;
(3) Arranging load carbon in vacuum, connecting two sides of the load carbon cloth through a copper electrode clamp, applying direct current according to 45W power and 9V constant voltage, and carrying out Joule heating on the load carbon cloth to obtain Cu-CeO 2 CC electrocatalyst. In order to improve the catalytic performance, the loaded carbon cloth is subjected to Joule heating for a plurality of times, the energizing time of each heating is 30s, the heating is performed for 3 times, and the temperature is reduced for 1s after the heating is completed, and then the next heating is performed.
XRD and SEM tests were carried out on the sample of this example, and the XRD patterns and SEM patterns obtained are shown in FIG. 2, respectively. As can be seen from FIG. 2, the Cu in the sample is in the form of elemental copper and cuprous oxide, and the PDF card numbers Cu are 85-1326 and Cu 2 O: 99-0041。
Example 2
The sample prepared in this example was Ag-CeO 2 The procedure for the CC electrocatalyst is as follows:
step 1: cleaning the carbon cloth:
firstly, taking 3cm multiplied by 1cm carbon cloth, adding 200ml acetone, and ultrasonically cleaning for 30min; then placing carbon in 100ml of nitric acid solution, and ultrasonically cleaning for 15min; then placing carbon in deionized water for ultrasonic cleaning for 10min; finally, the carbon is arranged in absolute ethyl alcohol and ultrasonically cleaned for 10min. The cleaned carbon cloth is put into a vacuum drying oven and dried at 60 ℃.
Step 2: joule heat activation is carried out on the carbon cloth to obtain an activated carbon cloth substrate:
3cm multiplied by 1cm carbon is arranged in vacuum, two sides of the carbon cloth are connected through a copper electrode clamp, direct current is applied according to constant voltage of 8V with power of 45W, and joule heating is carried out on the carbon cloth, so that an activated carbon cloth substrate is obtained. Heating for 60s each time for 3 times, cooling for 1s after heating, and heating for the next time.
Step 3: preparation of Ag-CeO by using Joule heat 2 CC electrocatalyst:
(1) Preparing 50mL of precursor solution, wherein the precursor solution is a mixed aqueous solution of cerium nitrate and silver nitrate, the molar ratio of the cerium nitrate to the silver nitrate is 1:1, and the total metal ion concentration in the precursor solution is 0.1mol/L; dipping the activated carbon cloth substrate in the precursor solution and keeping stirring for 12 hours until the activated carbon cloth substrate is loaded with the precursor to obtain the loaded carbon cloth;
(2) Putting the loaded carbon cloth into a blast drying oven, and drying at 60 ℃;
(3) Arranging the load carbon in an argon atmosphere, connecting two sides of the load carbon cloth through a copper electrode clamp, applying direct current according to 45W power and 9V constant voltage, and carrying out Joule heating on the load carbon cloth to obtain Ag-CeO 2 CC electrocatalyst. In order to improve the catalytic performance, the loaded carbon cloth is subjected to Joule heating for a plurality of times, the energizing time of each heating is 30s, the heating is performed for 3 times, and the temperature is reduced for 1s after the heating is completed, and then the next heating is performed.
XRD test is carried out on the sample of the embodiment, the obtained XRD spectrum is shown in figure 2, and the Ag in the sample is represented by elemental copper, and the PDF card number is Ag 87-0717.
Example 3
The sample prepared in this example was Cu/TiO 2 The procedure for the CC electrocatalyst is as follows:
(1) Preparing a copper nitrate solution with the metal ion concentration of 0.1mol/L as a precursor solution, immersing a comparative sample in the precursor solution, and keeping stirring for 12 hours;
(2) Putting the impregnated carbon cloth into a blast drying oven, and drying at 60 ℃;
(3) Arranging carbon in nitrogen atmosphere, connecting two sides of carbon cloth by copper electrode clamp, applying direct current according to 45W power and 8V constant voltage, joule heating carbon cloth to obtain Cu/TiO 2 CC electrocatalyst. In order to improve the catalytic performance, the carbon cloth is subjected to Joule heating for a plurality of times, the energizing time of each heating is 30s, the heating is carried out for 3 times, and the temperature is reduced for 1s after the heating is finished, and then the next heating is carried out.
XRD and SEM tests were carried out on the sample of this example, and the obtained XRD patterns and SEM patterns are shown in FIGS. 1 and 4, respectively. As can be seen from fig. 1, tiO 2 Rutile phase, PDF card number: 86-0147; cu is simple substance copper, and PDF card number Cu is 85-1326. As can be seen from fig. 4, the nano particles are highly dispersed on the surface of the carbon cloth, so that the nano particles have good dispersibility, and the heterostructure has good uniformity, so that active site agglomeration on a heterogeneous catalytic interface can be avoided.
As can be seen from the XRD patterns of fig. 1 and 2, when the precursor is supported on the carbon cloth, the joule heat is generated by applying the direct current to the carbon cloth, and the hetero-phase-free hetero-structure can be obtained. Copper nitrate is reduced by carbon at high temperature to generate copper metal simple substance, meanwhile, a metal simple substance/metal oxide heterostructure is prepared in an ultra-fast Joule heating process by means of high affinity of Ce-O and Ti-O, and copper surface charges are rearranged by utilizing synergistic effect of the Ce-O and the Ti-O, so that different catalytic active sites are formed at an interface, and reaction kinetics and stability of the catalyst are improved. The carbon dioxide electroreduction activity of the catalyst can be characterized by electrochemical properties.
Comparative example sample TiO Using an H-cell 2 Electrochemical test is carried out on the/CC electrocatalyst, and the electrolyte is 0.1mol/L KHCO 3 Adopting a three-electrode system, wherein an Ag/AgCl electrode and a platinum sheet are respectively used as a reference electrode and a counter electrode, the cathode and the anode are separated by a Nafion117 proton exchange membrane, and the cathode side electrolyte is respectively passed through N 2 And CO 2 To compare TiO 2 CO by CC electrocatalyst 2 Is selected from the group consisting of (1). The test results are shown in FIG. 5, which shows the sample at CO 2 Atmosphere and N 2 Cyclic voltammogram under atmosphere, from which it can be seen that the sample is specific to CO 2 Is more remarkable.
Electrochemical tests were performed on the comparative and example samples using an H-cell with an electrolyte of 0.1 mol/LKHCO 3 Adopting a three-electrode system, wherein an Ag/AgCl electrode and a platinum sheet are respectively used as a reference electrode and a counter electrode, the cathode and the anode are separated by a Nafion117 proton exchange membrane, and the cathode side electrolyte passes through CO 2 . The test results are shown in FIG. 6, which shows the linearity of the sampleThe voltammetric curve is scanned. As can be seen from fig. 6, the performance of the single metal/metal oxide heterostructure electrocatalyst is significantly improved. TiO when the voltage is-1.2V (vs. RHE) 2 The current density of the/CC electrocatalyst was 14mA/cm 2 ，Cu-CeO 2 CC electrocatalyst and Ag-CeO 2 The current density of the/CC electrocatalyst was 16mA/cm 2 ，Cu/TiO 2 Current density of/CC is 30 mA/cm 2 。
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.
Claims (9)
1. A method for rapidly synthesizing a heterostructure electrocatalyst by joule heat, comprising:
(1) Carrying out Joule heat activation on the carbon cloth in vacuum or inert atmosphere to obtain an activated carbon cloth substrate;
(2) Dipping the activated carbon cloth substrate in a precursor solution or dripping the precursor solution on the activated carbon cloth substrate to obtain a load carbon cloth; the precursor solution contains transition metal ions and/or rare earth metal ions;
(3) And carrying out joule heating on the loaded carbon cloth in vacuum or inert atmosphere to obtain the metal simple substance/metal oxide heterostructure electrocatalyst.
2. The method for rapidly synthesizing a heterostructure electrocatalyst by joule heating according to claim 1, wherein:
in the step (1), heating power for performing Joule thermal activation on the carbon cloth is 30W-70W, constant voltage is 6V-10V, heating time is 5s-60s, heating times are 2-4 times, cooling is performed for 1s-10s after each heating, and next heating is performed.
3. The method for rapidly synthesizing a heterostructure electrocatalyst by joule heating according to claim 1, wherein:
in the step (2), the total concentration of metal ions in the precursor solution is 0.05mol/L to 0.2mol/L.
4. The method for rapidly synthesizing a heterostructure electrocatalyst by joule heating according to claim 1, wherein:
in the step (2), the precursor solution is a salt solution of one or more of cerium, copper and silver.
5. The method for rapidly synthesizing the heterostructure electrocatalyst by joule heating according to claim 4, wherein:
the precursor solution is nitrate solution of one or more of cerium, copper and silver.
6. The method for rapidly synthesizing a heterostructure electrocatalyst by joule heating according to claim 1, wherein:
in the step (3), the heating power of Joule heating is 30W-70W, the voltage is 7V-9V, the heating time is 5s-60s each time, the heating times are 2-4 times, the temperature is reduced for 1s-10s each time after each heating, and the next heating is performed.
7. The method for rapidly synthesizing a heterostructure electrocatalyst by joule heating according to claim 1, wherein:
the method further comprises the following steps before the step (2): dipping the activated carbon cloth substrate in a first precursor solution or dripping the first precursor solution on the activated carbon cloth substrate, and then carrying out Joule heating on the activated carbon cloth substrate in vacuum or inert atmosphere to obtain the Ti 0-loaded carbon cloth substrate 2 Is characterized by comprising an activated carbon cloth substrate;
the first precursor solution is a mixed solution of tetrabutyl titanate.
8. The method for rapidly synthesizing a heterostructure electrocatalyst by joule heating according to claim 7, wherein:
the first precursor solution takes isopropanol, benzene, ethanol, methanol or diethyl ether as a solvent.
9. Use of a synthetic heterostructure electrocatalyst according to any one of claims 1 to 8 as CO 2 Use in electrocatalysts.
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| JAEWAN AHN: "Rapid Joule Heating Synthesis of Oxide-Socketed High-Entropy Alloy Nanoparticles asCO2 Conversion Catalysts", ACS NANO, 25 May 2023 (2023-05-25) * |
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