CN114959788B - Preparation of aerophilic metal doped network PdH/C and application thereof in electrocatalytic oxidation of ethanol - Google Patents
Preparation of aerophilic metal doped network PdH/C and application thereof in electrocatalytic oxidation of ethanol Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 68
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 18
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical group [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 91
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000002484 cyclic voltammetry Methods 0.000 description 25
- 238000010586 diagram Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000012430 stability testing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 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
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- -1 palladium hydride Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
- C25B3/23—Oxidation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of an aerophilic metal doped network type PdH/C and application thereof in electrocatalytic oxidation of ethanol, wherein the preparation method is simple and one-step synthesis is adopted, the obtained M-PdH/C nano catalyst can exist stably under the environmental condition, has a complex network structure, and can expose more active sites to improve the catalytic performance. The introduction of the low-cost oxophilic metal reduces the cost and simultaneously ensures that the M-PdH/C nano catalyst prepared by the invention has higher quality activity and toxicity resistance compared with commercial Pd/C.
Description
Technical Field
The invention relates to the field of electrocatalytic of fuel cells, in particular to preparation of an oxygen-philic metal doped network type PdH/C and application thereof in electrocatalytic oxidation of ethanol.
Background
A Direct Ethanol Fuel Cell (DEFC) is a green energy device that uses ethanol as a fuel and can directly convert chemical energy into electrical energy. Ethanol is of great interest because of its abundance and low toxicity compared to other alcohol fuels. Palladium (Pd) has a superior potential in alkaline media as an anode catalyst. Current research is mainly focused on developing a high performance, low cost Pd-based catalyst.
It has been found that the introduction of other oxophilic metals or non-metals into Pd changes its electronic structure, which is advantageous in promoting the further oxidation of toxic intermediates, and in that the catalytic properties are correspondingly improved, hydrogen atoms being one example. Early palladium hydride (PdH) was obtained by treatment in a high pressure hydrogen atmosphere or with the addition of borohydride, but the resulting PdH structure was unstable and hydrogen in the palladium lattice was easily released under ambient conditions, which limited its search in the electrocatalytic field. Recent researches have found that certain solvents can release hydrogen in situ under specific conditions, the prepared PdH has a relatively stable structure, for example, stable PdH nanocubes are successfully prepared by N, N-Dimethylformamide (DMF), the electrocatalytic oxidation performance of methanol under alkaline conditions is promoted, but the poisoning resistance to carbon monoxide (CO) is weakened; researchers have also used the repeated addition of hydrazine solution (N) 2 H 4 ) The PdH nano catalyst is synthesized, and the activity and stability of formic acid oxidation are enhanced. The structure and composition of the catalyst can greatly affect its activity and selectivity. The large-area structure can expose more active sites, so that the catalytic activity of the structure is improved; the synergistic effect between the different components can also change the adsorption and desorption capacity of the catalyst to molecules in the reaction process. Therefore, replacing noble metals with partially inexpensive metals is an effective strategy to save costs while guaranteeing catalytic performance. Most of the PdH nanocatalysts reported in the literature are particle-based, but PdH having a network structure has not been reported yet.
Based on the problems, the design of the PdH nano catalyst with high activity, high toxicity resistance and low cost has important industrial application significance.
Disclosure of Invention
The invention aims to provide a preparation method of an aerophilic metal doped network type PdH/C and application thereof in electrocatalytic oxidation of ethanol so as to improve activity and stability of Pd-based catalysts.
The invention relates to a preparation method of an aerophilic metal doped network type PdH/C, which comprises the following steps:
step 1: palladium acetylacetonate (Pd (acac) 2 ) Placing the oxophilic metal precursor in a glass bottle, adding solvent 1-octadecene and amine solution, and performing ultrasonic dissolution to form uniformly dispersed solution;
step 2: placing the glass bottle in the step 1 into an oil bath pot, heating to 150-190 ℃ from room temperature, and reacting for 4-8 hours;
step 3: naturally cooling to room temperature after the reaction is finished, washing with a mixed solution of ethanol and cyclohexane, and centrifuging for several times to finally obtain the M-PdH nano catalyst (M= Fe, co, ni, bi) with a network structure;
step 4: and (3) placing activated carbon into cyclohexane for ultrasonic dispersion, adding the M-PdH nano catalyst obtained in the step (3) into the cyclohexane, continuing ultrasonic dispersion uniformly, washing and centrifuging with acetic acid and cyclohexane, and drying to obtain the M-PdH/C nano catalyst with a network structure. The load of the noble metal Pd is between 15 and 20 percent.
In step 1, the oxophilic metal precursor is selected from Fe (acac) 2 、Co(acac) 2 、Ni(acac) 2 Or Bi (OAc) 3 Preferably Bi (OAc) 3 。
In step 1, pd (acac) in the system 2 The concentration of the precursor of the oxophilic metal is 2mg/mL, and the concentration of the precursor of the oxophilic metal is 0.1 mg/mL-1 mg/mL. Further preferably, bi (OAc) 3 The optimal concentration of (C) is 0.24mg/mL.
In the step 1, the amine solution is oleylamine; and the volume ratio of the oleylamine to the 1-octadecene is 3:2. For example, the volume of oleylamine is 3mL and the volume of 1-octadecene is 2mL.
The application of the network-shaped PdH/C nano catalyst doped with the oxophilic metal is that the catalyst is used in the process of electrocatalytic oxidation of ethanol under alkaline conditions.
Specifically, a standard three-electrode system is used, a platinum sheet electrode is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and a net M-PdH-And the glassy carbon electrode of the C nano catalyst is a working electrode. The electrolyte contains 1mol/L KOH and 1mol/LC 2 H 5 The OH mixed solution was purged to saturation with nitrogen prior to testing. Cyclic voltammetry is carried out at a scanning rate of 0.05V/s within a potential range of-0.9-0.3V, and the cyclic voltammetry is compared with commercial Pd/C to explore the quality activity and the toxicity resistance of the cyclic voltammetry; and a stability test at-0.13V (vs Hg/HgO) was performed for 5000 seconds.
The beneficial effects of the invention are as follows:
under the solvothermal synthesis method, the M-PdH/C nano catalyst with a network structure is successfully prepared by adding palladium acetylacetonate and a precursor of an oxophilic metal into an amine and 1-octadecene system. The complex network structure can expose more active sites, and the introduction of the low-cost oxophilic metal not only reduces the preparation cost, but also further improves the ethanol oxidation performance under alkaline conditions by the synergistic effect of the oxophilic metal and palladium. Meanwhile, the introduction of the oxophilic metal also improves the antitoxic performance of the catalyst on toxic intermediates (such as CO), which shows that the catalyst has excellent stability in the electrocatalytic oxidation process.
Drawings
The technical solution of the present invention will be further described with reference to the accompanying drawings and examples, and it should be noted that these drawings are not limited to the scope of the present invention, but serve as an explanation of the technical solution of the present invention.
Fig. 1a is a transmission electron microscope image (TEM) of the PdH nanocatalyst prepared in example 1, and fig. 1b is a corresponding X-ray diffraction image (XRD).
FIG. 2a is a Cyclic Voltammogram (CV) of the PdH/C nanocatalyst prepared in example 1 and commercial Pd/C in 1mol/LKOH solution, FIG. 2b is a graph of the two in 1mol/LKOH and 1mol/LC 2 H 5 CV diagram in OH mixed solution.
FIG. 3 shows the PdH nanocatalyst prepared in example 1 and commercial Pd/C at 1mol/LKOH and 1mol/LC 2 H 5 Chronoamperometric graph in OH mixed solution.
Fig. 4a is a TEM image of the Bi-PdH nanocatalyst prepared in example 2, and fig. 4b is an XRD comparison image of the PdH in example 1 and the Bi-PdH nanocatalyst in example 2.
FIG. 5 is an X-ray photoelectron spectrum (XPS) of the Bi-PdH nanocatalyst prepared in example 2.
FIG. 6a is a CV diagram of the Bi-PdH/C nanocatalyst prepared in example 2 and commercial Pd/C in 1mol/LKOH solution, FIG. 6b is a CV diagram of the Bi-PdH/C nanocatalyst prepared in example 2 in 1mol/LKOH and commercial Pd/C in 1mol/L C 2 H 5 CV diagram in OH mixed solution.
FIG. 7 shows the PdH/C nanocatalyst prepared in example 2 and commercial Pd/C at 1mol/LKOH and 1mol/L C 2 H 5 Chronoamperometric graph in OH mixed solution.
FIG. 8a is a CV diagram of the Bi-PdH/C nanocatalyst prepared in example 3 and commercial Pd/C in 1mol/LKOH solution, FIG. 8b is a CV diagram of the Bi-PdH/C nanocatalyst prepared in example 3 in 1mol/LKOH and commercial Pd/C in 1mol/L C 2 H 5 CV diagram in OH mixed solution.
FIG. 9 shows the Bi-PdH/C nanocatalyst prepared in example 3 and commercial Pd/C at 1mol/L KOH and 1mol/LC 2 H 5 Chronoamperometric graph in OH mixed solution.
FIG. 10a is a CV diagram of the Bi-PdH/C nanocatalyst prepared in example 4 and commercial Pd/C in 1mol/LKOH solution, FIG. 10b is a CV diagram of the Bi-PdH/C nanocatalyst prepared in example 4 in 1mol/LKOH and commercial Pd/C in 1mol/L C 2 H 5 CV diagram in OH mixed solution.
FIG. 11 shows the Bi-PdH/C nanocatalyst prepared in example 4 and commercial Pd/C at 1mol/L KOH and 1mol/LC 2 H 5 Chronoamperometric graph in OH mixed solution.
FIG. 12 shows the M-PdH/C (M=Fe, co, ni) nanocatalyst prepared in example 5 at 1mol/LKOH and 1mol/LC 2 H 5 CV comparison graph in OH mixed solution.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific examples, and it should be noted that the following specific descriptions of examples are only for illustrating the synthesis, characterization and performance of the catalyst, and should not be construed as limiting the invention, and those examples not directly mentioned herein may still be obtained by combining these technical solutions.
Example 1:
the preparation method of the network-shaped PdH/C nano catalyst without the doping of the oxophilic metal comprises the following steps:
1. 10mg Pd (acac) was weighed out 2 2mL of 1-octadecene and 3mL of oleylamine are added into a glass bottle, the small cap is closed, and the ultrasonic treatment is performed for about 20 minutes until the precursor is completely dissolved to form a uniform mixture.
2. The mixture was placed in an oil bath, heated from room temperature to 170 ℃, and held for 6 hours.
3. After the reaction was completed, naturally cooled to room temperature, washed with a mixed solution of cyclohexane and ethanol, and the product was collected by centrifugation at 9300 rpm, and repeatedly operated three times, and the obtained product was dissolved in 5mL of cyclohexane for use.
4. 8.0mg of activated carbon is weighed into a centrifuge tube, 5mL of cyclohexane is added for ultrasonic treatment for 30 minutes, and the activated carbon is uniformly dispersed.
5. Adding the product obtained in step 3 into the active carbon dispersed in step 4, continuing to carry out ultrasonic treatment for 1 hour, centrifuging, washing with acetic acid and cyclohexane, finally washing once with cyclohexane, and drying the product to obtain the net-shaped PdH/C nano catalyst.
Fig. 1a is a TEM image of the PdH nanocatalyst prepared in example 1, and it can be seen that the sample exhibits an intertwined network structure. FIG. 1b is an XRD pattern of the PdH nanocatalyst prepared in example 1, showing that the XRD diffraction peak of the sample has significantly shifted negatively with respect to the metal Pd (JCPDS: 46-1043), indicating the formation of PdH, and that the negative shift of the diffraction peak can be attributed to the expansion of the Pd lattice due to the introduction of hydrogen.
FIG. 2a is a cyclic voltammogram of the PdH/C nanocatalyst prepared in example 1 and a commercial Pd/C in 1mol/LKOH solution; FIG. 2b shows the results of both KOH at 1mol/L and KOH at 1mol/L C 2 H 5 Cyclic voltammogram in OH mixed solution, can be seen and commercial Pd/C (0.77 Amg Pd -1 ) Compared with the PdH/C nano-catalyst, the catalyst has higher quality activity and reaches 3.80 and 3.80Amg Pd -1 About 5.0 times that of commercial Pd/C, indicating that the PdH/C nanocatalyst prepared in example 1 has better ethanol oxidation properties.
FIG. 3 shows the PdH/C nanocatalyst prepared in example 1 and commercial Pd/C at 1mol/LKOH and 1mol/L C 2 H 5 Timing current graph in OH mixed solution the PdH/C nanocatalyst prepared in example 1 still had higher current density after 5000 seconds stability test, indicating that it had higher stability during electrocatalytic oxidation, compared to commercial Pd/C.
Example 2:
the preparation of the bismuth-doped network-shaped Bi-PdH/C nano-catalyst in the embodiment comprises the following steps:
1. 10mg Pd (acac) was weighed out 2 And 1.2mg Bi (OAc) 3 2mL of 1-octadecene and 3mL of oleylamine are added into a glass bottle, the small cap is closed, and the ultrasonic treatment is performed for about 20 minutes until the precursor is completely dissolved to form a uniform mixture.
2. The mixture was placed in an oil bath, heated from room temperature to 170 ℃, and held for 6 hours.
3. After the reaction was completed, naturally cooled to room temperature, washed with a cyclohexane/ethanol mixed solution, and centrifuged at 9300 rpm to collect the product, and the operation was repeated three times to dissolve the obtained product in 5mL of cyclohexane for use.
4. 8.0mg of activated carbon is weighed into a centrifuge tube, 5mL of cyclohexane is added for ultrasonic treatment for 30 minutes, and the activated carbon is uniformly dispersed.
5. Adding the product obtained in step 3 into the active carbon dispersed in step 4, continuing to carry out ultrasonic treatment for 1 hour, centrifuging, washing with acetic acid and cyclohexane, finally washing once with cyclohexane, and drying the product to obtain the network Bi-PdH/C nano catalyst.
Fig. 4a is a TEM image of the Bi-PdH nanocatalyst prepared in example 2, and it can be seen that the sample still exhibits an intertwined network structure. FIG. 4b is an XRD contrast pattern of the Bi-PdH nanocatalyst of example 1 and example 2, where the XRD diffraction peak positions are substantially identical.
Fig. 5 is an XPS diagram of the Bi-PdH nanocatalyst prepared in example 2, in which the presence of bismuth element in the catalyst can be seen, and in combination with XRD and TEM patterns, it is shown that we have successfully prepared the Bi-PdH nanocatalyst having a network structure.
FIG. 6a is a cyclic voltammogram of the Bi-PdH/C nanocatalyst prepared in example 2 and a commercial Pd/C in 1mol/LKOH solution; FIG. 6b shows the results of the two reactions at 1mol/LKOH and 1mol/L C 2 H 5 Cyclic voltammogram in OH mixed solution, can be seen and commercial Pd/C (0.77 Amg Pd -1 ) Compared with Bi-PdH/C nano-catalysis, the nano-catalyst has higher quality activity, and reaches 8.02Amg Pd -1 About 10.4 times that of commercial Pd/C, indicating that the PdH/C nanocatalyst prepared in example 2 has better ethanol oxidation properties.
FIG. 7 shows the Bi-PdH/C nanocatalyst prepared in example 2 and commercial Pd/C at 1mol/L KOH and 1mol/LC 2 H 5 The timing current graph in the OH mixed solution shows that the Bi-PdH/C nanocatalyst prepared in example 2 still has higher current density after 5000 seconds of stability testing, indicating that it has higher stability during electrocatalytic oxidation, as compared to commercial Pd/C.
Example 3:
Bi-PdH/C nanocatalyst was prepared according to the method described in example 2, leaving the other conditions unchanged, and only Bi (OAc) 3 The mass of (2) was changed to 2.4mg.
FIG. 8a is a cyclic voltammogram of the Bi-PdH/C nanocatalyst prepared in example 3 and a commercial Pd/C in 1mol/LKOH solution; FIG. 8b shows the results of the two reactions at 1mol/LKOH and 1mol/L C 2 H 5 Cyclic voltammogram in OH mixed solution, can be seen and commercial Pd/C (0.77 Amg Pd -1 ) Compared with Bi-PdH/C nano-catalysis, the nano-catalyst has higher quality activity, and reaches 6.30Amg Pd -1 8.1 times that of commercial Pd/C, indicating that the PdH/C nanocatalyst prepared in example 3 has better ethanol oxidation properties.
FIG. 9 shows the Bi-PdH/C nanocatalyst prepared in example 3 and commercial Pd/C at 1mol/L KOH and 1mol/LC 2 H 5 The timing current profile in the OH mixture solution shows that the Bi-PdH/C nanocatalyst prepared in example 3 still has higher current density after 5000 seconds of stability testing, indicating that it has higher stability during electrocatalytic oxidation, compared to commercial Pd/CSex.
Example 4:
Bi-PdH/C nanocatalyst was prepared according to the method described in example 2, leaving the other conditions unchanged, and only Bi (OAc) 3 The mass of (2) was changed to 0.6mg.
FIG. 10a is a cyclic voltammogram of the PdH/C nanocatalyst prepared in example 4 and a commercial Pd/C in 1mol/LKOH solution; FIG. 10b shows the results of the two reactions at 1mol/LKOH and 1mol/L C 2 H 5 Cyclic voltammogram in OH mixed solution, can be seen and commercial Pd/C (0.77 Amg Pd -1 ) Compared with Bi-PdH/C nano-catalysis, the nano-catalyst has higher quality activity and reaches 6.16Amg Pd -1 8.0 times that of commercial Pd/C, indicating that the PdH/C nanocatalyst prepared in example 4 has better ethanol oxidation properties.
FIG. 11 shows the Bi-PdH/C nanocatalyst prepared in example 4 and commercial Pd/C at 1mol/L KOH and 1mol/LC 2 H 5 The timing current graph in the OH mixed solution shows that the Bi-PdH/C nanocatalyst prepared in example 4 still has higher current density after 5000 seconds of stability testing, indicating that it has higher stability during electrocatalytic oxidation, as compared to commercial Pd/C.
Example 5:
preparation of iron, cobalt, nickel oxophilic Metal doped network PdH/C nanocatalyst according to the method described in example 2, leaving the other conditions unchanged, bi (OAc) alone 3 2.3mg of Fe (acac) was respectively replaced 2 2.2mg Co (acac) 2 2.0mg of Ni (acac) 2 。
FIG. 12 shows the M-PdH/C (M=Fe, co, ni) nanocatalyst prepared in example 5 at 1mol/LKOH and 1mol/LC 2 H 5 Comparison of cyclic voltammograms in OH mixed solution shows that the catalyst prepared in example 5 has higher mass activity than commercial Pd/C, indicating that doping other oxophilic metals can also enhance the ethanol oxidation performance of the PdH/C nanocatalyst.
Claims (3)
1. The application of the network-shaped PdH/C nano catalyst doped with the oxophilic metal is characterized in that:
the network-shaped PdH/C nano catalyst doped with the oxophilic metal is used as a catalyst in the process of electrocatalytic oxidation of ethanol under an alkaline condition;
the network-shaped PdH/C doped with the oxophilic metal is prepared by the following steps:
step 1: placing palladium acetylacetonate and an oxophilic metal precursor into a glass bottle, adding a solvent 1-octadecene and an amine solution, and performing ultrasonic dissolution to form a uniformly dispersed solution;
step 2: placing the glass bottle in the step 1 in an oil bath pot, heating to 150-190 ℃ from room temperature, and reacting for 4-8 hours;
step 3: naturally cooling to room temperature after the reaction is finished, washing with a mixed solution of ethanol and cyclohexane, and centrifuging for several times to finally obtain the M-PdH nano catalyst with a network structure, wherein M=Fe, co, ni or Bi;
step 4: placing activated carbon into cyclohexane for ultrasonic dispersion, adding the M-PdH nano catalyst obtained in the step 3 into the cyclohexane, continuing ultrasonic dispersion uniformly, washing and centrifuging with acetic acid and cyclohexane, and drying to obtain the M-PdH/C nano catalyst with a network structure;
in step 1, the oxophilic metal precursor is selected from Fe (acac) 2 、Co(acac) 2 、Ni(acac) 2 Or Bi (OAc) 3 ；
In step 1, pd (acac) in the system 2 The concentration of the precursor of the oxophilic metal is 2mg/mL, and the concentration of the precursor of the oxophilic metal is 0.1 mg/mL-1 mg/mL;
in the step 1, the amine solution is oleylamine.
2. The use according to claim 1, characterized in that:
the volume ratio of the amine solution to the 1-octadecene is 3:2.
3. The use according to claim 1, characterized in that:
using a standard three-electrode system, taking a platinum sheet electrode as a counter electrode, a Hg/HgO electrode as a reference electrode, and a glassy carbon electrode with a netlike M-PdH/C nano catalyst coated on the surface as a reference electrodeWorking electrode, electrolyte is formed by KOH and C 2 H 5 Mixed solution of OH.
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