CN111686719A - Palladium metal/carbon paper catalyst and preparation method and application thereof - Google Patents
Palladium metal/carbon paper catalyst and preparation method and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 86
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 230000007935 neutral effect Effects 0.000 claims abstract description 31
- 230000000694 effects Effects 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 20
- 238000006722 reduction reaction Methods 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 239000002159 nanocrystal Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 229920000557 Nafion® Polymers 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 230000035040 seed growth Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims 1
- 230000010757 Reduction Activity Effects 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 10
- 239000012456 homogeneous solution Substances 0.000 description 8
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 150000002829 nitrogen Chemical class 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108010020943 Nitrogenase Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention belongs to the field of new energy material technology and electrochemical catalysis, and particularly relates to a palladium metal/carbon paper catalyst and a preparation method and application thereof. The catalyst has catalytic activity on nitrogen reduction reaction under acidic neutral alkaline conditions, and is particularly prominent under neutral conditions, wherein the palladium nanocubes have high activity and good stability, and particularly have higher nitrogen reduction activity under low overpotential.
Description
Technical Field
The invention belongs to the field of new energy material technology and electrochemical catalysis, and particularly relates to a palladium metal/carbon paper catalyst and a preparation method and application thereof.
Background
NH as a raw material for the manufacture of fertilizers, explosives, pharmaceuticals, fuels, and the like3Plays an especially important role in agricultural production, chemistry and pharmacy and national defense safety. Currently, NH in the conventional industry3The production process of (A) relies mainly on the Haber-Bosch technique, in which process, except for NH3In addition to the formation, a large amount of CO is also accompanied2This, in turn, undoubtedly exacerbates the greenhouse effect. Furthermore, the technical requirements of high temperature and high pressure also require a lot of energy, so that the process is not economical and environmentally friendly in the long run. Over the past decades, scientists have studied various alternative methods of ammonia synthesis, including enzymatic reduction by nitrogenase; biological/inorganic hybrid photocatalytic methods, biomimetic colloidal gels, pure inorganic semiconductors, and electrocatalytic methods using precious metals, non-precious metal-based materials, and non-metallic materials. Wherein N is2The electrochemical reduction of (a) is favored because of its advantages of simplicity, sustainability, high energy conversion efficiency, and avoidance of the use of expensive reagents. However, although hitherto, N has been treated under room temperature conditions2Fixed studies have made some progress, but designed N2The immobilized electrocatalyst still maintains low activity, high potential and poor stability.
In order to achieve high activity and excellent stability of nitrogen reduction reaction catalysts (NRR), various electrocatalyst adjustment methods, such as element doping, defects, control of crystalline phases and surface modification, etc., have been implemented with the efforts of many researchers. Crystal plane control also greatly affects catalytic activity in many electrocatalytic reactions. However, currently, there is no systematic study on the relationship between electrocatalyst and NRR activity.
Disclosure of Invention
In view of the deficiencies of the prior art and the need for research and application in the art, it is an object of the present invention to provide a palladium nanocrystal catalyst that exposes different crystal planes; the method is characterized in that ascorbic acid is used as a reducing agent, palladium chloride acid is reduced into palladium metal with different morphologies by a seed growth method under hydrothermal conditions and different temperatures and potassium iodide concentrations are used as control conditions, and the palladium metal is a palladium nanocube surrounded by (100) crystal faces, a palladium octahedron surrounded by (111) crystal faces and a palladium dodecahedron surrounded by (110) crystal faces.
The second purpose of the invention is to provide a palladium nanocrystal catalyst with different exposed crystal faces for electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions under low overpotential:
dispersing 1.0mg palladium nano-crystal in a solution containing 0.5mL ethanol and 0.5mL H2O and 50. mu.L of Nafion (5 wt%) in ethanol Nafion, sonicating for 1 hour until a homogeneous solution is formed, dropping the resulting homogeneous solution onto a sheet of 1 × 1cm2The total load amount on the carbon paper is 0.2mg, and the carbon paper electrode is prepared and used for catalyzing the electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
(a) Nitrogen reduction activity of alkaline, neutral, acidic electrolytes
The nitrogen reduction activity of the palladium nanocubes surrounded by (100) crystal faces is measured by placing the palladium nanocubes in alkaline neutral acidic electrolyte, and the result shows that the activity is obviously higher in the neutral electrolyte, and the ammonia yield is 5-25 mu g mg under low overpotential-1 cath-1The Faraday efficiency is 0.5-40%.
(b) Nitrogen reduction activity at different potentials
The palladium nanocubes surrounded by (100) crystal faces were placed in a neutral electrolyte to measure the nitrogen reduction activity, and as a result, it was found that the activity was significantly higher at 0vvs. When the voltage range is-0.3 to 0.1V vs. RHE, the ammonia yield is 4 to 30 mu gmg-1 cath-1And the Faraday efficiency is 1-40%.
(c) Nitrogen reduction activity of different morphologies
Three palladium nanocrystallines are placed in neutral electrolyte to measure the nitrogen reduction activity of the three palladium nanocrystallines, and the palladium nanocubes surrounded by the (100) crystal faces have higher activity obviously. Under low overpotential, the ammonia yield is 4-30 mu gmg-1 cath-1And the Faraday efficiency is 1-40%.
The palladium metal/carbon paper catalyst provided by the invention is used for electrocatalytic nitrogen reduction, ascorbic acid is used as a reducing agent, palladium chloride palladium acid is reduced into palladium metal with different morphologies by a seed growth method under hydrothermal conditions and different temperatures and potassium iodide concentrations as control conditions, wherein the palladium metal is a palladium nanocube surrounded by a (100) crystal face, a palladium octahedron surrounded by a (111) crystal face and a palladium dodecahedron surrounded by a (110) crystal face, and the palladium nanocube is proved to be the catalyst with the best activity among the three.
The present invention is exemplified by palladium, which is reported to have NRR activity at low overpotentials. We studied systematically Pd nanocrystals by a seed-mediated growth method, selectively exposing the (100) planes, (111) planes and (110) planes of NRR under mild conditions, which appear as cubes, octahedrons and rhombohedrons, respectively. Experiments show that the Pd cube can realize high activity under low overpotential, only 0V vs. RHE is needed, and the activity can be realized in 0.1M Li2SO4To achieve 24.3 mug mg-1 cath-1NH of (2)3The yield and Faradaic Efficiency (FE) of 36.6% were 2.7 and 5.3 times higher than Pd octahedron and Pd rhombohedral, respectively. After 24 hours of stability testing, the activity of the catalyst decreased negligibly. Calculations of Density Functional Theory (DFT) further indicate that Pd (100) can lower NNH generation free energy and weaken nh adsorption, and barrier energy is lower, compared to the other two surfaces. In the presence of a catalyst consisting of NH3Formation of NH3Pd (100) may also form NH at a minimum voltage in the rate determining step of (1)3And exhibits a low energy barrier.
Compared with the prior art, the invention has the following main advantages and beneficial effects:
1) the palladium nanocrystalline catalyst material provided by the invention has the advantages that the raw materials are easy to purchase and prepare, the reaction conditions are easy to control, the equipment is simple, the operation is easy, and the preparation is convenient;
2) the palladium nanocrystalline catalyst material provided by the invention has good catalytic activity under alkaline neutral acidic conditions, and the neutral conditions are particularly prominent;
3) compared with the other two nanocrystals, the palladium nanocube catalyst material provided by the invention has better nitrogen reduction activity and has obvious advantages compared with the nitrogen reduction activity of the palladium metal catalyst reported in the current research;
4) the palladium nanocube catalyst material provided by the invention can realize the highest activity of the Pd metal catalytic nitrogen reduction reaction so far under a lower overpotential;
5) the stability of the palladium nanocube catalyst provided by the invention is proved, and the good catalytic activity of at least 24h can be maintained in the nitrogen reduction process;
drawings
FIG. 1 is a transmission electron microscope a, an octahedral transmission electron microscope b and a rhombic dodecahedron transmission electron microscope c of palladium nanocubes exposing different crystal planes obtained in example 1.
Fig. 2 is a linear sweep voltammogram of the Pd nanocubes obtained in example 1 in a saturated nitrogen and argon atmosphere in a lithium sulfate solution.
FIG. 3 is a graph of I-t of the Pd nanocubes obtained in example 1 under saturated nitrogen in a lithium sulfate solution.
FIG. 4 is a diagram showing the UV-VIS absorption spectra of Pd nanocubes obtained in example 1 at various potentials.
FIG. 5 shows the ammonia yield and the corresponding Faraday efficiency at each potential of the Pd nanocubes obtained in example 1.
FIG. 6 shows the stability test of the Pd nanocubes obtained in example 1; wherein the a-picture is six consecutive nitrogen reduction cycles of the Pd nanocubes at 0V vs. rhe in the lithium sulfate solution, and the b-picture is the results of twenty-four consecutive hours of nitrogen reduction testing of the Pd nanocubes at 0V vs. rhe in the lithium sulfate solution.
FIG. 7 shows the nitrogen reduction activity of palladium nanocrystals in the alkaline neutral acidic electrolyte obtained in example 2; wherein a is a linear sweep voltammogram of a Pd nanocube in N2 saturated 0.1M Li2SO4, 0.1M KOH and 0.1M HCl electrolyte, and the sweep rate is 20mV s-1; b is I-t diagram of Pd nanocubes in three solutions; the c-plot is the ammonia production and corresponding faradaic efficiency of Pd nanocubes at 0V vs. rhe in three solutions.
FIG. 8 shows the nitrogen reduction activity of palladium nanocrystals with different morphologies obtained in example 3; wherein a is a linear sweep voltammogram of cubic Pd (100), octahedral Pd (111) and dodecahedral Pd (110) with different morphologies in a lithium sulfate solution; b is an I-t diagram of three nanocrystals in three solutions; and c is a graph of ammonia yield and corresponding Faraday efficiency of the three nanocrystals at 0V vs.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples and drawings, which are not intended to limit the invention in any way.
Example 1:
reducing chloropalladate into palladium nanocrystals with different morphologies by a seed growth method under hydrothermal conditions and with different temperatures and potassium iodide concentrations as control conditions, wherein the palladium nanocrystals are respectively a palladium nanocube surrounded by a (100) crystal face, a palladium octahedron surrounded by a (111) crystal face and a palladium dodecahedron surrounded by a (110) crystal face; the method is applied to electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
Dispersing 1.0mg palladium nano-crystal in a solution containing 0.5mL ethanol and 0.5mL H2O and 50. mu.L of Nafion (5 wt%) in ethanol Nafion, sonicating for 1 hour until a homogeneous solution is formed, dropping the resulting homogeneous solution onto a sheet of 1 × 1cm2The total load amount on the carbon paper is 0.2mg, and the carbon paper electrode is prepared and used for catalyzing the electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
Nitrogen reduction activity at different potentials
The nitrogen reduction activity of the palladium nanocubes surrounded by the (100) crystal faces was measured by placing the nanocubes in a neutral electrolyte, and as a result, it was found that the activity was significantly higher at 0V vs. When the voltage range is-0.3 to 0.1V vs. RHE, the ammonia yield is 4 to 30 mu gmg-1 cath-1And the Faraday efficiency is 1-40%.
FIG. 1 is a transmission electron microscope a, an octahedral transmission electron microscope b and a rhombic dodecahedron transmission electron microscope c of palladium nanocubes exposing different crystal planes obtained in example 1. As can be seen from the graph a, the palladium nanocrystals mainly exposing the (100) crystal planes exhibit a cubic morphology, the palladium nanocrystals mainly exposing the (111) crystal planes exhibit a regular octahedral morphology, and the palladium nanocrystals mainly exposing the (110) crystal planes exhibit a rhombic dodecahedral morphology.
Fig. 2 is a linear sweep voltammogram of the Pd nanocubes obtained in example 1 in a saturated nitrogen and argon atmosphere in a lithium sulfate solution. As shown, the current density increased significantly below-0.3V vs. rhe, and dominated by Hydrogen Evolution (HER), so our nitrogen reduction reaction proceeded from 0.1V to-0.3V vs. rhe.
FIG. 3 is a graph of I-t of the Pd nanocubes obtained in example 1 under saturated nitrogen in a lithium sulfate solution. As shown, the current density decreases sequentially from 0.1V to-0.3V vs. rhe. Therefore, the NG/LDH catalyst shows good OER catalytic stability in an alkaline solution and has long service life.
FIG. 4 is a diagram showing the UV-VIS absorption spectra of Pd nanocubes obtained in example 1 at various potentials. Rhe has the highest absorption at 0V vs. rhe followed by-0.1V vs. rhe, which, in comparison, performs poorly at-0.3V vs. rhe.
FIG. 5 shows the ammonia yield and the corresponding Faraday efficiency at each potential of the Pd nanocubes obtained in example 1. The results showed that Pd nanocubes reached 24.3. mu.g mg-1 cath-1NH3Yield and faradaic efficiency of 36.6%.
Fig. 6 is a stability test of the Pd nanocubes obtained in example 1. Results in FIG. 6, a shows NH3The yield of the catalyst is changed little, and the corresponding Faraday efficiency is overall stable, which shows that the Pd nanocubular catalyst still keeps high activity after continuous 6 times of circulation. The results are shown in fig. 6 b, where the current density for 24h electrolysis varies little over time, again demonstrating the stability of the catalyst.
Example 2:
reducing chloropalladate into palladium nanocrystals with different morphologies by a seed growth method under hydrothermal conditions and with different temperatures and potassium iodide concentrations as control conditions, wherein the palladium nanocrystals are respectively a palladium nanocube surrounded by a (100) crystal face, a palladium octahedron surrounded by a (111) crystal face and a palladium dodecahedron surrounded by a (110) crystal face; the method is applied to electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
Dispersing 1.0mg palladium nano-crystal in the solution0.5mL ethanol, 0.5mL H2O and 50. mu.L of Nafion (5 wt%) in ethanol Nafion, sonicating for 1 hour until a homogeneous solution is formed, dropping the resulting homogeneous solution onto a sheet of 1 × 1cm2The total load amount on the carbon paper is 0.2mg, and the carbon paper electrode is prepared and used for catalyzing the electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
And (3) measuring the nitrogen reduction activity of the alkaline, neutral and acidic electrolyte:
the nitrogen reduction activity of the palladium nanocubes surrounded by (100) crystal faces is measured by placing the palladium nanocubes in alkaline neutral acidic electrolyte, and the result shows that the activity is obviously higher in the neutral electrolyte, and the ammonia production amount is 5-25 mu gmg under low overpotential-1 cath-1The Faraday efficiency is 0.5-40%.
FIG. 7 shows the nitrogen reduction activity of palladium nanocrystals in the alkaline neutral acidic electrolyte obtained in example 2. The nitrogen reduction activity of the palladium nanocubes surrounded by (100) crystal faces is measured by placing the palladium nanocubes in alkaline neutral acidic electrolyte, and the result shows that the activity is obviously higher in the neutral electrolyte, and the ammonia yield is 5-25 mu g mg under low overpotential-1 cath-1The Faraday efficiency is 0.5-40%.
Example 3:
reducing chloropalladate into palladium nanocrystals with different morphologies by a seed growth method under hydrothermal conditions and with different temperatures and potassium iodide concentrations as control conditions, wherein the palladium nanocrystals are respectively a palladium nanocube surrounded by a (100) crystal face, a palladium octahedron surrounded by a (111) crystal face and a palladium dodecahedron surrounded by a (110) crystal face; the method is applied to electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
Dispersing 1.0mg palladium nano-crystal in a solution containing 0.5mL ethanol and 0.5mL H2O and 50. mu.L of Nafion (5 wt%) in ethanol Nafion, sonicating for 1 hour until a homogeneous solution is formed, dropping the resulting homogeneous solution onto a sheet of 1 × 1cm2The total load amount on the carbon paper is 0.2mg, and the carbon paper electrode is prepared and used for catalyzing the electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
And (3) determining the nitrogen reduction activity of the palladium nanocrystals with different morphologies:
three palladium nanocrystallines are placed in neutral electrolyte to measure the nitrogen reduction activity of the three palladium nanocrystallines, and the palladium nanocubes surrounded by the (100) crystal faces have higher activity obviously. Under low overpotential, the ammonia yield is 4-30 mug mg-1 cath-1And the Faraday efficiency is 1-40%.
FIG. 8 shows the nitrogen reduction activity of palladium nanocrystals with different morphologies obtained in example 3. Three palladium nanocrystallines are placed in neutral electrolyte to measure the nitrogen reduction activity of the three palladium nanocrystallines, and the palladium nanocubes surrounded by the (100) crystal faces have higher activity obviously. Under low overpotential, the ammonia yield is 4-30 mug mg-1 cath-1And the Faraday efficiency is 1-40%.
Claims (7)
1. The palladium metal/carbon paper catalyst is characterized in that the catalyst is palladium nanocrystallines with different morphologies and comprises palladium nanocubes surrounded by (100) crystal faces, palladium octahedrons surrounded by (111) crystal faces and palladium dodecahedrons surrounded by (110) crystal faces.
2. The method of claim 1, comprising the steps of: the method is characterized in that ascorbic acid is used as a reducing agent, palladium chloride acid is reduced into palladium nano-crystals with different morphologies by a seed growth method under hydrothermal conditions and different temperatures and potassium iodide concentrations as control conditions, wherein the palladium nano-crystals are respectively a palladium nano-cube surrounded by a (100) crystal face, a palladium octahedron surrounded by a (111) crystal face and a palladium dodecahedron surrounded by a (110) crystal face.
3. The application of the palladium metal/carbon paper catalyst in the electrocatalytic nitrogen reduction reaction is characterized in that the catalyst is used for the electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
4. The application according to claim 3, wherein the specific steps of the application comprise: dispersing 1.0mg palladium nano-crystal in a solution containing 0.5mL ethanol and 0.5mL H2O and 50. mu.L of ethanol (5 wt.%) ofAdding Nafion solution, ultrasonic treating for 1 hr until uniform solution is formed, dropping the obtained uniform solution onto a sheet of 1 × 1cm2The total load amount on the carbon paper is 0.2mg, and the carbon paper electrode is prepared and used for catalyzing the electrocatalytic nitrogen reduction reaction under neutral, acidic and alkaline conditions.
5. Use according to claim 4, wherein the catalyst is most active in a neutral electrolyte; under the low overpotential of neutral, acidic and alkaline solutions, the ammonia yield is 5-25 mug mg-1 cath-1The Faraday efficiency is 0.5-40%.
6. Use according to claim 4, wherein the catalyst has a maximum activity at 0V vs. RHE; when the voltage range is-0.3-0.1V vs. RHE, the ammonia yield is 4-30 mug mg-1 cath-1And the Faraday efficiency is 1-40%.
7. Use according to claim 4, characterized in that the palladium nanocrystals surrounded by (100) crystal planes are the most active; under low overpotential, the ammonia production amount of the nanocrystal surrounded by the three crystal faces is 4-30 mu g mg-1 cath-1And the Faraday efficiency is 1-40%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775638A (en) * | 2010-03-24 | 2010-07-14 | 中国科学院长春应用化学研究所 | Preparation method of palladium nano crystal |
| CN105702973A (en) * | 2014-11-24 | 2016-06-22 | 中国科学院大连化学物理研究所 | Surface modification method of catalyst used for fuel cells |
| CN110302777A (en) * | 2018-03-20 | 2019-10-08 | 天津大学 | Palladium nano-particles-absorbent charcoal composite material and its application in carbon dioxide electro-catalysis reduction |
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| JYUN-SIAN YE，ET AL: ""Sequential and Transient Electrocatalysis of Glucose Oxidation Reactions by Octahedral, Rhombic Dodecahedral, and Cubic Palladium Nanocrystals"", 《ELECTROCHIMICA ACTA》 * |
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