CN110575835A - Self-supporting porous gold film nitrogen reduction electrocatalyst and preparation method thereof - Google Patents
Self-supporting porous gold film nitrogen reduction electrocatalyst and preparation method thereof Download PDFInfo
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 76
- 239000010931 gold Substances 0.000 title claims abstract description 76
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 33
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 26
- 235000019441 ethanol Nutrition 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002791 soaking Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012467 final product Substances 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 12
- 239000012498 ultrapure water Substances 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 48
- 239000010409 thin film Substances 0.000 claims description 33
- 239000010408 film Substances 0.000 claims description 32
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 42
- 229910021529 ammonia Inorganic materials 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009620 Haber process Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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Abstract
a self-supporting porous gold film nitrogen reduction electrocatalyst is prepared by a method comprising the following steps of preparing a piece of 0.1-4 cm2Soaking the foamed nickel in 1-6M hydrochloric acid solution for 5-30 min, removing a surface oxidation layer, washing with water and ethanol, and drying; preparing 5-50 mM chloroauric acid solution for later use; weighing 1-50 mg of PVP-co-PS, dissolving in 1-5 mL of tetrahydrofuran, adding 1-3 mL of absolute ethyl alcohol, 1-5 mL of ultrapure water and 1-4 mL of chloroauric acid solution, and magnetically stirring the prepared solution for 10-60 minutes; using foamed nickel as working electrode, using electrochemical workstation to make deposition at-0.3-0.7Vperforming electrodeposition for 500-4000 seconds under reduced pressure; and soaking the product in isopropanol for 10-14 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting porous gold film. The invention exhibits outstanding activity and stability.
Description
Technical Field
the invention relates to a self-supporting porous gold film nitrogen reduction electrocatalyst and a preparation method thereof, and the catalyst can be used for the research of electrocatalytic ammonia synthesis reaction.
Background
in order to maintain the geochemical nitrogen balance, it is necessary to convert atmospheric nitrogen into ammonia. Meanwhile, ammonia is a carbon-free substance, and has attracted wide attention due to the characteristics of high hydrogen density and low-pressure liquefaction. Industrially, the haber-bosch process is the leading technology for synthesizing ammonia by nitrogen catalytic hydrogenation. However, the process is catalyzed by an iron-based catalyst and also needs to be carried out under severe conditions (350-550 ℃, 150-350 atm), so that 1-2% of energy is globally required for industrial synthesis of ammonia every year (P.Wang, F.Chang, W.Gao, J.Guo, G.Wu, T.He, P.Chen, Nat.Chem.2016,9, 64; C.Choi, S.Back, N. -Y.Kim, J.Lim, Y. -H.Kim, Y.Jung, ACSCatal.2018,8, 7517-7525). There is therefore a continuing development of simple and sustainable alternative processes for the ammonia synthesis industry. At present, nitrogen is driven to be reduced into ammonia by electricity, and the ammonia can be synthesized under the environmental condition, so that the method is an optional method.
The key point of the electrochemical synthesis of ammonia is to design an efficient electrocatalyst. Although theoretical and experimental studies have confirmed that noble metals (e.g., rhodium, gold, ruthenium, palladium) are suitable catalysts for electrochemical synthesis of ammonia, the ammonia production efficiency and high faradaic efficiency of nitrogen reduction reactions are still low, and thus the need to develop high-performance active metal catalysts remains a great challenge. Recently, porous noble metals have proven to be effective electrocatalysts in electrochemical energy conversion and storage. Therefore, in the field of nitrogen reduction, porous noble metals are also a worthy direction to be explored. Traditionally, porous precious metals have been commonly alloyed and hard-templated (l.wang, y.yamauchi, j.am.chem.soc.2009,131, 9152-9153; h.wang, h.y.jeong, m.imura, l.wang, l.radhakushinan, n.fujita, t.castle, o.terasaki, y.yamauchi, j.am.chem.soc.2011,133, 14526-14529), but these synthetic processes are often very complicated and time consuming. In addition, most porous metal materials need to be fixed on the electrode surface with a high molecular binder during electrocatalysis, which reduces conductivity and prevents active site reactions. In response to these problems, the synthesis of porous metal thin films directly on conductive substrates is a promising approach. The use of block copolymers to construct porous gold films on three-dimensional porous metal foams can be used directly as binderless electrodes, a promising but difficult material to implement.
disclosure of Invention
The invention provides a self-supporting porous gold film nitrogen reduction electrocatalyst and a preparation method thereof, and the catalyst can be used for the research of electrocatalytic ammonia synthesis reaction.
The technical scheme adopted by the invention is as follows:
a self-supporting porous gold film nitrogen reduction electrocatalyst is prepared by the following method:
(1) Putting a block of 0.1-4 cm2Soaking the foamed nickel in 1-6M hydrochloric acid solution for 5-30 min, removing a surface oxidation layer, washing with water and ethanol, and drying;
(2) Preparing 5-50 mM chloroauric acid solution for later use;
(3) weighing 1-50 mg of PVP-co-PS, dissolving in 1-5 mL of tetrahydrofuran, adding 1-3 mL of absolute ethyl alcohol, 1-5 mL of ultrapure water and 1-4 mL of chloroauric acid solution, and magnetically stirring the prepared solution for 10-60 minutes;
(4) Taking foamed nickel as a working electrode, and performing electrodeposition for 500-4000 seconds at a deposition voltage of-0.3-0.7V by using an electrochemical workstation; and soaking the product in isopropanol for 10-14 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting porous gold film.
The choice of reaction conditions has a significant impact on the structure of the self-supporting porous gold film produced. The surface active agent PVP-co-PS plays an important role in preparing the self-supporting porous gold film, and as a micelle template, the surface active agent PVP-co-PS can adsorb a chloroauric acid precursor, and PS balls in the surface active agent PS can play a role in pore forming.
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) putting a block of 0.1-4 cm2Soaking the foamed nickel in 1-6M hydrochloric acid solution for 5-30 min, removing a surface oxidation layer, washing with water and ethanol, and drying；
(2) Preparing 5-50 mM chloroauric acid solution for later use;
(3) weighing 1-50 mg of PVP-co-PS, dissolving in 1-5 mL of tetrahydrofuran, adding 1-3 mL of absolute ethyl alcohol, 1-5 mL of ultrapure water and 1-4 mL of chloroauric acid solution, and magnetically stirring the prepared solution for 10-60 minutes;
(4) taking foamed nickel as a working electrode, and performing electrodeposition for 500-4000 seconds at a deposition voltage of-0.3-0.7V by using an electrochemical workstation; and soaking the product in isopropanol for 10-14 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting porous gold film.
Further, the concentration and volume of the chloroauric acid, the type of the surfactant, the volume of tetrahydrofuran, the deposition area of the foamed nickel, and the deposition voltage and time are controlled to control the morphology and structure of the gold catalyst.
Carrying out electrochemical catalytic nitrogen reduction reaction at normal temperature and normal pressure, wherein the performance test operation process comprises the following steps:
(1) Cut 0.25-1 cm2the gold thin film is used as a working electrode;
(2) The electrochemical ammonia synthesis experiment is carried out in an H-shaped electrolytic cell, a self-supporting porous gold catalyst is used as a working electrode, and a saturated Ag/AgCl electrode and a carbon rod are respectively used as a reference electrode and a counter electrode. Before testing, nitrogen is introduced into the solution for 30min until the solution is saturated by the nitrogen, test programs of a linear sweep cyclic voltammetry method and a chronoamperometry method are selected, and the current conditions of the working electrode under different potentials are monitored by a computer. And then testing the concentration of ammonia in the catalyzed electrolyte by an ultraviolet-visible spectrophotometer, and finally calculating the ammonia production rate and the Faraday efficiency of the catalyst.
the controllable preparation method of the self-supporting porous gold film nitrogen reduction electrocatalyst provided by the invention has the following main beneficial effects:
(1) the surface active agent PVP-co-PS is reasonably used as a soft template and a pore-forming agent, and the synthesized porous gold film has uniform appearance and high yield.
(2) the synthesis is simple, and the homogeneous porous gold film catalyst can be obtained in a short time by adopting the electrodeposition method.
(3) the synthesized porous gold film catalyst shows outstanding activity and stability in nitrogen reduction reaction and has very high application prospect.
Drawings
FIG. 1 is an SEM image of a porous gold thin film catalyst according to embodiment 1 of the present invention.
FIG. 2 is HRTEM image of porous gold thin film catalyst of embodiment 1 of the present invention
fig. 3 is an XRD pattern of the porous gold thin film catalyst according to embodiment 1 of the present invention.
FIG. 4 is an XPS plot of a porous gold thin film catalyst according to example 1 of the present invention.
FIG. 5 is a diagram showing the electric double layer capacitance of the porous gold thin film catalyst according to embodiment 1 of the present invention.
Fig. 6 is a graph showing the performance of the porous gold thin film catalyst in catalytic nitrogen reduction for ammonia production according to embodiment 1 of the present invention.
FIG. 7 is a graph showing the stability of the porous gold thin film catalyst according to embodiment 1 of the present invention.
FIG. 8 is an SEM image of a gold thin film catalyst according to embodiment 2 of the present invention.
Fig. 9 is a diagram showing an electric double layer capacitance of a gold thin film catalyst according to embodiment 2 of the present invention.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Referring to fig. 1 to 9, in this example, the performance test of nitrogen reduction of the gold catalyst was performed on a CHI 660E electrochemical workstation, and the operation process was as follows:
Firstly, shearing 0.25-1 cm2The gold thin film is used as a working electrode;
and secondly, performing an electrochemical ammonia synthesis experiment in an H-shaped electrolytic cell, wherein a self-supporting porous gold catalyst is used as a working electrode, and a saturated Ag/AgCl electrode and a carbon rod are respectively used as a reference electrode and a counter electrode. Before testing, nitrogen is introduced into the solution for 30min until the solution is saturated by the nitrogen, test programs of a linear sweep cyclic voltammetry method and a chronoamperometry method are selected, and the current conditions of the working electrode under different potentials are monitored by a computer. And then testing the concentration of ammonia in the catalyzed electrolyte by an ultraviolet-visible spectrophotometer, and finally calculating the ammonia production rate and the Faraday efficiency of the catalyst.
Example 1:
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) A block of 2cm2soaking the foamed nickel in 3M hydrochloric acid solution for 15min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) Preparing 20mM chloroauric acid solution for later use;
(3) Weighing 30mg of PVP-co-PS, dissolving the PVP-co-PS in 3mL of tetrahydrofuran, adding 1.5mL of absolute ethyl alcohol, 1.5mL of ultrapure water and 2mL of chloroauric acid solution, and magnetically stirring the prepared solution for 45 minutes;
(4) Taking foamed nickel as a working electrode, and electrodepositing for 2000 seconds at a deposition voltage of-0.5V by using an electrochemical workstation; and soaking the product in isopropanol for 12 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting porous gold film.
the SEM image of the obtained porous gold thin film catalyst is shown in fig. 1. The HRTEM of the obtained porous gold thin film catalyst is shown in fig. 2. The XRD pattern of the obtained porous gold thin film catalyst is shown in fig. 3. The XPS pattern of the obtained porous gold thin film catalyst is shown in fig. 4. The electric double layer capacitance diagram of the obtained porous gold thin film catalyst is shown in fig. 5. The performance diagram of the obtained porous gold thin film catalyst for preparing ammonia by catalytic nitrogen reduction is shown in figure 6. The stability of the obtained porous gold thin film catalyst is shown in fig. 7.
As seen from the SEM image, the surface of the porous gold film can clearly see a continuous pore structure, the pore diameter is 40-80 nm, and the thickness is 400 nm. By HRTEM and XRD analysis, the formation of a face-centered cubic structure of the metal is proved, and the porous gold film catalyst mainly exposes a (111) crystal face. The existence of zero-valent gold is analyzed by XPS, and the gold precursor is reduced into simple substance gold. The material has higher active specific surface area according to the double electric layer capacitance curve. Root of herbaceous plantAccording to the test calculation of an ultraviolet visible spectrophotometer, the ammonia production rate of the catalyst under the neutral condition (-0.2V) reaches 9.42 mu g h–1cm–2the Faraday efficiency reaches 13.36%.
example 2:
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) A block of 2cm2Soaking the foamed nickel in 3M hydrochloric acid solution for 15min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) preparing 20mM chloroauric acid solution for later use;
(3) Weighing 10mg of PVP, dissolving the PVP in 3mL of tetrahydrofuran, adding 1.5mL of absolute ethyl alcohol, 1.5mL of ultrapure water and 2mL of chloroauric acid solution, and magnetically stirring the prepared solution for 45 minutes;
(4) taking foamed nickel as a working electrode, and electrodepositing for 2000 seconds at a deposition voltage of-0.5V by using an electrochemical workstation; and soaking the product in isopropanol for 10 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting gold thin film catalyst.
the SEM image of the obtained gold thin film catalyst is shown in fig. 8, and the electric double layer capacitance image of the obtained gold thin film catalyst is shown in fig. 9.
As seen from the SEM image, the reaction formed a gold thin film, and no pore structure was observed on the surface. The material has higher active specific surface area according to the double electric layer capacitance curve.
example 3:
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) A block of 2cm2Soaking the foamed nickel in 3M hydrochloric acid solution for 15min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) Preparing 5mM chloroauric acid solution for later use;
(3) Weighing 30mg of PVP-co-PS, dissolving the PVP-co-PS in 3mL of tetrahydrofuran, adding 1.5mL of absolute ethyl alcohol, 1.5mL of ultrapure water and 2mL of chloroauric acid solution, and magnetically stirring the prepared solution for 45 minutes;
(4) taking foamed nickel as a working electrode, and electrodepositing for 2000 seconds at a deposition voltage of-0.5V by using an electrochemical workstation; and soaking the product in isopropanol for 14 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting gold thin film catalyst.
In the synthesis process, the concentration of chloroauric acid is too low, the reaction rate is slow, a uniform pore structure cannot grow on the surface of the foamed nickel, the thickness of the gold film is small, and a self-supporting porous gold film catalyst is difficult to obtain.
example 4:
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) A block of 2cm2Soaking the foamed nickel in 3M hydrochloric acid solution for 15min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) preparing a chloroauric acid solution with the concentration of 50mM for later use;
(3) Weighing 30mg of PVP-co-PS, dissolving the PVP-co-PS in 3mL of tetrahydrofuran, adding 1.5mL of absolute ethyl alcohol, 1.5mL of ultrapure water and 2mL of chloroauric acid solution, and magnetically stirring the prepared solution for 45 minutes;
(4) Taking foamed nickel as a working electrode, and electrodepositing for 2000 seconds at a deposition voltage of-0.5V by using an electrochemical workstation; and soaking the product in isopropanol for 12 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting gold thin film catalyst.
In the synthesis process, the concentration of the chloroauric acid is too high, the reaction rate is too high, a uniform pore structure cannot grow on the surface of the foamed nickel, the thickness of the gold film is very large, and the self-supported porous gold film catalyst is difficult to obtain.
Example 5
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) a block of 2cm2Soaking the foamed nickel in 3M hydrochloric acid solution for 15min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) Preparing 20mM chloroauric acid solution for later use;
(3) adding 3mL of absolute ethyl alcohol, 5mL of ultrapure water and 1mL of chloroauric acid solution into 5mL of tetrahydrofuran, and magnetically stirring the prepared solution for 60 minutes;
(4) taking foamed nickel as a working electrode, and electrodepositing for 4000 seconds at a deposition voltage of-0.7V by using an electrochemical workstation; and soaking the product in isopropanol for 12 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting gold thin film catalyst.
because no surfactant is used for pore forming, the obtained catalyst has no pore structure.
example 6
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) A block of 2cm2soaking the foamed nickel in 3M hydrochloric acid solution for 15min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) preparing 20mM chloroauric acid solution for later use;
(3) weighing 50mg of PVP-co-PS, dissolving in 1mL of tetrahydrofuran, and adding 4mL of chloroauric acid solution;
(4) taking foamed nickel as a working electrode, and performing electrodeposition for 500 seconds at a deposition voltage of-0.3V by using an electrochemical workstation; and soaking the product in isopropanol for 12 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting gold thin film catalyst.
because the added chloroauric acid solution is too much, the potential set in the electrodeposition process is too positive, the reaction rate is too slow, and the deposition time is too short, a self-supported porous gold thin film catalyst cannot be obtained.
example 7
A preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) A block of 4cm2Soaking the foamed nickel in 6M hydrochloric acid solution for 30min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) preparing a chloroauric acid solution with the concentration of 50mM for later use;
(3) weighing 50mg of PVP-co-PS, dissolving the PVP-co-PS in 5mL of tetrahydrofuran, adding 3mL of absolute ethyl alcohol, 5mL of ultrapure water and 4mL of chloroauric acid solution, and magnetically stirring the prepared solution for 60 minutes;
(4) Taking foamed nickel as a working electrode, and electrodepositing for 4000 seconds at a deposition voltage of-0.7V by using an electrochemical workstation; and soaking the product in isopropanol for 14 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting gold thin film catalyst.
because the hydrochloric acid concentration is too high in the pretreatment process of the foamed nickel, the treatment time is too long, the appearance of the foamed nickel is damaged, and the subsequent electrodeposition process is influenced, the self-supporting porous gold film catalyst is not easy to obtain.
example 8
a preparation method of a self-supporting porous gold film nitrogen reduction electrocatalyst comprises the following steps:
(1) A block of 0.1cm2soaking the foamed nickel in 1M hydrochloric acid solution for 5min to remove a surface oxidation layer, washing with water and ethanol, and drying;
(2) preparing 5mM chloroauric acid solution for later use;
(3) Weighing 1mg of PVP-co-PS, dissolving the PVP-co-PS in 1mL of tetrahydrofuran, adding 1mL of absolute ethyl alcohol, 1mL of ultrapure water and 1mL of chloroauric acid solution, and magnetically stirring the prepared solution for 10 minutes;
(4) Taking foamed nickel as a working electrode, and performing electrodeposition for 500 seconds at a deposition voltage of-0.3V by using an electrochemical workstation; and soaking the product in isopropanol for 10 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting gold thin film catalyst.
Because the hydrochloric acid concentration in the pretreatment process of the foamed nickel is too low, the treatment time is too short, and an oxide layer shown by the foamed nickel is not removed, the subsequent electrodeposition process is influenced, so that the self-supporting porous gold thin film catalyst is difficult to obtain.
Claims (3)
1. a self-supporting porous gold thin film nitrogen reduction electrocatalyst, characterized in that the catalyst is prepared by the following method:
(1) Putting a block of 0.1-4 cm2bulb ofSoaking the foamed nickel in 1-6M hydrochloric acid solution for 5-30 min, removing a surface oxidation layer, washing with water and ethanol, and drying;
(2) Preparing 5-50 mM chloroauric acid solution for later use;
(3) Weighing 1-50 mg of PVP-co-PS, dissolving in 1-5 mL of tetrahydrofuran, adding 1-3 mL of absolute ethyl alcohol, 1-5 mL of ultrapure water and 1-4 mL of chloroauric acid solution, and magnetically stirring the prepared solution for 10-60 minutes;
(4) Taking foamed nickel as a working electrode, and performing electrodeposition for 500-4000 seconds at a deposition voltage of-0.3-0.7V by using an electrochemical workstation; and soaking the product in isopropanol for 10-14 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting porous gold film.
2. A method of preparing the self-supporting porous gold thin film nitrogen reduction electrocatalyst according to claim 1, comprising the steps of:
(1) putting a block of 0.1-4 cm2Soaking the foamed nickel in 1-6M hydrochloric acid solution for 5-30 min, removing a surface oxidation layer, washing with water and ethanol, and drying;
(2) Preparing 5-50 mM chloroauric acid solution for later use;
(3) Weighing 1-50 mg of PVP-co-PS, dissolving in 1-5 mL of tetrahydrofuran, adding 1-3 mL of absolute ethyl alcohol, 1-5 mL of ultrapure water and 1-4 mL of chloroauric acid solution, and magnetically stirring the prepared solution for 10-60 minutes;
(4) taking foamed nickel as a working electrode, and performing electrodeposition for 500-4000 seconds at a deposition voltage of-0.3-0.7V by using an electrochemical workstation; and soaking the product in isopropanol for 10-14 hours, washing with water and ethanol, and drying to obtain the final product, namely the self-supporting porous gold film.
3. the method of claim 2, wherein the gold catalyst morphology and structure are controlled by controlling the concentration and volume of chloroauric acid, the type of surfactant, the volume of tetrahydrofuran, the area of nickel foam deposition, and the deposition voltage and time.
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| CN109126786A (en) * | 2018-09-27 | 2019-01-04 | 浙江工业大学 | A kind of flower-shaped Au catalyst of electrochemistry formated ammonia of structure-controllable and preparation method thereof |
| CN109234755A (en) * | 2018-10-30 | 2019-01-18 | 江苏大学 | A kind of layered double hydroxide composite construction elctro-catalyst and preparation method |
| CN109701550A (en) * | 2018-11-27 | 2019-05-03 | 浙江工业大学 | A kind of mesoporous platinum ruthenium film oxygen reduction electro-catalyst of nickel foam self-supporting and preparation method thereof |
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| CN109126786A (en) * | 2018-09-27 | 2019-01-04 | 浙江工业大学 | A kind of flower-shaped Au catalyst of electrochemistry formated ammonia of structure-controllable and preparation method thereof |
| CN109234755A (en) * | 2018-10-30 | 2019-01-18 | 江苏大学 | A kind of layered double hydroxide composite construction elctro-catalyst and preparation method |
| CN109701550A (en) * | 2018-11-27 | 2019-05-03 | 浙江工业大学 | A kind of mesoporous platinum ruthenium film oxygen reduction electro-catalyst of nickel foam self-supporting and preparation method thereof |
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