CN113802141B - Pd/PdO heterojunction catalyst, preparation method and application thereof - Google Patents

Pd/PdO heterojunction catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN113802141B
CN113802141B CN202111205619.2A CN202111205619A CN113802141B CN 113802141 B CN113802141 B CN 113802141B CN 202111205619 A CN202111205619 A CN 202111205619A CN 113802141 B CN113802141 B CN 113802141B
Authority
CN
China
Prior art keywords
pdo
catalyst
heterojunction
heterojunction catalyst
ammonia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111205619.2A
Other languages
Chinese (zh)
Other versions
CN113802141A (en
Inventor
聂华贵
罗文杰
陈倩倩
张潇栋
金玉威
周学梅
杨硕
杨植
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wenzhou University
Original Assignee
Wenzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wenzhou University filed Critical Wenzhou University
Priority to CN202111205619.2A priority Critical patent/CN113802141B/en
Publication of CN113802141A publication Critical patent/CN113802141A/en
Application granted granted Critical
Publication of CN113802141B publication Critical patent/CN113802141B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/27—Ammonia
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of electrocatalysis synthesis of ammonia, and particularly relates to a Pd/PdO heterojunction catalyst, a preparation method and application thereof. The invention also provides a simple and green method for preparing the Pd/PdO heterojunction catalyst, the material prepared by the method has high activity, high selectivity, more exposed active sites and controllable components, and the prepared Pd/PdO heterojunction catalyst can properly adsorb N at the interface of two phases 2 While inhibiting HER reaction, the 'synergistic effect' of heterojunction can make N 2 Reduction proceeds with a remote association mechanism at low overpotential. Experiments prove that the Pd/PdO heterojunction catalyst has excellent NRR performance. Thus, the heterojunction catalyzesThe agent exhibits the advantage of facilitating large-scale ammonia production in terms of catalyzing nitrogen reduction.

Description

Pd/PdO heterojunction catalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of electro-catalysis ammonia synthesis, and particularly relates to a Pd/PdO heterojunction catalyst, a preparation method and application thereof.
Background
Ammonia (NH) 3 ) Is an important chemical substance in industrial production, the most extensive application is chemical fertilizers, including directly applied nitrogen compounds such as anhydrous ammonia, urea, ammonium nitrate, ammonium phosphate and other agricultural raw materials, and the demand of ammonia in countries in the world, especially in the greater population of countries, is increasing year by year due to the degradation of the agriculturally available soil and the increasing dependence of crops on fertilizers. Ammonia may also be used to produce other compounds including explosives, plastics, synthetic fibers and resins, and the like. In addition, liquid ammonia absorbs a large amount of heat when vaporized, rapidly lowering the ambient temperature, and is therefore also commonly used as a refrigerant. Ammonia contains up to 17.6% hydrogen, compared to other energy carriers, and is ideally H 2 Compared with compressed hydrogen, the storage medium has the advantages that the storage energy consumption of ammonia is obviously reduced, and the transportation is more economical. More importantly, ammonia is the only carbon-free energy carrier so far, and no CO is discharged during final decomposition 2 Therefore, ammonia is of great strategic importance in future energy economy.
Today, the worldwide annual production of ammonia is over 4 million tons, 90% of which are the reduction of nitrogen and hydrogen to the traditional coal-or natural gas-based Haber-Bosch processAmmonia (N) 2 + 3H 2 ↔ 2NH 3 ) The process requires high temperature and high pressure>500 ℃，>300 bar), which is accompanied by a large consumption of fossil energy. Therefore, the development of a novel technology capable of synthesizing ammonia at normal temperature and pressure is urgently needed. In recent years, there have been breakthrough advances in artificial nitrogen fixation, and many artificial nitrogen fixation methods such as bamboo shoots in spring after rain, and among them, the methods widely used for achieving artificial nitrogen fixation at normal temperature and pressure include biological nitrogen fixation, photocatalytic synthesis of ammonia, and electrocatalytic synthesis of ammonia. The electrocatalysis synthesis of ammonia is regarded as the most promising method for realizing artificial nitrogen fixation at normal temperature and normal pressure due to the advantages of environmental protection, low energy consumption and the like.
The electrochemical nitrogen reduction (NRR) is nitrogen (N) dissolved in electrolyte solution by a catalyst under a specific potential at normal temperature and normal pressure 2 ) The novel technology for converting ammonia into ammonia has the advantages of low energy consumption, greenness, no pollution and the like, and is widely concerned by people. As is well known, N 2 Is an inert gas, has high nitrogen-nitrogen triple bond energy (941.69 kJ/mol), so that N is generated in the process of electrochemically synthesizing ammonia 2 Adsorption and activation at the catalyst surface is critical to affect the efficiency of the overall catalytic reaction. Meanwhile, in an aqueous electrolyte solution, because the overpotential of the Hydrogen Evolution Reaction (HER) and the overpotential of the nitrogen reduction reaction are very close, a severe HER competition reaction is often accompanied in the process of electrochemically synthesizing ammonia, so that the efficiency of electrocatalytic nitrogen reduction is reduced, and therefore, in addition to the research on how to improve the yield of ammonia, how to improve the selectivity of a catalyst to the nitrogen reduction reaction is another key problem of the research in the field. Therefore, it is necessary to develop a simple and inexpensive preparation method for obtaining a nitrogen reduction catalyst having high activity and selectivity.
Of the noble metal catalysts, palladium (Pd) is in group viii of the fifth period of the periodic table, and Pd is currently well-documented as a Hydrogen Evolution (HER) catalyst. There is great potential for applying Pd-based catalysts to NRRs. The use of Pd-based catalysts in NRR has been reported in the subject group, but their NRR performance is poor and the mechanism of catalysis is not clear.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a Pd/PdO heterojunction catalyst, a preparation method and application thereof.
The technical scheme adopted by the invention is as follows: a preparation method of a Pd/PdO heterojunction catalyst comprises the following steps:
(1) preparing a plating solution, wherein the plating solution is PdCl2 aqueous solution;
(2) and performing electrodeposition to obtain the Pd/PdO heterojunction catalyst.
Preferably, the oxide content in the heterojunction catalyst is regulated by introducing oxygen or argon during electroplating.
Preferably, the electrodeposition uses carbon cloth as the working electrode.
Preferably, the carbon cloth is obtained after hydrophilic treatment.
Preferably, the hydrophilic treatment comprises the following specific processes: and (3) placing the carbon cloth in a sulfuric acid solution, stirring, and after the treatment is finished, placing the carbon cloth in the sulfuric acid solution for storage and standby.
Preferably, before electroplating, the carbon cloth is electrochemically treated by cyclic voltammetry and then washed by deionized water.
Preferably, carbon cloth is used as a working electrode, a graphite rod is used as a counter electrode, a calomel electrode is used as a reference electrode in the electrodeposition process, and the CV method is utilized for electroplating.
The Pd/PdO heterojunction catalyst prepared by the preparation method of the Pd/PdO heterojunction catalyst is obtained.
The Pd/PdO heterojunction catalyst is applied as a catalyst in the electro-catalytic synthesis of ammonia.
The invention also provides a simple and green method for preparing the Pd/PdO heterojunction catalyst, the material prepared by the method has high activity, high selectivity, more exposed active sites and controllable components, and the prepared Pd/PdO heterojunction catalyst can properly adsorb N at the interface of two phases 2 While inhibiting HER response. The Pd/PdO heterojunction catalyst increases the affinity of Pd sites for N2, and is more favorable for forming Pd-N bonds and heterogeneouslyThe "synergistic effect" of the junction may be such that N is 2 Reduction proceeds with a remote association mechanism at low overpotential. Experiments prove that the Pd/PdO heterojunction catalyst has excellent NRR performance. Thus, the heterojunction catalyst exhibits advantages in catalyzing nitrogen reduction that facilitate large-scale ammonia production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
In FIG. 1, (a-b) and (c) are respectively the scanning electron microscope, transmission electron microscope and selected area electron diffraction pattern of the oxygen-poor catalysis sample, (d-e) and (f) are respectively the transmission electron microscope and selected area electron diffraction pattern of the medium-oxygen catalysis sample, and (g-h) and (i) are respectively the scanning electron microscope, transmission electron microscope and selected area electron diffraction pattern of the oxygen-rich catalysis sample;
FIG. 2 is a bar graph of elemental mapping ratio distribution of a scanning transmission electron microscope sample of medium oxygen catalyst;
FIG. 3 is an X-ray photoelectron spectrum of a sample of a medium oxygen catalyst;
FIG. 4 is a schematic view of an electrolysis apparatus;
FIG. 5 is a graph of UV-Vis spectra under different test conditions; respectively introducing argon gas to the working potential, introducing N2 to the open-circuit potential, introducing N2 to pure carbon cloth, and purifying the electrolyte;
in FIG. 6, (a, b) are ammonia standard curves and linear relations, and (c, d) are hydrazine standard curves and linear equations;
FIG. 7 is a graph of the nitrogen reduction performance of a medium oxygen catalytic material: (a) an ampere-hour curve under different potentials, (b) ultraviolet-visible spectra under different potentials, (c) ammonia yield and Faraday efficiency under different potentials, (d) an isotope-labeled nuclear magnetic resonance spectrogram, (e) a histogram of ammonia yield and Faraday efficiency of three catalysts, and (f) a catalyst stability test;
FIG. 8 is a UV-Vis spectrum (a) of by-produced hydrazine and the content (b) of hydrazine in the electrolyte solution;
FIG. 9 is a scanning electron microscope photograph of three catalysts after a catalytic reaction; (a-c) is a low-oxygen sample, (d-f) is a medium-oxygen sample, and (g-i) is an oxygen-rich sample.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1: preparation of medium oxygen Pd/PdO heterojunction catalyst
(1) Pretreatment of the carbon cloth: a carbon cloth (Taiwan carbon energy science and technology Co., Ltd., China) was cut into strips of 1X 2cm, stirred in a 1M sulfuric acid solution at 80 ℃ for 2 hours, and then stored in 0.5M sulfuric acid for further use. Before the material is deposited, in order to further remove impurities on the surface of the carbon cloth, the carbon cloth after hydrophilic treatment needs to be subjected to electrochemical treatment by Cyclic Voltammetry (CV) at a scanning speed of 10 mV/s within the range of-1.0V (vs.
(2) Preparing an electroplating solution: PdCl was added to deionized water (100 mL) 2 (0.0177 g). Store in brown reagent bottle for use.
(3) Preparation of Pd/PdO heterojunction catalyst: and (3) soaking the carbon cloth subjected to electrochemical treatment in the step (1) in the electroplating solution prepared in the step (2) diluted by 40 times with water, and electroplating by using a CV method by using a graphite rod as a Counter Electrode (CE), a calomel electrode as a Reference Electrode (RE) and bare carbon cloth as a Working Electrode (WE). The scanning potential is minus 0.1 to minus 0.8V, the scanning speed is 2mV/s, and the operating temperature is 25 ℃. The plating time is 1-200 min. And placing the prepared Pd/PdO heterojunction catalyst in deionized water for storage to obtain the medium oxygen (O-M) Pd/PdO heterojunction catalyst.
In addition, in the electroplating process, oxygen or argon is introduced to obtain the Pd/PdO heterojunction catalyst with different oxide contents. Specifically, other experimental conditions are unchanged, oxygen is introduced to enable the electrolyte solution to contain saturated oxygen, and then deposition is carried out to obtain the oxygen-enriched Pd/PdO heterojunction catalyst (O-R); and other experimental conditions are unchanged, the electrolyte solution contains saturated argon by introducing the argon, then deposition is carried out, and the argon is continuously introduced in the whole preparation process so as to avoid the oxidation by air as much as possible, and the oxygen-less Pd/PdO heterojunction catalyst (O-P) is obtained.
The micro-topography of the three catalysts synthesized therein is shown in fig. 1.
Wherein the elemental compositions of the medium oxygen Pd/PdO heterojunction catalyst are shown in FIGS. 2 and 3.
The following are electrochemical test procedures and results for the three catalysts.
1. Electrolytic cell device preparation
Before the electrocatalytic synthesis of ammonia, a Nafion 115 membrane (DuPont) is firstly placed in 5% H2O2 and 0.5M H2SO4 respectively and treated for 1H at 80 ℃, and then is washed clean by deionized water for standby. All electrochemical performance tests were performed at room temperature and pressure on the CHI 760E electrochemical workstation. The H-type cells were separated with a treated Nafion 115 membrane prior to testing.
The cell arrangement is shown in figure 4.
2. Electrochemical testing techniques
In the process of electro-catalysis ammonia synthesis, carbon cloth modified by a Pd/PdO heterojunction catalyst is used as a working electrode, a platinum net is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and 0.1M KOH containing saturated N2 or Ar is used as an electrolyte solution. Scanning the electrode modified by the Pd/PdO heterojunction catalyst at the speed of 10 mV/s by utilizing a Linear Sweep Voltammetry (LSV) method, and preliminarily judging whether the catalyst has the performance of catalyzing and synthesizing ammonia and the main tested potential range. N at a specific potential by Chronoamperometry (CA) 2 Reduction (all electrochemical tests were carried out in a three-electrode system H-type electrolytic cell), and product detection was carried out after 2H. All potentials in this patent are converted to relative RHE potentials by E (vs. RHE) = E (vs. Ag/AgCl) + 0.928V.
3. Quantitative detection of ammonia
And (3) carrying out quantitative detection on ammonia by adopting an indoxyl blue color reaction method. The specific mode is as follows: 2 mL of the electrolyte solution which is treated for 2 hours by the chronoamperometry is added into 2 mL of 1M NaOH solution (containing 5 wt% of salicylic acid and 5 wt% of sodium citrate), mixed evenly, added with 1 mL of 0.05M NaClO and 0.2 mL of 1 wt% of sodium nitroprusside, and reacted for 2 hours in a dark place. The absorption spectrum was measured with an ultraviolet-visible spectrophotometer. And (3) taking the absorbance at 655 nm as the quantitative analysis wavelength of ammonia in the electrolyte, carrying out an ammonia concentration-absorbance working curve according to the absorbance values of standard ammonium chloride solutions with different concentrations, and obtaining the ammonia yield in the electrolyte solution by using the working curve.
The ammonia working curve is shown in fig. 6 (a, b) and the uv-vis spectrum of ammonia is shown in fig. 7 (b), and the ammonia yield at each potential is calculated by linear fitting of the standard curve. Comparing three catalysts, the medium oxygen Pd/PdO heterojunction catalyst has the best catalytic performance. The maximum ammonia yield of the medium-oxygen Pd/PdO heterojunction catalyst is up to 11.0 mu g.h < -1mg < -1 > cat under the condition that the external potential is 0.03V vs. RHE, the Faraday Efficiency (FE) is up to 22.2 percent, and the good NRR catalytic performance of the Pd/PdO heterojunction catalyst sample is proved.
4. Determination of hydrazine
And (3) measuring the content of the hydrazine as a byproduct in the electrolyte by using a Watt-Crisers method. 2 g of 4-dimethylaminobenzaldehyde, 10 mL of 12 mol/L hydrochloric acid and 100mL of ethanol are mixed to obtain the color developing agent. This developer (5 mL) was added to the electrolyte (5 mL) after electrolysis, and the mixture was reacted at room temperature for 15 min. The absorbance of the resulting solution has a distinct characteristic peak at a wavelength of 455 nm. The specific hydrazine content can be calculated by utilizing the linear relation between the hydrazine concentration and the absorbance.
The working curve of hydrazine is shown in fig. 6 (c, d), and the ultraviolet-visible spectrum of hydrazine is shown in fig. 8, and it can be seen that no hydrazine is detected as a by-product in the electrolyte after catalytic reduction, indicating that the catalyst has good selectivity for the main product ammonia in the NRR process.
As can be seen,
5. ammonia Faraday efficiency calculation method
Faradaic=nVcF/it
i is the total current; n is the number of transfer electrons for producing 1mol of ammonia, and is 6; v is catholyte volume (mL); c is the ammonia concentration (M); f is the Faraday constant (96485 C.mol.) -1 ) (ii) a t is the electrolysis time. The Faraday Efficiency (FE) of the medium-oxygen Pd/PdO heterojunction catalyst is calculated to be as high as 22.2.
6.15N 2 Isotope labeling experiment
The isotope labeling experiment is key for verifying the performance of the catalyst, and 15N is used 2 Isotope labeling experiments were performed with 0.1M KOH electrolyte as the gas source (Sigma, 99 atom% 15N 2). Continuously reacting for 10 hours at the potential of 0.1V vs. RHE, taking 10 mL of electrolyte, adjusting the pH value to 3 with 0.5M H2SO4, and then heating to 70 ℃ and concentrating to 2 mL. 0.05 mL of DMSO-d was added to 0.95 mL of the concentrated solution 6 (99%) was used as an internal standard for 1H NMR testing (1 HNMR, Bruker Avance III 500 MHz).
The 1H NMR result is shown in FIG. 7 (d), and 15N is used 2 The labelled electrocatalytic reduction product 15NH was detected as a reactant in the reduced electrolyte solution 3 The result proves that the unique structure of the Pd/PdO heterojunction catalytic material can effectively promote N under normal temperature and normal pressure 2 Electrocatalytic conversion to ammonia.
7. Control experiment
To prove the effectiveness of the invention, a control experiment needs to be carried out on the results. Respectively introducing argon at working potential and introducing N at open-circuit potential 2 Pure carbon cloth through N 2 And testing the ultraviolet spectrum under the condition of pure electrolyte. The results are shown in FIG. 5, which shows that the effect of the present invention is not caused by contamination.
8. Durability is also an important indicator for evaluating good electrocatalysts. After 12 h of multiple cycles, the ammonia yield and FE can be kept at a higher level, and the decay rate is smaller, which indicates that the catalyst has good cycle stability and durability.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.

Claims (5)

1. A preparation method of a Pd/PdO heterojunction catalyst is characterized by comprising the following steps:
(1) pretreatment of the carbon cloth: carrying out hydrophilic treatment on the carbon cloth;
(2) preparing an electroplating solution: 0.0177g of PdCl was added to 100mL of deionized water 2 ；
(3) Preparation of Pd/PdO heterojunction catalyst: soaking the carbon cloth subjected to hydrophilic treatment in the step (1) in the electroplating solution diluted by 40 times by water and prepared in the step (2) to serve as a working electrode, and electroplating by using a CV (constant-voltage capacitor) method; the scanning potential is minus 0.1 to minus 0.8V, and the scanning speed is 2 mV/s; the plating time is 1-200 min; and placing the prepared Pd/PdO heterojunction catalyst in deionized water for storage to obtain the Pd/PdO heterojunction catalyst.
2. The method for preparing a Pd/PdO heterojunction catalyst as claimed in claim 1, wherein: the hydrophilic treatment comprises the following specific processes: and (3) placing the carbon cloth in a sulfuric acid solution, stirring, and after the treatment is finished, placing the carbon cloth in the sulfuric acid solution for storage and standby.
3. The method for preparing a Pd/PdO heterojunction catalyst as claimed in claim 1, wherein: in the electrodeposition process, a graphite rod is used as a counter electrode, and a calomel electrode is used as a reference electrode.
4. The Pd/PdO heterojunction catalyst prepared by the method for preparing the Pd/PdO heterojunction catalyst as defined in any one of claims 1 to 3.
5. Use of the Pd/PdO heterojunction catalyst of claim 4 as a catalyst in the electrocatalytic nitrogen synthesis of ammonia.
CN202111205619.2A 2021-10-15 2021-10-15 Pd/PdO heterojunction catalyst, preparation method and application thereof Active CN113802141B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111205619.2A CN113802141B (en) 2021-10-15 2021-10-15 Pd/PdO heterojunction catalyst, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111205619.2A CN113802141B (en) 2021-10-15 2021-10-15 Pd/PdO heterojunction catalyst, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113802141A CN113802141A (en) 2021-12-17
CN113802141B true CN113802141B (en) 2022-08-30

Family

ID=78897820

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111205619.2A Active CN113802141B (en) 2021-10-15 2021-10-15 Pd/PdO heterojunction catalyst, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113802141B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475093A (en) * 2014-11-26 2015-04-01 中国石油大学(北京) Pd/PdO nano particle loaded carbon nano tube composite material as well as preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475093A (en) * 2014-11-26 2015-04-01 中国石油大学(北京) Pd/PdO nano particle loaded carbon nano tube composite material as well as preparation method and application thereof

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
An overview on noble metal (Group VIII)-based heterogeneous electro-catalysts for the nitrogen reduction reaction;Qianqian Chen et al.;《Chemistry - An Asian Journal》;20201125;第4131-4152页 *
Construction of PdO–Pd interfaces assisted by laser irradiation for enhanced electrocatalytic N2 reduction reaction;Jiali Lv et al.;《J. Mater. Chem. A》;20190425;第12627-12634页 *
Pd/PdO Electrocatalysts Boost Their Intrinsic Nitrogen Reduction Reaction Activity and Selectivity via Controllably Modulating the Oxygen Level;Qianqian Chen et al.;《ACS Applied Materials & Interfaces》;20220429;第20988-20996页 *
Pulsed Electrodeposition of Palladium Thin-Film from Alkaline Solutions Containing Pd(II)–Cyanide Complexes: An Electrochemical and XPS Investigation;Innocenzo G. Casella;《Journal of The Electrochemical Society》;20080925;D723-D729页 *
基于Pd基异质结在电化学合成氨中的应用与研究;陈倩倩;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》;20220415;第B014-574页 *
电催化氮气还原合成氨催化材料研究进展;郑沐云等;《化工学报》;20200121(第06期);第2481-2491页 *
电沉积纳米钯修饰玻碳电极对甲醛的电催化氧化;上官灵芝等;《武汉大学学报(理学版)》;20081224(第06期);第661-664页 *

Also Published As

Publication number Publication date
CN113802141A (en) 2021-12-17

Similar Documents

Publication Publication Date Title
Meng et al. Electrosynthesis of urea from nitrite and CO2 over oxygen vacancy-rich ZnO porous nanosheets
Li et al. Recent progress of inorganic metal-based catalysts in electrocatalytic synthesis of ammonia
Xi et al. Water activation for boosting electrochemiluminescence
CN113136597B (en) Copper-tin composite material and preparation method and application thereof
Zhang et al. Unveiling Cutting‐Edge Developments in Electrocatalytic Nitrate‐to‐Ammonia Conversion
CN112430829A (en) MoS2Preparation method of/S-NiCoCr-LDH composite material
Kaneco et al. High-efficiency electrochemical CO 2-to-methane reduction method using aqueous KHCO 3 media at less than 273 K
CN113789526B (en) Method for preparing ammonia gas by nitric oxide electrochemical reduction
CN110639490A (en) Preparation method and application of porous carbon-based nitrogen reduction catalyst
CN112921351B (en) Preparation method and application of self-supporting catalytic electrode
Li et al. Introducing oxygen vacancies in a bi-metal oxide nanosphere for promoting electrocatalytic nitrogen reduction
CN109675640A (en) A kind of preparation method and application of carbon nitrogen base iron cobalt/cobalt oxide nano-cluster MOF catalyst
CN113582241A (en) Electrocatalytic material echinoid Co for ENRR3O4Preparation method of (1)
CN113802141B (en) Pd/PdO heterojunction catalyst, preparation method and application thereof
CN113862717B (en) Rose-type catalyst VS 2 @Bi 2 O 3 Preparation method of/CC and application thereof in nitrogen reduction
CN111632593A (en) Preparation method of ruthenium-rhodium alloy nano flower ball catalyst and application of ruthenium-rhodium alloy nano flower ball catalyst in electrocatalysis nitrogen reduction
CN113322487A (en) MoS based on supported electrocatalysis nitrogen reduction catalyst2-Fe3O4Preparation method of (1)
Wang et al. Halogen-induced planar defects in Cu catalysts for ammonia electrosynthesis at an ampere-level current density
CN113293400A (en) Electro-catalytic nitrogen reduction catalyst MoS2-Mo2Preparation method of C
CN112458485A (en) CoFe2O4/F-Ag2MoO4Method for preparing composite material
CN110721687A (en) Self-supporting porous Fe2O3Nanorod array electrocatalyst and preparation method thereof
CN113789541B (en) Phosphorus and oxygen co-doped copper-based catalyst and preparation method and application thereof
CN114703504B (en) Transition metal-loaded carbon fiber catalyst, preparation thereof and application thereof in electrocatalytic synthesis of hydrogen peroxide
CN113089019B (en) Preparation method of high-efficiency catalyst Ni/Fe/Cr-based composite material for oxygen evolution reaction
Wang et al. Recent Advances in Electrocatalytic Nitrogen Reduction to Produce Ammonia Under Ambient Conditions.

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant