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CN-122013239-A - Low-antimony palladium-based catalyst for electrocatalytic carbon dioxide reduction, preparation method and application

CN122013239ACN 122013239 ACN122013239 ACN 122013239ACN-122013239-A

Abstract

The invention discloses a trace antimony (Sb) -doped palladium (Pd) base catalytic material and a preparation method and application thereof, and belongs to the technical field of electrocatalytic carbon dioxide reduction. The catalytic material is prepared by adding a structure directing agent into an alkaline mixed solvent by taking a palladium precursor and an antimony precursor as metal sources and adopting a one-step solvent hydrothermal method. According to the invention, trace Sb elements are introduced, so that the electronic structure of Pd is effectively regulated and controlled, and the adsorption behavior of a reaction intermediate is optimized, thereby remarkably improving the performance of Pd in the electrocatalytic carbon dioxide reduction reaction. Electrochemical tests show that under neutral conditions (0.5M KHCO 3 ), the catalytic material can improve the Faraday efficiency of Pd carbon monoxide from 40% to 80%, and has excellent catalytic activity and good stability. The method has the advantages of simple synthesis process, mild conditions and good repeatability, and the obtained catalytic material has a controllable structure and wide application prospect in the field of electrocatalytic carbon dioxide reduction.

Inventors

  • ZHANG TINGTING
  • FAN KE

Assignees

  • 武汉科技大学

Dates

Publication Date
20260512
Application Date
20260323

Claims (8)

  1. 1. A trace amount of antimony (Sb) doped palladium (Pd) base catalytic material for electrocatalytic carbon dioxide reduction is characterized by having a nano-aggregation structure, wherein the chemical formula of the Pd base catalytic material is Pd x Sb, the doping amount of Sb is kept constant, x is the relative content of Pd, the value range of x is 30-70, pd is taken as a main active component of the catalytic material, and the electronic structure of Pd is regulated and controlled by introducing Sb, so that the adsorption behavior of a reaction intermediate is optimized, and the catalyst with excellent catalytic performance is obtained.
  2. 2. A micro-Sb-doped Pd-based catalyst for electrocatalytic carbon dioxide reduction as set forth in claim 1, wherein the preferred structure of the Sb-doped Pd-based catalyst Pd x Sb is Pd 50 Sb.
  3. 3. The micro-Sb-doped Pd-based catalyst for electrocatalytic carbon dioxide reduction as set forth in claim 1, wherein the Sb-doped Pd-based catalyst is in a black powder state, and the nanocluster particle size of the Sb-doped Pd-based catalyst is 20-80nm.
  4. 4. A method for preparing a micro Sb-doped Pd-based catalyst for electrocatalytic carbon dioxide reduction according to any one of claims 1-3, comprising the steps of: Firstly, mixing a palladium precursor and an antimony precursor with an alkaline solution prepared from KOH, N-N Dimethylformamide (DMF) and ethylene glycol, then adding a structure directing agent, and uniformly stirring to obtain a mixed solution, wherein the molar ratio of the palladium precursor to the antimony precursor is 30-70:1, and the adding amount of the antimony precursor is kept constant. And secondly, transferring the mixed solution obtained in the first step into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6-12 hours at 120-250 ℃. And thirdly, centrifugally separating a product obtained by the reaction, alternately washing the product with deionized water and ethanol for a plurality of times, and then drying the product in a vacuum drying oven to obtain the trace Sb-doped Pd-based catalytic material.
  5. 5. The method of preparing a micro-Sb-doped Pd-based catalyst for electrocatalytic carbon dioxide reduction as set forth in claim 4, wherein in the first step, the Pd precursor is at least one selected from sodium chloropalladate, palladium nitrate and palladium acetate, and the Sb precursor is at least one selected from antimony trichloride, antimony acetate and antimony oxide.
  6. 6. The method of preparing a micro-Sb-doped Pd-based catalyst for electrocatalytic carbon dioxide reduction of claim 4, wherein the molar ratio of the palladium precursor to the antimony precursor in the first step is 50:1.
  7. 7. The method for preparing a trace amount of Sb-doped Pd-based catalyst for use in electrocatalytic carbon dioxide reduction as set forth in claim 4, wherein in the third step, the drying temperature is 50-80℃and the drying time is 6-10 hours.
  8. 8. Use of a micro Sb-doped Pd-based catalyst for electrocatalytic carbon dioxide reduction according to any one of claims 1 to 3, for electrocatalytic carbon dioxide reduction to carbon monoxide.

Description

Low-antimony palladium-based catalyst for electrocatalytic carbon dioxide reduction, preparation method and application Technical Field The invention belongs to the technical field of electrocatalytic carbon dioxide reduction reaction under alkaline conditions, and relates to a trace antimony doped palladium-based catalytic material, a preparation method and application of the material in high-efficiency stable electrocatalytic carbon dioxide reduction reaction under alkaline conditions. Technical Field The electrocatalytic carbon dioxide reduction reaction (CO 2 RR) can utilize renewable energy sources to convert CO 2 into high value-added fuels and chemicals, which is an important way to realize carbon resource recycling. Wherein carbon monoxide (CO) is used as a key component of synthesis gas, and the high-selectivity preparation of the carbon monoxide (CO) has remarkable industrial value (Liu Z, Qian J, Zhang G, et al. Electrochemical CO2-to-CO conversion: A comprehensive review of recent developments and emerging trends[J]. Separation and Purification Technology, 2024, 330: 125177.). Palladium (Pd) -based catalysts are of great interest because of their unique electronic structure and product tunability, and can produce formic acid or CO with high selectivity at different potential intervals. However, pd-based catalysts face a key bottleneck in the process of preparing CO, namely, pd surface is too strong for adsorbing a CO intermediate, so that a product cannot be desorbed in time, an active site is occupied, catalyst poisoning is caused, and the activity is quickly attenuated and the stability is reduced (Wu P, Zaffran J, Xu D, et al. First-principles-based microkinetic simulations of CO2 hydrogenation to methanol over intermetallic GaPd2: method development to include complex interactions between surface adsorbates[J]. The Journal of Physical Chemistry C, 2020, 124(29): 15977-15987.)., so that how to regulate and control the adsorption strength of Pd on the CO intermediate and improve the poisoning resistance of Pd is a core difficult problem in the field. In recent years, the introduction of foreign elements to regulate the electronic structure of Pd has proven to be a viable path. Research shows that in the field of CO 2 RR, antimony (Sb) shows potential for regulating and controlling the selectivity of a catalyst product by virtue of the unique electronic effect and the atomic size, which provides an important suggestion (Xue J, Dong X, Liu C, et al. Turning copper into an efficient and stable CO evolution catalyst beyond noble metals[J]. Nature Communications, 2024, 15(1): 5998.). for optimizing the surface adsorption behavior of a Pd-based catalyst by Sb. The strategy preparation method is simple, the product structure is stable, the effective unification of high CO selectivity, preparation simplicity and excellent operation stability is realized, and a feasible new scheme is provided for the application of the Pd-based catalyst in the field of CO 2 reduction preparation of CO. Disclosure of Invention Based on the problems, the invention provides a Pd-based catalytic material, a preparation method thereof and application of the material in electrocatalytic carbon dioxide reduction. The micro Sb doping strategy is used, the electronic structure of the Pd is regulated and controlled on the premise of not changing the lattice structure of the Pd main body, the adsorption energy of Pd on a CO intermediate is effectively weakened, the Pd x Sb catalytic material which is stable in structure and has good CO selectivity in the long-term electrolysis process is obtained, the material with the optimal performance is Pd 50 Sb, the CO Faraday efficiency of the Pd is 80% in the 0.5M KHCO 3 electrolyte, and the Pd can continuously and stably catalyze the reduction reaction of carbon dioxide with high efficiency to about 10 h, so that a new design thought is provided for developing a CO 2 electric reduction catalyst with high efficiency and stability. In order to achieve the above object, the technical scheme of the present invention is as follows: A trace Sb doped Pd-based catalytic material for electrocatalytic carbon dioxide reduction has a nano-aggregation structure, and a chemical formula of the Pd-based catalytic material is Pd x Sb, wherein the doping amount of Sb is kept constant, x is the relative content of Pd, and the value range of x is 30-70, and the catalytic material takes Pd as a main active component, and adjusts and controls the electronic structure of Pd by introducing Sb, so that the adsorption behavior of a reaction intermediate is optimized, and a catalyst with excellent catalytic performance is obtained. Further, in the trace Sb doped Pd-based catalyst Pd x Sb, the preferable structure is Pd 50 Sb. Further, the trace Sb doped Pd-based catalyst exhibits a black powder state. Further, the nanocluster of the micro Sb-doped Pd-based catalyst is 20-80 nm A method for preparing a micro Sb-