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CN-122013247-A - Non-noble metal@MOF topology regulation catalyst synthesized by interface method and preparation method and application thereof

CN122013247ACN 122013247 ACN122013247 ACN 122013247ACN-122013247-A

Abstract

The method comprises the steps of synthesizing a non-noble metal@MOF topology regulation catalyst by an interface method, preparing a metal salt aqueous solution, preparing a solution A, preparing a functional ligand organic solution, preparing a solution B, performing room-temperature interface reaction on the solution A and the solution B to obtain a non-noble metal@MOF topology regulation catalyst precursor, washing and drying the precursor to obtain the non-noble metal@MOF topology regulation catalyst, and preparing a C 2 product by electrocatalytic CO 2 reduction. The Faraday efficiency of the C 2 product reaches 93.1 percent, and the C 2 product stably runs for 10 hours under the current density of 502.7 mA.cm ‑2 , and has the advantages of low price, high selectivity of the C 2 product and excellent stability.

Inventors

  • HU YUXIANG
  • GAO YINGYING
  • ZHAO SHENLONG
  • LONG YONGDE
  • XU YANG
  • XIE XINGMING

Assignees

  • 北京工业大学

Dates

Publication Date
20260512
Application Date
20260227

Claims (10)

  1. 1. The preparation method for synthesizing the non-noble metal@MOF topology regulation catalyst by a room-temperature interface one-step method is characterized by comprising the following steps of: (1) Preparing a metal salt aqueous solution, wherein the solution A; (2) Preparing a functionalized ligand organic solution, namely a solution B; (3) Performing room-temperature interface reaction on the solution A and the solution B to obtain a non-noble metal@MOF topology regulation catalyst precursor; (4) And washing and drying the precursor to obtain the non-noble metal@MOF topology regulation catalyst.
  2. 2. The preparation method according to claim 1, wherein the non-noble metal salt and the stabilizer are added into the water solvent, and the mixture is ultrasonically dispersed until the non-noble metal salt and the stabilizer are completely dissolved; The non-noble metal salt is selected from any one of copper acetate (Cu (Ac) 2 ·2H 2 O), cobalt acetate (Co (Ac) 2 .4H2O), nickel acetate (Ni (Ac) 2 ·4H 2 O), copper chloride (CuCl 2 ·2H 2 O) and cobalt chloride (CoCl 2 ·6H 2 O); the stabilizer is polyvinylpyrrolidone (PVP) K30, and the mass ratio of the non-noble metal salt to the stabilizer is 15:1-45:1; the solvent is deionized water, the concentration of the non-noble metal salt is 50-100 mg/mL, and the concentration of the stabilizer is 10.0-30.0 mg for every 4-8 mL of solvent.
  3. 3. The preparation method of the functionalized ligand solution according to claim 1, wherein the preparation method of the functionalized ligand solution in the step (2) comprises dispersing the functionalized dicarboxylic acid ligand in a mixed solvent, and performing ultrasonic dispersion for 5-10 minutes to completely dissolve; The functionalized dicarboxylic acid ligand is selected from any one of 2-methyl terephthalic acid, 2, 5-dimethyl terephthalic acid and terephthalic acid; The mixed solvent is a mixed solution of N, N-dimethylacetamide (DMAc) and ethyl acetate, the volume ratio is 1:1, and each 8-16 mL of the mixed solvent corresponds to 20.0-35.0 mg of the functionalized dicarboxylic acid ligand.
  4. 4. The preparation method according to claim 1, wherein the room temperature interfacial reaction in the step (3) is carried out by slowly dropping the solution A into the solution B, and standing at 25 ℃ for 8-16 hours without additional stirring or heating.
  5. 5. The preparation method of the water-based paint according to claim 1, wherein in the step (4), the washing is performed for 2-3 times by adopting N, N-dimethylacetamide and absolute ethyl alcohol, and the drying is freeze drying, and the drying time is 10-14 hours.
  6. 6. A catalyst prepared according to the method of any one of claims 1-5.
  7. 7. Use of a catalyst prepared according to the method of any one of claims 1-5 for electrocatalytic CO 2 RR to produce C 2 product.
  8. 8. The method according to claim 7, wherein the three-electrode reaction system of the flow electrolytic cell is adopted, the working electrode is a Gas Diffusion Electrode (GDE) for supporting the catalyst, the reference electrode is Ag/AgCl (saturated KCl), the counter electrode is foam nickel, the electrolyte of the reaction system is 0.5-1.5M KOH solution, the electrolyte is saturated with CO 2 gas for 20-40 min before use, and CO is continuously introduced into the system during the reaction 2; The reaction condition of the electrocatalytic CO 2 RR is that the reaction temperature is 20-25 ℃, the applied potential range is-1.4V to-1.9V (vs. RHE), the gas flow rate of CO 2 is 20-30 mL min < -1 >, and the circulating flow rate of electrolyte is 2.5-4.0 mL min < -1 >.
  9. 9. Use according to claim 8, the corresponding current density being 200-500 mA/cm 2 and operating continuously for 10 hours at high current density (500 mA/cm 2 ).
  10. 10. Use according to any one of claims 7 to 9 for the electrocatalytic carbon dioxide reduction (CO 2 RR) to produce a C 2 product, the C 2 product comprising one or more of ethylene, ethanol.

Description

Non-noble metal@MOF topology regulation catalyst synthesized by interface method and preparation method and application thereof Technical Field The invention belongs to the field of catalytic synthesis, and particularly relates to a non-noble metal@MOF topology regulation catalyst synthesized by a room-temperature interface one-step method, and a preparation method and a path thereof, wherein a catalytic reaction system is used for preparing a C 2 product (such as ethylene, ethanol and the like) in an electrocatalytic carbon dioxide reduction reaction (CO 2 RR). Background The global carbon emission problem is increasingly severe, and serious problems of environmental pressure and carbon resource waste are caused. The electrocatalytic CO 2 reduction reaction (CO 2 RR) for converting carbon dioxide into a high added value C 2 product (such as C 2H4、C2H5 OH) can realize the high-efficiency utilization of carbon resources and the development of carbon negativity. In recent years, various CO 2 conversion technologies including thermocatalytic reduction, photocatalytic reduction, electrocatalytic reduction and the like are widely designed and developed, wherein electrocatalytic CO 2 RR has one of the most industrial application prospect methods due to the advantages of mild reaction conditions, easy regulation and control of product selectivity and the like. The core of the electrocatalytic CO 2 RR is the coupling reaction of CO intermediate generation and C-C, and at present, a Metal Organic Frameworks (MOFs) become a main stream candidate catalyst of CO 2 RR by virtue of the advantages of ultra-high specific surface area, adjustable active sites and the like. However, the traditional MOF catalyst has obvious defects, the selectivity of the C 2 product is low, the long-term stability is poor, and the preparation process needs high temperature, high pressure or complex post-treatment steps, so that the practical application is limited. The Non-noble metal@MOF topology-regulated materials serving as a novel catalytic material is a two-dimensional nano-structure material formed by self-assembling a functional ligand and a Non-noble metal through an interface. Compared with the traditional catalyst, the material has the characteristics of unique control topological structure, high active site exposure, short transmission path and the like, combines the low-cost advantage of non-noble metal and the structural adjustability of MOF, and remarkably improves the selectivity and stability of C 2. These characteristics make the non-noble metal@MOFtopology regulating material have great potential in the field of electrochemical catalysis, but at present, the research of taking the material as a catalyst for preparing C 2 products from CO 2 RR is still reported. Disclosure of Invention Aiming at the problems of the prior art, one of the purposes of the invention is to provide a simple preparation method of a non-noble metal@MOF topology regulation catalyst, which can be used for preparing a C 2 product by electrocatalytic CO 2 reduction, has the characteristics of high activity and excellent stability, and has mild reaction conditions and universality. In order to achieve the above purpose, the invention adopts the following technical scheme: a method for preparing a non-noble metal @ MOF topology regulating catalyst, the method comprising the steps of: (1) Preparing a metal salt aqueous solution, wherein the solution A; (2) Preparing a functionalized ligand organic solution, namely a solution B; (3) Performing room-temperature interface reaction on the solution A and the solution B to obtain a non-noble metal@MOF topology regulation catalyst precursor; (4) And washing and drying the precursor to obtain the non-noble metal@MOF topology regulation catalyst which is used for preparing a C 2 product through electrocatalytic CO 2 reduction. Preferably, the preparation method of the metal salt aqueous solution in the step (1) comprises the following steps: adding non-noble metal salt and stabilizer into water solvent, ultrasonic dispersing until it is completely dissolved, and maintaining the natural dispersion state of the solution. Preferably, the non-noble metal salt is selected from any one of copper acetate (Cu (Ac) 2·2H2 O), cobalt acetate (Co (Ac) 2.4h2o), nickel acetate (Ni (Ac) 2·4H2 O), copper chloride (CuCl 2·2H2 O), cobalt chloride (CoCl 2·6H2 O). Preferably, the stabilizer is polyvinylpyrrolidone (PVP) K30, and the mass ratio of the non-noble metal salt to the stabilizer is 15:1-45:1. Preferably, the solvent is deionized water, and the concentration of the non-noble metal salt is 50-100 mg/mL. Every 4-8 mL of solvent corresponds to 10.0-30.0 mg of stabilizer. Preferably, the preparation method of the functionalized ligand solution in the step (2) comprises the steps of dispersing the functionalized dicarboxylic acid ligand in a mixed solvent, and performing ultrasonic dispersion for 5-10 minutes to completely dissol