CN115449839A - For matching cathode CO 2 Use of reduced NiCo-MOF anodization catalysts - Google Patents

For matching cathode CO 2 Use of reduced NiCo-MOF anodization catalysts Download PDF

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CN115449839A
CN115449839A CN202211125866.6A CN202211125866A CN115449839A CN 115449839 A CN115449839 A CN 115449839A CN 202211125866 A CN202211125866 A CN 202211125866A CN 115449839 A CN115449839 A CN 115449839A
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邱介山
杨琪
亓军
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Beijing University of Chemical Technology
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    • 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
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    • 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
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Abstract

A preparation method of NiCo-MOF anode oxidation catalyst for matching cathode CO2 reduction belongs to the technical field of electrocatalysis and fine chemical synthesis. Based on ion etching in a hydrothermal environment, niCo-MOF electrocatalyst with a uniform nanometer flower-like structure grows on the surface of a substrate such as foamed nickel. The catalyst shows excellent catalytic activity on the oxidation of glycerin and the oxidation of glucose due to the regulation and control effect of cobalt on the distribution of nickel electron cloud in an active center, and can realize the concentration as high as 400mA cm by only 1.398V ‑2 The Tafel slope is only 42.3mV dec ‑1 The performance of stable circulation for 100 hours is not attenuated, and the Faraday efficiency of the main product formic acid is up to more than 90 percent. The catalyst has the advantages of simple synthesis method, low cost, good catalytic activity and selectivity, and good stabilityThe qualitative is excellent, and the industrial application prospect is good in the small molecule electrooxidation coupling carbon dioxide electroreduction co-production formate industry.

Description

For matching cathode CO 2 Use of reduced NiCo-MOF anodization catalysts
Technical Field
The invention belongs to the field of electrocatalysis and fine chemical synthesis, and particularly relates to a method for matching cathode CO 2 A preparation method and application of a reduced NiCo-MOF anodic oxidation catalyst.
Background
The development of green low-carbon energy technology and carbon utilization technology, except reducing carbon emission from the source, how to realize carbon dioxide (CO) 2 ) The comprehensive utilization of the method becomes a hotspot and a difficulty of research, and is about the whole layout of the ecological civilization construction of the country and the development of the economic society.
Despite the continuous development of new energy industry, fossil energy still dominates the global energy structure, and the use of fossil energy brings a large amount of CO 2 Emissions, leading to global warming. For protecting ecological environment and reducing CO in atmosphere 2 The content is not very slow. Electrocatalytic CO 2 Restoration is one of the most promising techniques to solve this dilemma. At normal temperature, CO is realized by means of a series of novel clean energy such as wind energy, solar energy and the like 2 And converted into high-economic-value fuels and chemicals (such as formic acid, methanol, methane, ethylene and the like). With the development of a novel catalyst having high selectivity and high stability and the design of a novel electrolysis apparatus, CO is electrocatalyzed 2 The reduction technology shows good industrial application prospect. However, currently most of the CO 2 The anode in the electroreduction process generates Oxygen Evolution Reaction (OER), the four-electron transfer process needs higher anode potential to drive, and the CO is obviously increased 2 The energy consumption of the electroreduction process correspondingly generates secondary carbon emission. More importantly, oxygen, as an anode reaction product, which is of low practical economic value, is typically discharged directly into the air.
The development of a novel anode reaction with low initial potential and operating potential opens up a new idea for solving the problem of high energy consumption of OER reaction. While the research on catalysts has been carried out most extensively with nickel-based catalysts, such as Ni 2 Metal hybrids represented by P and NiS, and doped bimetallic oxides of high-valence metals Mo, mn, W, and the like. The catalysts show excellent catalytic activity and stability to small-molecule organic substrates. However, the synthesis process of the above catalyst often needs to be realized by means of introducing heteroatoms through high-temperature treatment, and thus, the synthesis process faces the challenges of obvious scale preparation and high energy consumption cost. Thus, development of novel nickelThe preparation method of the alcohol oxidation catalyst realizes the unification of high activity, high selectivity, long service life, large-scale preparation and low cost of the catalyst, and is used for promoting the conversion of fine chemicals and coupling electrocatalysis CO 2 Industrial application in the field of reduction is of great importance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of an electrocatalyst which is low in cost and can be prepared in a large scale, and the preparation method is applied to electrochemical oxidation of small organic molecules to couple cathode electrocatalysis CO 2 Reduction to promote the development of low-cost carbon utilization technology. The method is simple to operate, low in cost and energy consumption, and shows excellent catalytic activity, product selectivity and stability in electrochemical oxidation of small molecular alcohol. And small molecular organic matters such as methanol, ethanol, isopropanol, glycerol, 5-hydroxymethylfurfural, urea, hydrazine, glucose and the like can be used as reaction substrates to carry out anodic oxidation reaction in a mode of being lower than the OER reaction potential.
In order to achieve the above purpose and solve the problems in the prior art, the invention adopts the technical scheme of matching cathode CO 2 A method for preparing a reduced NiCo-MOF anodization catalyst, comprising the steps of:
step 1, soaking a substrate commercial Nickel Foam (NF) in 1-3mol/L HCl solution for 30min by ultrasonic treatment, and then repeatedly washing the substrate commercial Nickel Foam (NF) with ethanol and deionized water to remove an oxide layer on the surface of the nickel foam. The foamed nickel can be replaced by foamed copper, foamed iron, foamed titanium and carbon fiber paper and carbon cloth, or a substrate is not used, and the appearance of the catalyst is hardly influenced.
Step 2, adding 1mmol of Ni (NO) 3 ) 3 ·6H 2 O and 0.5mmol Co (NO) 3 ) 3 ·6H 2 O was dissolved in 15mL of methanol as a solution A, and 4mmol of 2-methylimidazole was dissolved in 15mL of methanol as a solution B. After stirring for 20min, solution B was then quickly poured into solution a and stirring continued for 5-10min to form a uniform blue turbid solution. The ratio of nickel and cobalt is adjustable within the range of 1The adding proportion of nickel and cobalt in the precursor is the key of the application of the catalyst to different substrates, according to the research, the difference of the nickel and cobalt proportion does not cause too great influence on the appearance, and is only the difference of the catalytic performance: compared with other proportions, the proportion of Ni and Co has the best catalytic performance for the electrooxidation of small molecular alcohol near 2. In the previous step, the molar ratio of the 2-methylimidazole to the cobalt salt is 6 to 10, wherein the molar ratio is adjustable.
And 3, transferring the mixed solution into a 50mL polytetrafluoroethylene stainless steel-lined high-pressure hydrothermal kettle, adding pretreated nickel foam, putting into an oven, and keeping the temperature of 60-80 ℃ for 6-12h. After cooling, the foam nickel with NiCo-MOF is washed by deionized water and ethanol for a plurality of times, and then dried overnight at 60 ℃, thus obtaining the self-supporting NiCo-MOF electrocatalyst with uniform nanometer flower shape.
And 4, taking the electrocatalyst as a working electrode, taking Hg/HgO as a reference electrode and a carbon rod as a counter electrode, performing CV activation in a standard three-electrode system, scanning for 10-20min with a voltage interval of 0-0.5V (vs. Hg/HgO), and completing activation of NiCo-MOF so as to directly use the NiCo-MOF in electrocatalytic oxidation of small molecular alcohols (such as glycerol, methanol, glucose and the like).
The existence of the substrate in the catalyst improves the uniformity of the nano flower-shaped structure, avoids the use of a binder when the catalyst is used as the catalyst, eliminates partial charge transfer resistance, and is the key of the catalyst for showing more excellent catalytic activity. The substrate can be foamed nickel, and can also be replaced by foamed copper, foamed iron, foamed titanium, carbon fiber paper and carbon cloth, and the appearance of the catalyst is hardly influenced.
Different from the conventional Ni-MOF, the redox characteristics of Ni and Co are utilized in a mode of taking trimesic acid as a precursor and 2-methylimidazole as a precursor, so that Ni is realized 2+ The method can also be expanded to CuCo-MOF, ruCo-MOF and the like by etching ZIF-67 and forming NiCo-MOF nanoflowers on the surface of the ZIF-67.
NiCo-MOF electrocatalyst shows excellent catalytic activity for novel anodic oxidation reaction, especially methanol and glycerol, can be oxidized into final product potassium formate under the drive of electric energy, and has faradaic efficiency of over 90%, yield of nearly 100%, and stability of over 100 h.
The invention has the advantages that: the electrocatalyst synthesis method provided by the invention can be used for preparing the NiCo-MOF catalyst with uniform nanometer flower shape, is simple, has low raw material cost and low energy consumption, and is suitable for large-scale preparation. Meanwhile, the catalyst shows excellent catalytic activity, selectivity and stability for electrooxidation of small-molecular alcohol-based compounds, and particularly when the ratio of nickel to cobalt is 2:1, the anode potential of only 1.38V (vs. RHE) is required to achieve 400mA cm -2 The industrial current density of (2) can maintain the stability of 100h at the potential of 1.4V (vs. RHE) with almost no reduction of the catalytic performance. Active sites are provided by introducing Ni, and meanwhile, the existence of Co completes the regulation and control of the distribution of Ni electron clouds, so that the conversion of Ni electron clouds from bivalent to trivalent is improved, and excellent catalytic performance is further shown. Most importantly, the catalyst has high selectivity to formic acid when catalyzing the oxidation of glycerol, and the faradaic efficiency of the formic acid as a main product exceeds 90%, and the selectivity is close to 100%. In coupling electrocatalytic CO 2 In a reduction system, the reduction of energy consumption can be realized, the energy-saving potential is realized, the high added value conversion of fine chemicals is realized, the same product, namely potassium formate, is obtained at the anode and the cathode, the use of an ion exchange membrane is avoided, and the electrocatalysis further reduced 2 The reduction cost is reduced, and the operation period of the device is prolonged.
The NiCo-MOF catalyst not only has excellent catalytic activity on glycerol, but also is suitable for the electro-oxidation of other micromolecular alcohol-based chemicals such as methanol, glucose and the like, can be further expanded to the oxidation of urea and hydrazine and is used for coupling electro-catalysis of CO 2 The commercial development of reduction provides a new low-cost route and has wide prospect.
Drawings
FIG. 1 is a scanning electron micrograph of a NiCo-MOF electrocatalyst.
FIG. 2 is an XRD pattern of an NiCo-MOF electrocatalyst
FIG. 3 is a polarization curve comparing glycerol oxidation and OER in example 1.
FIG. 4 is a polarization curve comparing glucose oxidation and OER in example 2.
Detailed Description
The present invention will be further described with reference to the following examples.
EXAMPLE 1 preparation of the catalyst
A method for preparing a self-supporting NiCo-MOF electrocatalyst, comprising the steps of:
step 1, soaking a substrate commercial Nickel Foam (NF) in 1mol/L HCl solution for 30min by ultrasonic treatment, and then repeatedly washing the substrate commercial Nickel Foam (NF) with ethanol and deionized water to remove an oxide layer on the surface of the nickel foam. The foamed nickel can be replaced by foamed copper, foamed iron, foamed titanium and carbon fiber paper and carbon cloth, or a substrate is not used, and the appearance of the catalyst is hardly influenced.
Step 2, adding 1mmol of Ni (NO) 3 ) 3 ·6H 2 O and 0.5mmol Co (NO) 3 ) 3 ·6H 2 O was dissolved in 15mL of methanol as solution A, and 4mmol of 2-methylimidazole was dissolved in 15mL of methanol as solution B. After stirring for 20min, solution B was then quickly poured into solution a and stirring continued for 7min to form a uniform blue turbid solution.
And 3, transferring the mixed solution into a 50mL polytetrafluoroethylene-lined stainless steel high-pressure hydrothermal kettle, adding pretreated nickel foam, putting into an oven, and keeping at the temperature of 60 ℃ for 12 hours. After cooling, the foam nickel with NiCo-MOF is washed by deionized water and ethanol for a plurality of times, and then dried overnight at 60 ℃, so that the self-supporting NiCo-MOF electrocatalyst with uniform nano flower shape is obtained.
Example 2
Because the catalyst prepared by the invention belongs to a self-supporting structure, the foam nickel loaded with the NiCo-MOF catalyst in the example 1 is cut into 1 multiplied by 1cm without using Nafion solution as a binder 2 The test piece is large and used as a working electrode, hg/HgO is used as a reference electrode, a carbon rod is used as a counter electrode, the electrolyte adopts a solution containing 0.3mol/L of glycerol and 1mol/L of KOH, and electrochemical performance test is carried out in a standard three-electrode electrolytic cell by utilizing a Chi 760E workstation in Shanghai ChenghuaTo verify the activity of the catalyst. Specifically, argon is used as circulating gas, before electrochemical test, argon is introduced for 20min to discharge other gases in an electrolytic cell, then an electrochemical workstation is used for CV activation, the voltage setting interval is 0-0.5V (vs.Hg/HgO), and the sweep rate is 10mV s -1 Circularly scanning for 40 circles to complete the activation of the NiCo-MOF catalyst, and then testing a polarization curve, wherein the voltage setting range is-0.2-0.6V, and the sweeping speed is 10mV s -1 Setting the iR offset to 85%, the results of the polarization curves are shown in FIG. 2, ni 2 Co 1 The MOF catalyst exhibits excellent catalytic activity for glycerol oxidation, requiring only 1.25V, 1.305V, 1.341V and 1.398V to achieve 10mA cm -2 、100mA cm -2 、200mA cm -2 And 400mA cm -2 The current density of (2) is obviously superior to the electrode potential of OER reaction, and the polarization potential is reduced by up to 300mV. Further Tafel slope results show that Ni 2 Co 1 The MOF had the lowest Tafel slope, only 42.3mV dec -1 Showing Ni 2 Co 1 MOFs have faster catalytic reaction kinetics. In addition, the invention also compares the electrochemical impedance with the electrochemical active surface area, and shows Ni 2 Co 1 The MOF catalyst has very small charge transfer resistance and large electrochemical active surface area, on one hand, the MOF catalyst has abundant pore channels due to uniform nanoflower morphology, electrolyte infiltration and product transmission are facilitated, more active sites are provided, and the three-dimensional conductive self-supporting material structure avoids the use of a binder, so that the charge transfer resistance is remarkably reduced. The stability test result shows that Ni 2 Co 1 The MOF catalyst showed good durability to glycerol oxidation with little change in catalytic activity in electrolysis tests continued for up to 110 h.
The invention utilizes nuclear magnetic resonance hydrogen spectrum to carry out qualitative and quantitative analysis on the electrolysis product, and the result shows that the concentration of glycerol is gradually reduced along with the progress of the reaction, the concentration of the product potassium formate is gradually increased, the potassium formate is the only liquid-phase product for oxidizing glycerol, the Faraday efficiency exceeds 90 percent, and the Ni shows that 2 Co 1 The MOF catalyst has good selectivity to formate.
Example 3
A method for preparing a self-supporting NiCo-MOF electrocatalyst, comprising the steps of:
step 1, soaking commercial Nickel Foam (NF) serving as a substrate in 1mol/L HCl solution for 30min by ultrasonic treatment, and then repeatedly washing the substrate with ethanol and deionized water to remove an oxide layer on the surface of the nickel foam.
Step 2, adding 1.5mmol of Ni (NO) 3 ) 3 ·6H 2 O and 0.5mmol Co (NO) 3 ) 3 ·6H 2 O was dissolved in 15mL of methanol as solution A, and 4mmol of 2-methylimidazole was dissolved in 15mL of methanol as solution B. After stirring for 20min, solution B was then quickly poured into solution a and stirring continued for 10min to form a uniform blue turbid solution.
And 3, transferring the mixed solution into a 50mL polytetrafluoroethylene-lined stainless steel high-pressure hydrothermal kettle, adding pretreated nickel foam, putting into an oven, and keeping at the temperature of 60 ℃ for 12 hours. After cooling, the foam nickel with NiCo-MOF is washed by deionized water and ethanol for a plurality of times, and then dried overnight at 60 ℃, thus obtaining the self-supporting NiCo-MOF electrocatalyst with uniform nanometer flower shape.
Example 4
The self-supporting NiCo-MOF electrocatalyst prepared in example 3 is applied to oxidation of small molecular glucose, an electrolyte is a potassium hydroxide solution containing glucose, wherein the concentration of glucose is 0.5mol/L, and the universality of the catalyst is verified by performing a performance test of glucose electrooxidation in a standard three-electrode electrolytic cell by utilizing a Shanghai Hua CHI 760E workstation.
Specifically, before electrochemical test, argon is introduced for 20min to exhaust other gases in an electrolytic cell, then an electrochemical workstation is used for CV activation, the voltage setting interval is 0-0.5V (vs.Hg/HgO), and the sweep rate is 10mV s -1 And circularly scanning for 30 circles to complete the activation of the NiCo-MOF catalyst. The parameters of the polarization curve are set as: the voltage range is-0.2-0.6V, and the sweep rate is 10mV s -1 Setting the iR offset to 85% results are shown in FIG. 4, unlike sweetOil oxidation, the optimal ratio of Ni and Co for glucose oxidation is 3 3 Co 1 The MOF catalyst exhibits remarkable catalytic activity for glucose oxidation, and only 1.28V, 1.35V and 1.42V are needed to realize 10mA cm -2 、100mA cm -2 And 400mA cm -2 The current density of (2) and electrode potentials of 1.557v,1.667v and 1.78V are required for OER reaction, the polarization voltage is reduced by up to 300mV or more.
Further Tafel slope results show that Ni 3 Co 1 MOF has a lower Tafel slope, only 62.1mV dec -1 Showing Ni 3 Co 1 MOFs have faster catalytic reaction kinetics. Like the glycerol oxidation phase, ni 3 Co 1 The MOF catalyst also has very small charge transfer resistance and large electrochemical active surface area, and the abundant pore channel structure exposes more active sites, thereby facilitating the contact of reaction substrates and the catalyst and the desorption of products.
Analysis of the electrolysis products by nuclear magnetic resonance hydrogen spectrum shows that the glucose concentration is gradually reduced along with the reaction, the products are mainly glucaric acid, the selectivity is over 90 percent, and the Faraday efficiency is close to 90 percent. At the cathode CO 2 In the process of electro-reduction coupling, on one hand, energy saving is realized, on the other hand, conversion of products with high added values is realized, particularly glucaric acid which is an organic acid with high added values in nature is realized, and the organic acid is widely applied to the fields of food, chemical industry, medicine and the like, such as reduction of steroids and partial non-steroids, chemical cancer prevention and the like. According to the 2004 best and most valuable research report of producing bio-based products by biological method released by the U.S. department of energy, glucaric acid is considered as one of the most valuable bio-refining products, and the higher economic value further reduces the electrocatalytic CO 2 The cost of reduction, in turn, reduces the carbon emission contributing forces.
The influence of the ratio of Ni and Co on the application in the embodiments 2 and 4 is specifically analyzed, the influence of the ratio of Ni and Co on the morphology and the catalytic performance of the material is analyzed, ni is used as an active site of an anode small molecule oxidation reaction, the existence of Co plays a role in adjusting the distribution of Ni electron clouds, and the optimal electronic structure can have the most excellent catalytic performance. It was found in the present invention that when the ratio of Ni and Co is 2.
Example 5
A method for preparing a self-supporting NiCo-MOF electrocatalyst, comprising the steps of:
step 1, soaking a substrate commercial Nickel Foam (NF) in 1mol/L HCl solution for 30min by ultrasonic treatment, and then repeatedly washing the substrate commercial Nickel Foam (NF) with ethanol and deionized water to remove an oxide layer on the surface of the nickel foam.
Step 2, adding 1mmol of Ni (NO) 3 ) 3 ·6H 2 O and 0.5mmol Co (NO) 3 ) 3 ·6H 2 O was dissolved in 15mL of methanol as a solution A, and 4mmol of 2-methylimidazole was dissolved in 15mL of methanol as a solution B. After stirring for 20min, solution B was then quickly poured into solution a and stirring continued for 7min to form a uniform blue turbid solution.
And 3, transferring the mixed solution into a 50mL polytetrafluoroethylene stainless steel-lined high-pressure hydrothermal kettle, adding pretreated nickel foam, putting into an oven, and keeping at the temperature of 85 ℃ for 12 hours. After cooling, the foam nickel with NiCo-MOF is washed by deionized water and ethanol for a plurality of times, and then dried overnight at 60 ℃, so that the self-supporting NiCo-MOF electrocatalyst with uniform nano flower shape is obtained.
Example 6
The preparation method was the same as that of example 5 except that the hydrothermal reaction in step 3 was carried out at a temperature of 85 ℃ for 12 hours.
The other operation steps in the embodiment 5 and the embodiment 6 are the same as those in the embodiment 1, and the difference is mainly that the hydrothermal reaction temperature is different, the hydrothermal reaction temperature in the embodiment 5 is 85 ℃, the hydrothermal reaction temperature in the embodiment 6 is 120 ℃, and the prepared catalysts do not form the uniform nanoflower morphology; therefore, the hydrothermal temperature in the preparation method of the catalyst is a key parameter influencing the performance of the catalyst, the upper temperature limit cannot exceed 80 ℃, the lower temperature limit cannot be lower than 40 ℃, and otherwise, the nano flower-shaped structure supported by the foamed nickel cannot be synthesized. The nano flower-like structure is beneficial to the exposure of catalytic active sites, and the electrolyte goes deep, so that excellent catalytic performance can be shown.

Claims (6)

1. For matching cathode CO 2 The preparation method of the reduced NiCo-MOF anodic oxidation catalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Soaking the substrate in 1-3mol/L HCl solution for ultrasonic treatment, and then washing with ethanol and deionized water;
(2) Dissolving nickel salt and cobalt salt in methanol to obtain a solution A, and dissolving 2-methylimidazole in methanol to obtain a solution B; after stirring, quickly injecting the solution B into the solution A and continuously stirring for 5-10min to form a blue turbid mixed solution;
the molar ratio of the nickel salt to the cobalt salt is 1 to 4; the molar ratio of 2-methylimidazole to cobalt salt is 6 to 10;
(3) Transferring the mixed solution into a polytetrafluoroethylene-lined stainless steel high-pressure hydrothermal kettle, adding a pretreated substrate, putting the pretreated substrate into an oven, and keeping the temperature of 60-80 ℃ for 4-24 hours; after cooling, the foam nickel with NiCo-MOF is washed by deionized water and ethanol and dried to obtain the self-supporting NiCo-MOF catalyst.
2. The method of claim 1 for matching cathode CO 2 A preparation method of a reduced NiCo-MOF anodic oxidation catalyst is characterized by comprising the following steps: the substrate is made of foamed nickel, foamed copper, foamed iron, foamed titanium, carbon fiber paper or carbon cloth.
3. Be used for matching negative pole CO 2 Use of a reduced NiCo-MOF anodization catalyst, characterized in that: a self-supporting NiCo-MOF catalyst prepared by the method of claim 1;
use of a self-supporting NiCo-MOF catalyst: taking a NiCo-MOF catalyst as a working electrode, hg/HgO as a reference electrode, taking a carbon rod as a counter electrode, performing CV activation in a standard three-electrode system, scanning for 10-30min with a voltage interval of 0-0.5V relative to the reference electrode, and completing activation of the NiCo-MOF catalyst, wherein the activation is directly applied to electrocatalytic oxidation of small molecular alcohol.
4. A method for matching cathode CO according to claim 3 2 Use of a reduced NiCo-MOF anodization catalyst, characterized in that: the small molecular alcohol is glycerol, methanol, ethanol, isopropanol or glucose.
5. A method for matching cathode CO according to claim 3 2 Use of a reduced NiCo-MOF anodization catalyst, characterized in that: the molar ratio of the nickel salt and the cobalt salt influences the catalytic performance of the nickel salt and the cobalt salt on different small molecular alcohols: the molar ratio of nickel salt to cobalt salt is 2.
6. A method for matching cathode CO according to claim 3 2 Use of a reduced NiCo-MOF anodization catalyst, characterized in that: the molar ratio of the nickel salt to the cobalt salt influences the catalytic performance of the nickel salt to different small molecular alcohols: the molar ratio of nickel salt to cobalt salt is 3.
CN202211125866.6A 2022-09-16 2022-09-16 For matching cathode CO 2 Use of reduced NiCo-MOF anodization catalysts Pending CN115449839A (en)

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