CN115770621A - Preparation method and application of bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst - Google Patents
Preparation method and application of bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst Download PDFInfo
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method and application of a bimetallic MOF anchored Pt nanocluster catalyst, wherein the catalyst is Pt NC NiMn-MOF nano material, the catalyst is Pt NC NiMn-MOF nanomaterial, which in an X-ray diffraction spectrum of the nanomaterial has a monoclinic nickel-based metal organic framework (Ni-MOF) structure, wherein the corresponding XRD diffraction angles 2 theta range from 5 degrees to 50 degrees, and obvious XRD diffraction peaks with 2 theta angles of 8.9 degrees, 15.5 degrees, 28.3 degrees and 30.6 degrees and the like respectively correspond to (200), (400), (20-2) and (311) crystal faces, pt and Pt in the NiMn-MOF structure NC The NiMn-MOF composite nano material not only can produce hydrogen by fully decomposing urea for industrial application, but also can meet the requirements of urea wastewater treatment in various occasions such as industry, life and the like, and realizes the reclamation of wastewater and the maximization of energy utilization.
Description
Technical Field
The invention relates to the technical field of nano electro-catalytic materials, in particular to a preparation method and application of a bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst.
Background
The increasing energy crisis and environmental pollution have forced the search for sustainable alternative energy sources. The advantages of high combustion heat value, large energy density and no pollution of products of hydrogen energy are one of the clean energy with the most development potential. The green sustainable electrochemical water splitting hydrogen production is a mass production of high-purity H 2 The corresponding electrocatalytic Hydrogen Evolution Reaction (HER) is receiving extensive attention. Generally, whether electrochemical water splitting produces hydrogen efficiently or not depends on the catalytic activity and stability of the HER catalyst. Efficient HER electrocatalysts are required to accelerate slow reaction kinetics and reduce electrode overpotentials. Currently, commercial Pt/C remains the primary hydrogen production catalyst. However, the low abundance and high cost of platinum clearly hinders its large scale application. For this reason, the development of hydrogen-producing electrocatalysts which are efficient, stable and less costly has become increasingly urgent.
Meanwhile, the electrochemical water splitting anode Oxygen Evolution Reaction (OER) is a complex four-electron process, so that the driving voltage is large (generally more than or equal to 1.8V), the energy efficiency is low and the hydrogen production cost is high. Therefore, replacing OER with other anodic oxidation reactions with lower thermodynamic voltages would make energy efficient hydrogen production possible. Among the anodic oxidation reactions, the urea oxidation reaction (UOR, CO (NH) 2 ) 2 +6OH - →N 2 +CO 2 +5H 2 O+6e - ) It has attracted extensive research interest due to its inherently lower thermodynamic equilibrium potential (0.37V versus Reversible Hydrogen Electrode (RHE)) which makes the overall potential of UOR significantly lower than OER. The integrated urea electrolysis of the UOR coupled HER (HER (-) | UOR (+)) not only can realize low-energy hydrogen production, but also can purify the urea-rich wastewater, thereby showing thatHas great practical application potential.
In addition, most non-noble metal-based electrocatalysts exist in powder form, and thus require binders to be loaded on working electrodes such as glassy carbon, bisulfite plates, etc., and the manufacturing process is cumbersome, and in addition, most binder materials such as Nafion and polyvinylidene fluoride are expensive, which greatly limits the scale application thereof. The use of a binder not only reduces the amount of exposed active sites of the catalyst, but also reduces the overall conductivity of the product electrode. In addition, the degree of binder and electrocatalyst complexation is not able to withstand the stresses generated during high current density operation of large catalysts, resulting in a large compromise in catalyst stability. The effective strategy to solve the above problems is to grow-conductive three-dimensional porous skeleton composite nano-catalyst in situ.
A Metal Organic Framework (MOF) composed of metal nodes and organic ligands is regarded as a catalytic electrode material with great application prospect as an emerging three-dimensional porous composite nano structure. On the one hand, MOFs have abundant and uniformly dispersed catalytic metal nodes, giving them a large number of active sites. On the other hand, MOFs, as porous solid materials, can be used for both heterogeneous catalysis and homogeneous catalysis and can be recycled after the catalytic reaction is finished. However, for most MOF materials, poor intrinsic performance, relatively low conductivity, and poor stability are key issues. The electrocatalyst grows to the surface of the NF framework in situ, so that the close contact between the electrocatalyst and the substrate can be ensured, the charge transmission of the electrocatalyst/substrate interface is facilitated, and the mechanical stability of the corresponding catalytic electrode can be greatly improved. MOFs are rarely used directly as HER and UOR electrocatalysts, considering their poor conductivity and poor stability. Instead, it is generally a carbon-based composite catalyst used as a metal after heat treatment at a high temperature to become a catalytically active species. However, heat treatment may compromise the advantages of the ordered porous structure of the MOF, leading to aggregation of the metal centers and loss of active centers. Based on this, catalyst loading of MOFs on porous conductive substrates, such as in situ growth of MOFs on NF, is considered an effective approach to overcome the low conductivity and low mass permeability described above.
In order to further improve the conductivity and catalytic activity of the MOF-based catalytic electrode material, modifying a trace amount of noble metal on the surface of the MOF structure is considered to be an effective way, and further reducing the size of the modified noble metal to the size of a Nano-cluster (Nano-clusters) tends to greatly improve the catalytic activity and stability of the composite catalyst. This is because the nanocluster catalyst consisting of several atoms has a high atom utilization rate and has a unique electronic structure and geometric configuration, which can maximally perform material conversion during a catalytic reaction process, thereby accelerating a reaction rate. Although various noble metal nanoclusters have been continuously reported in the past few years and play an important role in the field of electrocatalysis. However, the cluster atom surface energy is large, so that the metal atoms are easy to migrate and aggregate, and the catalytic activity of the metal atoms is reduced, so that how to stabilize the nanocluster metal atoms on a certain carrier is the key for preparing the high-activity nanoclusters. Although many synthetic methods, such as chemical vapor deposition, pyrolysis, atomic layer deposition, and microwave heating, have proven to stabilize nanoclusters, most synthetic routes are complex and require high temperature or high pressure conditions. Therefore, developing and designing a general strategy with simple preparation and low cost to realize the metal organic framework nano material anchoring Pt nanoclusters is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Therefore, the main object of the present invention is to provide a preparation method and use of bimetallic MOF anchored Pt nanocluster catalyst to solve the problems existing in the background art.
The precursor of the Metal Organic Framework (MOF) prepared by the method is a catalytic material with wide application prospect, is constructed by metal ions/clusters and an organic connector, can provide clear structures and definite active centers, and is easy to regulate and control the electronic structures of metal sites; the MOF precursor is rich in pore structure and large in specific surface area, is easy to contact with electrolyte, is beneficial to accelerating mass transfer process and effectively reducing the overall energy consumption of the (HER (-) | UOR (+) electrolytic cell.
In order to solve the technical problems, the invention provides the following technical scheme:
a bimetallic MOF anchored Pt nanocluster catalyst is Pt NC A NiMn-MOF nanomaterial, which in an X-ray diffraction spectrum of the nanomaterial has a monoclinic nickel-based metal organic framework (Ni-MOF) structure, and has a corresponding XRD diffraction angle 2 theta in a range of 5-50 degrees, wherein obvious XRD diffraction peaks appearing at positions of 8.9 degrees, 15.5 degrees, 28.3 degrees and 30.6 degrees of the 2 theta angle respectively correspond to (200), (400), (20-2) and (311) crystal planes in the NiMn-MOF structure.
The invention also provides a preparation method of the bimetallic MOF anchored Pt nanocluster catalyst, wherein the catalyst is Pt NC /NiMn-MOF, the method is as follows: growing a NiMn-MOF precursor on foamed nickel in situ by taking metal nickel and manganese as metal nodes and terephthalic acid as an organic ligand, and loading a Pt nanocluster on the surface of the NiMn-MOF precursor by utilizing a room-temperature wet chemical etching method to obtain Pt NC A NiMn-MOF composite nano material.
Further, the preparation method comprises the following steps:
step (1): pretreating foamed nickel;
step (2): adding metal nickel salt, metal manganese salt and terephthalic acid into a solvent, and dissolving
The agent consists of ethanol, N-dimethylformamide and deionized water, and is uniformly stirred to obtain an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, preferably, the reaction temperature of the hydrothermal reaction is 120-160 ℃, and the reaction time is 12-24 hours;
and (4): taking out the reacted foam nickel, washing with alcohol, and drying at room temperature to obtain the nickel-based catalyst
A bimetallic organic framework NiMn-MOF precursor;
and (5): immersing the resulting NiMn-MOF precursor in an amount of chloroplatinic acid solution, chamber
Reacting for 1 h in a dark and warm environment, and then carrying out alcohol washing and vacuum drying on the reacted foam nickel to obtain Pt NC The concentration of the chloroplatinic acid solution is 1 mg/mL-3 mg/mL.
Pt NC The NiMn-MOF takes a NiMn-MOF nano material with regular nanosheet morphology and formed by taking Ni and Mn as metal sites and taking p-dibenzoic acid as an organic ligand as a precursor, and then a simple low-Pt-concentration room-temperature wet chemical etching method is utilized to prepare high-activity Pt NC the/NiMn-MOF composite nanometer material.
The method for preparing the nanocluster/MOF composite structure disclosed by the invention is simple, low in energy consumption and suitable for industrial production. The synthesized bifunctional MOF-anchored Pt nanocluster catalyst prepared by the method can be used as a catalyst for degrading heavy current HER, UOR and urea, so that the problem that the traditional catalyst has a single function is solved, the performance of the heavy current HER is superior to that of commercial Pt/C, and meanwhile, the method for preparing the nanoclusters is simple and easy, and a new thought is provided for synthesis of the high-activity nanocluster catalyst.
In the method for adjusting and synthesizing the bimetallic organic framework nano material by the one-step method, in the step (2), the metal nickel salt is nickel nitrate [ Ni (NO) 3 ) 2 Or Ni (NO) 3 ) 2 ·6H 2 O ] and nickel sulfate [ NiSO ] 4 、NiSO 4 ·H 2 O、NiSO 4 ·2H 2 O、NiSO 4 ·4H 2 O、NiSO 4 ·6H 2 O or NiSO 4 ·7H 2 O or nickel chloride [ NiCl ] 2 、NiCl 2 ·6H 2 O ]; the metal manganese salt is manganese nitrate [ Mn (NO) 3 ) 2 ∙4H 2 O or Mn (NO) 3 ) 2 ∙2H 2 O ] and manganese sulfate [ MnSO ] 4 ∙7H 2 O、MnSO 4 ·H 2 O or MnSO 4 ·4H 2 O ] or manganese chloride [ MnCl ] 2 、MnCl 2 ∙4H 2 O ]; the solvent consists of N, N-dimethylformamide, ethanol and deionized water.
Preferably, in the step (2), the molar ratio of the metallic nickel salt to the metallic manganese salt to the terephthalic acid is (0.1 to 1.0): (0.1 to 1.0): (0.1 to 1.0).
Preferably, in the step (2), the volume ratio of the solvent N, N-dimethylformamide to ethanol to deionized water is 4:3:1.
preferably, the drying temperature in the step (5) is 60 ℃ and the drying time is 8 h.
The invention also requests to protect the bimetallic MOF anchored Pt nanocluster catalyst prepared by the method, and the method for synthesizing the nanoclusters is characterized in that a nanometer material with a nanometer sheet structure formed by a metal organic frame is used as a precursor, and Pt is synthesized under the etching of a chloroplatinic acid aqueous solution at room temperature NC A NiMn-MOF composite nanomaterial; the material can be used as an electrocatalyst and applied to high-current HER, urea electrocatalysis and electrocatalysis urea degradation to improve the catalysis efficiency.
The technical scheme of the invention achieves the following beneficial technical effects:
the invention provides a novel bimetallic MOF anchored Pt nanocluster catalyst which is excellent in performance and has wide application.
The bimetallic MOF anchored Pt nanocluster catalytic electrode nanomaterial synthesized by the method firstly takes Ni and Mn as metal nodes and p-dibenzoic acid as an organic ligand to prepare a precursor of a NiMn-MOF nanomaterial; and then loading the Pt nanoclusters on the MOF precursor by using a room-temperature wet chemical etching method. The method overcomes the defect that the synthesis path of the nanocluster synthesized by other prior art is complex, and also overcomes the problems of instability and single function of the conventional MOF powder electrode.
Pt prepared by the invention NC The overpotential of 56 mV, 170 mV and 289 mV is only needed in the electrocatalytic hydrogen evolution process of the/NiMn-MOF composite nano material respectively, and the overpotential can reach 100 mA cm -2 、500 mA·cm -2 And 1000 mA · cm -2 The current density provides a new idea for preparing industrial hydrogen production materials. Meanwhile, the nano material can rapidly and efficiently degrade urea in the urea wastewater into N 2 And CO 2 Corresponding ureaThe degradation rate (1.0 mol/L KOH + 0.33 mol/L Urea of electrolyte) can reach 96.1 percent in a short time.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a bimetallic MOF anchored Pt nanocluster catalyst according to an embodiment of the present invention;
FIG. 2 XRD patterns of a bimetallic MOF anchored Pt nanocluster catalyst in an embodiment of the present invention (NiMn-MOF and Pt) NC /NiMn-MOF)；
FIG. 3 is a scanning electron microscope image of a bimetallic NiMn-MOF catalyst nanomaterial prepared in the example of the present invention, wherein a is an SEM picture and b is an EDS (electron-dispersive spectroscopy) spectrum of a material component;
FIG. 4 is a scanning electron micrograph of a bimetallic MOF anchored Pt nanocluster catalyst nanomaterial fabricated in an embodiment of the present invention, where a is Pt NC SEM picture of/NiMn-MOF, and b is EDS map.
FIG. 5 is a scanning Transmission Electron Microscopy (TEM) image of a bimetallic MOF-anchored Pt nanocluster catalyst prepared in an example of the present invention, where a and b are Pt NC TEM pictures of/NiMn-MOF and enlarged views of the corresponding positions;
fig. 6 is a graph of HER performance under high current conditions for a bimetallic MOF-anchored Pt nanocluster catalyst prepared in an example of the present invention and a control thereof, where a is the LSV polarization curve and b is the corresponding performance histogram. (ii) a
FIG. 7 UOR performance plots of a bimetallic MOF catalyst and a control thereof prepared in an example of the invention, where a is Pt NC The UOR polarization curves (LSV) of NiMn-MOF and its comparative samples are shown, and b is a comparison graph of the performance of the samples at different current densities.
FIG. 8 is a graph of HER and UOR stability tests of a bimetallic MOF anchored Pt nanocluster catalyst prepared in an example of the present invention, where a is Pt NC Comparative LSV Performance of NiMn-MOF after 1000 CV cycles in HER Process, b is Pt NC Comparative plot of LSV performance of NiMn-MOF after 1000 CV cycles in UOR process;
FIG. 9 is a graph of the urea degradation performance of Ni-MOF and NiMn-MOF catalysts prepared in an example of the present invention, where a is the urea degradation of Ni-MOF and b is the urea degradation performance of NiMn-MOF;
FIG. 10 Pt prepared in an example of the invention NC The urea degradation performance graph of the NiMn-MOF catalyst is shown, wherein a is the urea degradation performance graph of Pt/NiMn-MOF, and b is Pt NC Comparative urea degradation rate performance plots for NiMn-MOF, niMn-MOF, and Ni-MOF catalysts.
Detailed Description
Advantages and features of the present disclosure, and methods for achieving the same, will become apparent with reference to the following embodiments in conjunction with the accompanying drawings. However, the embodiments should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Unless otherwise defined, all terms (including technical and scientific terms) in this specification may be defined as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the present disclosure and the relevant art and will be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The chemical reagents used in the invention, unless otherwise specified, were used in analytical purity and were purchased from the market at a concentration of 99.99% ethanol.
The invention provides a bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst, which is Pt as shown in figure 2 NC A NiMn-MOF nanomaterial, which in an X-ray diffraction spectrum of the nanomaterial has a monoclinic nickel-based metal organic framework (Ni-MOF) structure, and has a corresponding XRD diffraction angle 2 theta in a range of 5-50 degrees, wherein obvious XRD diffraction peaks appearing at positions of 8.9 degrees, 15.5 degrees, 28.3 degrees and 30.6 degrees of the 2 theta angle respectively correspond to (200), (400), (20-2) and (311) crystal planes in the NiMn-MOF structure.
Example 1
A synthetic schematic diagram of a bimetallic MOF-anchored Pt nanocluster catalyst synthesized in two simple steps is shown in fig. 1, and specifically comprises the following steps:
step (1): pretreating the foam nickel NF, firstly carrying out ultrasonic treatment in 3M hydrochloric acid for 15 minutes, then carrying out ultrasonic treatment in ultrapure water for 10 minutes, finally carrying out ultrasonic treatment in ethanol for 5 minutes, and naturally air-drying for later use;
step (2): 1 mmol of metallic nickel salt Ni (NO) 3 ) 2 ·6H 2 O, 0.8 mmol of manganese metal salt Mn (NO) 3 ) 2 ·4H 2 O and 1 mmol of p-dibenzoic acid C 8 H 6 O 4 Adding the mixture into a solvent, wherein the solvent is composed of 15 mL of ethanol, 20 mL of N, N-dimethylformamide and 5 mL of deionized water, and uniformly stirring to form an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a 100 ml polytetrafluoroethylene reaction kettle, and reacting for 12 h at 120 ℃;
and (4): and washing the foam nickel with alcohol, and drying in vacuum to obtain the NiMn-MOF precursor.
And (5): placing the obtained NiMn-MOF precursor into 10 mL of 1 mg/mL chloroplatinic acid solution, reacting for 1 h in a dark environment at room temperature, washing the reacted foam nickel with alcohol, and drying in vacuum to obtain the bimetallic NiMn-MOF anchored Pt nanocluster catalytic nanomaterial, namely Pt NC /NiMn-MOF。
The drying temperature of the vacuum drying in the step (4) and the step (5) is 60 ℃, and the drying time is 8 h.
In the embodiment, a bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst is synthesized by a simple hydrothermal and room temperature wet chemical etching method in two steps, and a synthesis reference basis is provided for anchoring nanoclusters by an MOF structure; the synthesized material has the dual-function performance of HER and UOR, and can be applied to the hydrogen production of industrial large-current electrolytic water; the application to urea oxidation is mainly a urea degradation test.
FIG. 1 is a simple schematic diagram of MOF anchored Pt nanocluster synthesis for Pt synthesis by a simple hydrothermal and room temperature wet chemical etching two-step synthesis method NC A/NiMn-MOF nanocomposite.
FIG. 2 shows NiMn-MOF and Pt prepared in this example NC XRD of/NiMn-MOF,from the figure, it can be found that there is no X-ray diffraction peak of any metal Pt other than that of NiMn-MOF, and thus it can be presumed that Pt is not supported on NiMn-MOF in the form of nanoparticles. From fig. 3, it can be known that the main chemical components of NiMn-MOF are nickel, manganese, carbon and oxygen, and the corresponding microscopic nano-morphology is a self-supporting two-dimensional porous nano-sheet structure. FIG. 4 shows Pt prepared in this example NC Scanning electron microscope images of the NiMn-MOF nano material show that the main chemical components are platinum, nickel, manganese, carbon and oxygen, and the micro morphology of the NiMn-MOF precursor is not changed by the Pt load, so that the existence form of Pt in the MOF precursor can be presumed to be nano cluster doping. FIG. 5 shows Pt prepared in this example NC Dark field scanning transmission electron microscope (HAADF-STEM) photographs of/NiMn-MOF nanomaterials. In general, the brightness of each metal atom in HAADF mode is proportional to the 1.8 th power of the corresponding atomic number, and since the atomic number of Pt is the largest in this system, pt atoms are brighter than substrate atoms such as Ni, mn, O, etc. in NiMn-MOF. Therefore, the bright spots marked with circles one by one in fig. 5b are Pt clusters, i.e., pt exists in the catalyst in the form of nanoclusters.
Example 2
A synthetic schematic diagram of a bimetallic MOF-anchored Pt nanocluster catalyst synthesized in two simple steps is shown in fig. 1, and specifically comprises the following steps:
step (1): pretreating the foam nickel NF, firstly carrying out ultrasonic treatment in 3M hydrochloric acid for 15 minutes, then carrying out ultrasonic treatment in ultrapure water for 10 minutes, finally carrying out ultrasonic treatment in ethanol for 5 minutes, and naturally air-drying for later use;
step (2): 1 mmol of metallic nickel salt Ni (NO) 3 ) 2 ·6H 2 O, 0.8 mmol of manganese metal salt Mn (NO) 3 ) 2 ·4H 2 O and 1 mmol of p-dibenzoic acid C 8 H 6 O 4 Adding the mixture into a solvent, wherein the solvent is composed of 15 mL of ethanol, 20 mL of N, N-dimethylformamide and 5 mL of deionized water, and uniformly stirring to form an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a 100 ml polytetrafluoroethylene reaction kettle, and reacting for 12 h at the temperature of 140 ℃;
and (4): and washing the foam nickel with alcohol, and drying in vacuum to obtain the NiMn-MOF precursor.
And (5): placing the obtained NiMn-MOF precursor into 10 mL of 2 mg/mL chloroplatinic acid solution, reacting for 1 h in a dark environment at room temperature, washing the reacted foam nickel with alcohol, and drying in vacuum to obtain the bimetallic NiMn-MOF anchored Pt nanocluster catalytic nanomaterial, namely Pt NC /NiMn-MOF。
In the step (4) and the step (5), the drying temperature is 60 ℃, and the drying time is 8 h.
Example 3
A synthetic schematic diagram of a bimetallic MOF-anchored Pt nanocluster catalyst synthesized in two simple steps is shown in fig. 1, and specifically comprises the following steps:
step (1): pretreating the foam nickel NF, firstly carrying out ultrasonic treatment in 3M hydrochloric acid for 15 minutes, then carrying out ultrasonic treatment in ultrapure water for 10 minutes, finally carrying out ultrasonic treatment in ethanol for 5 minutes, and naturally air-drying for later use;
step (2): 1 mmol of metallic nickel salt Ni (NO) 3 ) 2 ·6H 2 O, 0.8 mmol of manganese metal salt Mn (NO) 3 ) 2 ·4H 2 O and 1 mmol of p-dibenzoic acid C 8 H 6 O 4 Adding the mixture into a solvent, wherein the solvent is composed of 15 mL of ethanol, 20 mL of N, N-dimethylformamide and 5 mL of deionized water, and uniformly stirring to form an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a 100 ml polytetrafluoroethylene reaction kettle, and reacting for 12 h at 160 ℃;
and (4): and washing and drying the foamed nickel by alcohol to obtain the NiMn-MOF precursor.
And (5): placing the obtained NiMn-MOF precursor into 10 mL of 3 mg/mL chloroplatinic acid solution, reacting for 1 h in a dark environment at room temperature, and then carrying out alcohol washing and vacuum drying on the reacted foam nickel to obtain the bimetallic NiMn-MOF anchored Pt nanocluster catalytic nanomaterial, namely Pt NC /NiMn-MOF。
In the step (4) and the step (5), the drying temperature is 60 ℃, and the drying time is 8 h.
Example 4
A preparation method of a bimetallic MOF anchored Pt nanocluster catalyst specifically comprises the following steps:
step (1): pretreating the foam nickel NF, firstly carrying out ultrasonic treatment in 3M hydrochloric acid for 15 minutes, then carrying out ultrasonic treatment in ultrapure water for 10 minutes, finally carrying out ultrasonic treatment in ethanol for 5 minutes, and naturally air-drying for later use;
step (2): 1 mmol of metallic nickel salt Ni (NO) 3 ) 2 ·6H 2 O, 0.8 mmol of manganese metal salt Mn (NO) 3 ) 2 ·4H 2 O and 1 mmol of p-dibenzoic acid C 8 H 6 O 4 Adding the mixture into a solvent, wherein the solvent is composed of 15 mL of ethanol, 20 mL of N, N-dimethylformamide and 5 mL of deionized water, and uniformly stirring to form an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a 100 ml polytetrafluoroethylene reaction kettle, and reacting for 12 h at the temperature of 120 ℃;
and (4): and (3) washing the foamed nickel with alcohol, and drying in vacuum (the drying temperature is 60 ℃, and the drying time is 8 h) to obtain the NiMn-MOF precursor.
And (5): placing the obtained NiMn-MOF precursor into 10 mL of 2 mg/mL chloroplatinic acid solution, reacting for 1 h in a dark environment at room temperature, washing the reacted foam nickel with alcohol, and drying in vacuum (the drying temperature is 60 ℃ and the drying time is 8 h)), so as to obtain the bimetallic NiMn-MOF anchored Pt nanocluster catalytic nanomaterial, namely Pt NC /NiMn-MOF。
Example 5
A preparation method of a bimetallic MOF anchored Pt nanocluster catalyst specifically comprises the following steps:
step (1): pretreating the foam nickel NF, firstly carrying out ultrasonic treatment in 3M hydrochloric acid for 15 minutes, then carrying out ultrasonic treatment in ultrapure water for 10 minutes, finally carrying out ultrasonic treatment in ethanol for 5 minutes, and naturally air-drying for later use;
step (2): 1 mmol of the metallic nickel salt NiCl 2 ·6H 2 O, 0.8 mmol of MnCl metal salt 2 ∙4H 2 O and 1 mmol of p-dibenzoic acid C 8 H 6 O 4 Adding the mixture into a solvent, wherein the solvent is composed of 15 mL of ethanol, 20 mL of N, N-dimethylformamide and 5 mL of deionized water, and uniformly stirring to form an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a 100 ml polytetrafluoroethylene reaction kettle, and reacting for 24h at 120 ℃;
and (4): and washing the foam nickel with alcohol, and drying in vacuum to obtain the NiMn-MOF precursor.
And (5): placing the obtained NiMn-MOF precursor into 10 mL of 1 mg/mL chloroplatinic acid solution, reacting for 1 h in a dark environment at room temperature, washing the reacted foam nickel with alcohol, and drying in vacuum to obtain the bimetallic NiMn-MOF anchored Pt nanocluster catalytic nanomaterial, namely Pt NC /NiMn-MOF。
In the steps (4) and (5), the drying temperature of vacuum drying is 60 ℃, and the drying time is 8 h.
Example 6
A preparation method of a bimetallic MOF anchored Pt nanocluster catalyst specifically comprises the following steps:
step (1): pretreating the foam nickel NF, firstly carrying out ultrasonic treatment in 3M hydrochloric acid for 15 minutes, then carrying out ultrasonic treatment in ultrapure water for 10 minutes, finally carrying out ultrasonic treatment in ethanol for 5 minutes, and naturally air-drying for later use;
step (2): 1 mmol of metallic nickel salt NiSO 4 ·6H 2 O, 0.8 mmol of MnSO 4 ·4H 2 O and 1 mmol of p-dibenzoic acid C 8 H 6 O 4 Adding the mixture into a solvent, wherein the solvent is composed of 15 mL of ethanol, 20 mL of N, N-dimethylformamide and 5 mL of deionized water, and stirring uniformly to form an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a 100 ml polytetrafluoroethylene reaction kettle, and reacting at 120 ℃ for 24 ℃;
and (4): and washing the foam nickel with alcohol, and drying in vacuum to obtain the NiMn-MOF precursor.
And (5): the resulting NiMn-MOF precursor was placed in 10 mL of a 3 mg/mL solution of chloroplatinic acidReacting in the solution for 1 h at room temperature in a dark environment, and then carrying out alcohol washing and vacuum drying on the reacted foam nickel to obtain the bimetallic NiMn-MOF anchored Pt nanocluster catalytic nanomaterial, namely Pt NC /NiMn-MOF。
The drying temperature of the vacuum drying in the step (4) and the step (5) is 60 ℃, and the drying time is 8 h.
For the bifunctional Pt prepared in the invention example 1 NC the/NiMn-MOF composite nano material is respectively subjected to tests on HER catalytic activity and UOR catalytic activity, and is used for urea degradation to test the urea degradation performance of the composite nano material.
(1) HER catalytic activity of prepared catalyst tested by three-electrode system
Taking Pt prepared in example NC The method comprises the following steps of taking NiMn-MOF (cut to be 1 cm multiplied by 1 cm) as a working electrode, taking a Pt electrode as an auxiliary electrode (the current is overlarge, a carbon rod can be corroded and fall off), taking an Hg/HgO electrode as a reference electrode, preparing 1 mol/L KOH (100 mL) as electrolyte, and testing HER catalytic performance under a large current condition.
As can be seen from FIG. 6a, pt prepared in the example NC NiMn-MOF as HER catalyst, driving 100 mA cm -2 The overpotential of the current density of (a) is only 56 mV. As can be seen in FIG. 6b, pt NC The HER catalytic activity of NiMn-MOF under high current density can be comparable to or even better than that of commercial Pt/C, which provides a new research idea for the development of an HER hydrogen production material system oriented to industrial application. The introduction of Pt clusters is considered to greatly improve the HER catalytic activity of NiMn-MOF, so that the Pt clusters are indirectly proved to be main active species of HER, in addition, the HER catalytic performances of Ni-MOF and NiMn-MOF are close to each other, the Ni and Mn sites are not real active sites of HER and mainly play a role in carrier synergy. Furthermore, as can be seen from FIG. 8a, pt NC After 10000 CV cycles of NiMn-MOF in HER process, the LSV performance of the NiMn-MOF is not changed greatly, which shows that the NiMn-MOF has better stability, and further proves that Pt NC The NiMn-MOF has great potential in the field of hydrogen production facing industrial water electrolysis.
In fig. 6 to 7, nickel Foam (NF): 1 cm x 1 cm, purchased from SpirariaA netting of netting material; ruthenium dioxide (RuO) 2 ): a microphone forest; ni-MOF and NiMn-MOF are precursors prepared by adopting the method of the embodiment under the synthesis conditions of 120 ℃ and 12 h, wherein the difference is that the types and the proportions of the added metal sources are different. Pt NC The NiMn-MOF is a Pt monatomic MOF loaded nano material prepared by taking NiMn-MOF as a precursor and utilizing a room-temperature wet chemical etching method.
(2) UOR catalytic activity of the prepared catalyst tested by a three-electrode system
Taking Pt prepared in example NC The method comprises the following steps of taking NiMn-MOF (cut to be 1 cm multiplied by 1 cm) as a working electrode, taking a graphite carbon rod and an Hg/HgO electrode as an auxiliary electrode and a reference electrode respectively, preparing 100 mL of 1 mol/L KOH and 0.33 mol/L urea as electrolyte, and testing the oxidation performance of the electrocatalytic urea.
As can be seen from FIGS. 7a and 7b, pt NC The UOR catalytic performance of the/NiMn-MOF is optimal and is 200 mA-cm -2 And 300 mA-cm -2 The driving voltage of UOR at current density is 1.34V and 1.35V, which are much lower than that of NiMn-MOF, ni-MOF and commercial RuO 2 A catalyst. Further, by comparing the LSV polarization curve in fig. 7a, it can be known that the UOR catalytic performance of the Ni-based two-dimensional MOF can be greatly improved by Mn doping, which may be attributed to that the electronic structure of Ni-MOF is regulated by high-valence Mn doping, and the adsorption and desorption of the intermediate in the urea oxidation process is optimized. In addition, the introduction of Pt clusters can further generate synergistic effect with NiMn-MOF so as to increase the conductivity and catalytic activity of the MOF carrier. From FIG. 8b, it can be seen that Pt NC The LSV polarization curve of the NiMn-MOF is not changed greatly after 1000 CV cycles in the UOR process, and the urea oxidation stability is proved to be better. As is well known, no matter basic research or industrial application oriented, the stability of the MOF material system is always a core problem in the research of the catalytic field, in the case, the catalytic activity and stability of the Ni-based two-dimensional MOF are greatly improved by means of nanocluster modification and atom doping, which provides a new insight for the development, design and application of MOF-based materials.
(3) Urea degradation performance of the prepared catalyst by two-electrode test
Urea dropTwo-electrode electrical degradation test of desorption, wherein self-supporting Pt is adopted for both the cathode and the anode NC The system is used for testing the degradation performance of urea and comparing the degradation performance of the urea by preparing 100 mL of 1 mol/L KOH + 0.33 mol/L urea solution as electrolyte after preparing a/NiMn-MOF or Ni-MOF nano material (4 cm multiplied by 4 cm).
FIGS. 9a-b and 10a-b are graphs of the performance of urea degradation tests. It can be seen from FIGS. 9a-b and 10a-b that the bifunctional Pt prepared in the examples NC the/NiMn-MOF composite nano material is used as a catalytic electrode to carry out electrocatalytic degradation on the urea-rich alkaline electrolyte, the degradation rate of urea in the system can reach 96.1 percent after three hours, the urea degradation performance is far superior to that of NiMn-MOF and Ni-MOF, and the result shows that Pt NC The NiMn-MOF has better degradation performance on urea, and provides a new strategy for treating the sewage rich in urea in daily life.
In summary, the above examples are merely examples for clearly illustrating the applications, and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.
Claims (10)
1. A bimetallic MOF anchored Pt nanocluster catalyst is characterized in that the catalyst is Pt NC A NiMn-MOF nanomaterial, which in its X-ray diffraction spectrum exhibits a monoclinic nickel-based metal organic framework (Ni-MOF) structure, the corresponding XRD diffraction angles 2 theta range from 5 DEG to 50 DEG, wherein the distinct XRD diffraction peaks at the positions of 8.9 DEG, 15.5 DEG, 28.3 DEG and 30.6 DEG of 2 theta angle respectively correspond to the (200), (400), (20-2) and (311) crystal planes in the NiMn-MOF structure.
2. Preparation method of bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst which is Pt NC /NiMn-MOF, the method is as follows: taking metal nickel and manganese as metal nodes and terephthalic acid as the main componentGrowing the NiMn-MOF precursor on foam nickel in situ by taking acid as an organic ligand, and loading the Pt nanocluster on the surface of the NiMn-MOF precursor by utilizing a room-temperature wet chemical etching method to obtain Pt NC the/NiMn-MOF composite nanometer material.
3. The method of claim 2, comprising the steps of:
step (1): pretreating foamed nickel;
step (2): adding metal nickel salt, metal manganese salt and terephthalic acid into a solvent, and dissolving
The agent consists of ethanol, N-dimethylformamide and deionized water, and is uniformly stirred to obtain an initial mixed solution;
and (3): transferring the initial mixed solution and the foamed nickel into a polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction, preferably, the reaction temperature of the hydrothermal reaction is 120-160 ℃, and the reaction time is 12-24 hours;
and (4): taking out the reacted foam nickel, washing with alcohol, and vacuum drying to obtain the final product
A bimetallic organic framework NiMn-MOF precursor;
and (5): immersing the resulting NiMn-MOF precursor in a quantity of chloroplatinic acid solution, and a chamber
Reacting for 1 h in a dark and warm environment, and then carrying out alcohol washing and vacuum drying on the reacted foam nickel to obtain Pt NC The NiMn-MOF nano material is preferably prepared by a chloroplatinic acid solution with the concentration of 1-3 mg/mL.
4. The method according to claim 3, wherein in the step (1), the pretreatment is carried out by: immersing foamed nickel with the size of 2 cm multiplied by 3 cm in 3 mol/L hydrochloric acid for ultrasonic treatment for 15 minutes, then performing ultrasonic treatment in ultrapure water for 10 minutes, finally performing ultrasonic treatment in ethanol for 5 minutes, and naturally drying for later use.
5. The method according to claim 3, wherein the metallic nickel salt in step (2) is one of nickel nitrate, nickel sulfate and nickel chloride, and the metallic manganese salt is one of manganese nitrate, manganese sulfate and manganese chloride.
6. The preparation method according to claim 3, wherein in the step (2), the molar ratio of the metal nickel salt to the metal manganese salt to the terephthalic acid in the synthesis of the MOF precursor is (0.1 to 1.0): (0.1 to 1.0): (0.1 to 1.0).
7. The preparation method according to claim 3, wherein in the step (2), the volume ratio of the solvent N, N-dimethylformamide to ethanol to deionized water is 4:3:1.
8. the method according to claim 3, wherein the drying temperature of the vacuum drying in the steps (4) and (5) is 60 ℃ and the drying time is 8 hours.
9. Pt according to claim 1 NC NiMn-MOF nano material or Pt prepared by using preparation method of any one of claims 2 to 9 NC Use of/NiMn-MOF nanomaterials as electrocatalysts.
10. Use according to claim 9, wherein the electrocatalyst is used for high current electrolysis of water for hydrogen production, urea oxidation or urea degradation.
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