Synthesis and application of low-platinum MOFs electrocatalytic hydrogen evolution material
By preparing PtSA-PtAC composite electrocatalytic materials, the problem of low activity of noble metal catalysts was solved, and low-cost, high-efficiency electrocatalytic hydrogen evolution under acidic conditions was achieved, exhibiting excellent catalytic performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-21
- Publication Date
- 2026-03-27
AI Technical Summary
Existing precious metal catalysts have low quality and activity in the field of electrocatalytic hydrogen evolution, resulting in high production costs and difficulty in industrial application.
PtTCPP@UIO-66 intermediates were synthesized via a hydrothermal method and then calcined at high temperature to obtain PtSA-PtAC composite electrocatalytic materials. By utilizing the synergistic effect of Pt single atoms and Pt clusters, low-platinum MOF electrocatalytic hydrogen evolution materials were prepared.
It exhibits excellent electrocatalytic hydrogen evolution performance under acidic conditions, with ultra-high Pt quality activity and stability, approaching the performance of commercial Pt/C.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of electrocatalytic hydrogen evolution technology, specifically to the synthesis and application of a low-platinum MOF electrocatalytic hydrogen evolution material. Background Technology
[0002] Energy is a vital material foundation for human survival and development. Hydrogen energy is well-known for its high energy density, renewability, and pollution-free nature. Hydrogen produced by water electrolysis can achieve a purity of over 99%, making it an important industrial method for hydrogen production. Converting electrical energy into relatively stable chemical energy, while producing hydrogen without generating other byproducts, is an environmentally friendly and sustainable method for hydrogen storage. However, the slow kinetics of the hydrogen evolution reaction (HER) limit the efficiency of water electrolysis, resulting in high energy consumption. Therefore, developing highly active and durable electrocatalysts is essential to accelerating these reactions and improving energy conversion efficiency. Research on catalytic materials is of great significance for electrocatalytic hydrogen production technology.
[0003] Metal-organic frameworks (MOFs) are materials composed of ordered metal nodes and organic ligands, possessing excellent specific surface area and functional tunability. They are considered important precursors for supporting metal species through pyrolysis to generate carbon-based materials. Crucially, various organic ligands containing heteroatoms serve as excellent attachment sites for individual metal atoms. In particular, effective chemical bonds between metal atoms and heteroatoms can anchor metal atoms, reducing migration and aggregation during pyrolysis. The catalytic performance of electrocatalysts is generally determined by two main factors: the number of catalytic active sites and the intrinsic activity of individual active sites. Recent studies have shown that reducing catalyst particle size can increase the number of catalytic active sites and the exposed active surface area, while adjusting the metal sites and electronic structure can enhance the intrinsic properties of the metal sites. Reducing catalyst particles to the atomic level provides an effective pathway to achieving maximum utilization efficiency of metal atoms and improving the intrinsic catalytic activity of catalysts. In this regard, compared to bulk Pt and Pt nanoparticles, Pt single-atom and Pt cluster catalysts have attracted considerable attention in recent years due to their larger geometric and electrochemical surface area, more exposed active centers, and maximized Pt utilization at a lower cost. However, as far as we know, the quality and activity of precious metal catalysts currently used in the field of electrocatalytic hydrogen evolution are generally not high, which increases production costs.
[0004] Therefore, synthesizing a low-platinum MOF electrocatalytic hydrogen evolution material and applying it to electrocatalytic hydrogen evolution research is a research direction for those skilled in the art. Summary of the Invention
[0005] In view of the above-mentioned shortcomings of the existing technology, the purpose of this invention is to synthesize a low-platinum MOF electrocatalytic hydrogen evolution material to solve the problems of high price, low storage and difficulty in industrial application of noble metal-based catalytic materials in the existing technology.
[0006] This invention also provides a method for preparing a low-platinum MOF electrocatalytic hydrogen evolution material, which can be used to prepare Pt electrocatalytic materials.
[0007] This invention also provides an application of a low-platinum MOF electrocatalytic hydrogen evolution material. The Pt electrocatalytic material prepared by the preparation method described in this invention is suitable for electrocatalytic hydrogen evolution reaction under acidic conditions.
[0008] The technical solution adopted in this invention is as follows: A method for preparing a low-platinum MOF electrocatalytic hydrogen evolution material includes the following steps: Step 1) Using ZrCl4, terephthalic acid, benzoic acid and tetracarboxyphenylporphyrin platinum as raw materials, the intermediate PtTCPP@UIO-66 was prepared by hydrothermal method; Step 2) After high-temperature calcination of the intermediate PtTCPP@UIO-66, the composite electrocatalytic material Pt is obtained. SA -Pt AC .
[0009] In step 1), the reaction temperature is 135 degrees Celsius and the reaction time is 12 hours. In step 2), the calcination temperature is 800 degrees Celsius and the time is 2 hours.
[0010] This invention also provides an application of a low-platinum MOF electrocatalytic hydrogen evolution material, characterized in that the Pt single atom and Pt cluster synergistic electrocatalytic material is prepared by the method described in claim 1; the Pt single atom and Pt cluster synergistic electrocatalytic material is suitable for electrocatalytic hydrogen evolution under acidic conditions and exhibits excellent performance.
[0011] Compared with the prior art, the present invention has the following advantages: 1. The method for preparing electrocatalytic materials based on metal-organic frameworks provided by this invention enables the obtaining of composite electrocatalytic materials Pt SA -Pt AC The morphology of PtTCPP@UIO-66 before calcination was maintained, which can fully expose the active sites. The addition of PtTCPP provides active sites Pt on the one hand, and on the other hand, the pyrrole N in the porphyrin structure anchors the metal Pt, preventing it from agglomerating into nanoparticles under high temperature calcination.
[0012] 2. The electrocatalytic material of Pt single atom and Pt cluster synergistic effect prepared by the present invention is suitable for electrocatalytic hydrogen evolution research under acidic conditions, and exhibits excellent hydrogen evolution effect, ultra-high Pt mass activity and stability. Attached Figure Description
[0013] Figure 1 XRD pattern of UIO-66 prepared for implementation 1.
[0014] Figure 2 SEM image of UIO-66 prepared for implementation 1.
[0015] Figure 3 XRD pattern of ZrOx / C prepared for implementation 1.
[0016] Figure 4 Electrocatalytic hydrogen evolution diagram of ZrOx / C prepared in step 1.
[0017] Figure 5 SEM images of TCPP@UIO-66 prepared for implementation 2.
[0018] Figure 6 XRD pattern of ZrOx / CN prepared for implementation 2.
[0019] Figure 7 Electrocatalytic hydrogen evolution diagram of ZrOx / CN prepared in step 2.
[0020] Figure 8 SEM images of PtTCPP@UIO-66 prepared for implementation 3.
[0021] Figure 9 Pt prepared for implementation 3 SA -Pt AC SEM image.
[0022] Figure 10 Pt prepared for implementation 3 SA -Pt AC XRD pattern.
[0023] Figure 11 Pt prepared for implementation 3 SA -Pt AC Electrocatalytic hydrogen evolution diagram.
[0024] Figure 12 Pt prepared for implementation 3 SA -Pt AC Electrocatalytic impedance diagram. Detailed Implementation
[0025] The present invention will be further described below with reference to the accompanying drawings and embodiments. Example
[0026] The preparation method of ZrOx / C material includes the following steps: (1) ZrCl4 (0.39 mg), terephthalic acid (0.277 g), and benzoic acid (6 g) were added to 20 mL of DMF and stirred for 30 minutes to fully dissolve the raw materials. The mixture was then placed in a reaction vessel and reacted at 135 degrees Celsius for 12 hours. After the reaction cooled, the solid was centrifuged and washed several times with DMF and ethanol. Finally, it was dried to obtain UIO-66. (2) 200 mg of UIO-66 was calcined at 800 degrees Celsius for 2 hours under flowing N2 conditions to obtain ZrOx / C; from Figure 1 The XRD pattern shows that UIO-66 was successfully synthesized. Figure 2 The SEM images show that the morphology of the prepared UIO-66 exhibits an octahedral structure. Figure 3 It can be seen that ZrOx was successfully generated after calcination, and there is crystal information of ZrOx.
[0027] The prepared ZrOx / C material was used in the electrocatalytic hydrogen evolution process, as follows: (1) Preparation of test electrode: Weigh 1 mg ZrOx / C material and add it to 490 uL ethanol / water solution (volume ratio 1:1). Add 10 uL Nafion solution and then sonicate for 30 minutes to disperse the catalytic material evenly. Take 4 uL of the ultrasonic mixed solution and drop it onto the glassy carbon electrode. Let it air dry naturally before use.
[0028] (2) Electrocatalytic hydrogen evolution test: The three-electrode test mode was selected. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod electrode, the working electrode was a glassy carbon electrode with catalytic material, and the acidic electrolyte was 0.5 M H2SO4.
[0029] Appendix Figure 4 The image shows the electrocatalytic hydrogen evolution results of the prepared ZrOx / C material. Example
[0030] The preparation method of ZrOx / CN material includes the following steps: (1) ZrCl4 (0.39 mg), terephthalic acid (0.277 g), benzoic acid (6 g), and TCPP (12 mg) were added to 20 mL of DMF and stirred for 30 minutes to fully dissolve the raw materials. The mixture was then transferred to a reaction vessel and reacted at 135°C for 12 hours. After the reaction cooled, the solid was centrifuged and washed several times with DMF and ethanol. Finally, it was dried to obtain TCPP@UIO-66. (2) 200 mg TCPP@UIO-66 was calcined at 800 degrees Celsius for 2 hours under flowing N2 conditions to obtain ZrOx / CN; from Figure 5 The SEM images show that the morphology of the prepared TCPP@UIO-66 exhibits an octahedral structure. Figure 6 The XRD pattern reflects the information of the ZrOx crystals generated after calcination.
[0031] The prepared ZrOx / CN material was used in electrocatalytic hydrogen evolution, as detailed below: (1) Preparation of test electrode: Weigh 1 mg ZrOx / CN material and add it to 490 uL ethanol / water solution (volume ratio of 1:1). Add 10 uL Nafion solution and then sonicate for 30 minutes to disperse the catalytic material evenly. Take 4 uL of the sonicated mixed solution and drop it onto the glassy carbon electrode. Let it air dry naturally before use.
[0032] (2) Electrocatalytic hydrogen evolution test: The three-electrode test mode was selected. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod electrode, the working electrode was a glassy carbon electrode with catalytic material, and the acidic electrolyte was 0.5 M H2SO4.
[0033] Appendix Figure 7 The image shows the electrocatalytic hydrogen evolution results of the prepared ZrOx / CN material. Example
[0034] Pt SA -Pt AC The preparation method of the material includes the following steps: (1) ZrCl4 (0.39 mg), terephthalic acid (0.277 g), benzoic acid (6 g), and PtTCPP (12 mg) were added to 20 mL of DMF and stirred for 30 minutes to fully dissolve the raw materials. The mixture was then transferred to a reaction vessel and reacted at 135°C for 12 hours. After the reaction cooled, the solid was centrifuged and washed several times with DMF and ethanol. Finally, it was dried to obtain PtTCPP@UIO-66. (2) 200 mg of PtTCPP@UIO-66 was calcined at 800°C for 2 hours under flowing N2 conditions to obtain Pt SA -Pt AC ; from Figure 8 and Figure 9 The SEM images show that the morphology of the prepared PtTCPP@UIO-66 exhibits an octahedral structure, and the Pt after calcination at 800 degrees Celsius... SA -Pt AC It still has an octahedral structure. Figure 10The XRD pattern reflects the information of the ZrOx crystals generated after calcination.
[0035] Prepared Pt SA -Pt AC The material is used in electrocatalytic hydrogen evolution, specifically as follows: (1) Preparation of test electrode: Weigh 1 mg Pt SA -Pt AC The material was added to 490 μL of ethanol / water solution (volume ratio 1:1), and 10 μL of Nafion solution was added. The mixture was then sonicated for 30 minutes to ensure uniform dispersion of the catalytic material. 4 μL of the sonicated mixture was dropped onto the glassy carbon electrode and allowed to air dry before use.
[0036] (2) Electrocatalytic hydrogen evolution test: The three-electrode test mode was selected. The reference electrode was a saturated calomel electrode, the counter electrode was a carbon rod electrode, the working electrode was a glassy carbon electrode with catalytic material, and the acidic electrolyte was 0.5 M H2SO4.
[0037] Appendix Figure 11 For the preparation of Pt SA -Pt AC The electrocatalytic hydrogen evolution results of the material show that it exhibits excellent electrocatalytic hydrogen evolution performance, which is comparable to that of commercial 20 wt% Pt / C. Figure 12 Electrocatalytic impedance testing revealed that it exhibits a relatively small impedance characteristic.
[0038] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the technical solutions. Those skilled in the art should understand that any modifications or equivalent substitutions to the technical solutions of the present invention without departing from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.
Claims
1. A low-platinum MOF electrocatalytic hydrogen evolution material synthesized in situ, characterized in that, The electrocatalytic material is a composite electrocatalytic material Pt. SA -Pt AC .
2. A method for preparing a low-platinum MOF electrocatalytic hydrogen evolution material, characterized in that, The preparation of the Pt single-atom and Pt cluster electrocatalytic materials as described in claim 1 comprises the following steps: Step 1) Using ZrCl4, terephthalic acid, benzoic acid and tetracarboxyphenylporphyrin platinum as raw materials, the intermediate PtTCPP@UIO-66 was prepared by hydrothermal method; Step 2) After high-temperature calcination of the intermediate PtTCPP@UIO-66, the composite electrocatalytic material Pt is obtained. SA -Pt AC .
3. The method for preparing the electrocatalytic material with synergistic effect of Pt single atoms and Pt clusters according to claim 2, characterized in that, In step 1), the molar ratio of ZrCl4, terephthalic acid, benzoic acid and PtTCPP is 1:1:20:0.
05.
4. The method for preparing the electrocatalytic material of synergistic effect between Pt single atoms and Pt clusters according to claim 2, characterized in that, In step 1), the raw material is added to the organic solvent DMF, and after the raw material is fully dissolved, it is loaded into a reaction vessel and reacted at 135 °C for 12 h.
5. The method for preparing the electrocatalytic material of synergistic effect between Pt single atoms and Pt clusters according to claim 2, characterized in that, In step 2), the calcination temperature is 800 ℃ and the calcination time is 2 h.
6. The application of a low-platinum MOF electrocatalytic hydrogen evolution material, characterized in that, The Pt single-atom and Pt cluster synergistic electrocatalytic material prepared by any of the preparation methods described in claims 2 to 5 is suitable for electrocatalytic hydrogen evolution reaction under acidic conditions.