{"title":"通过改善双金属节点的传质和电荷转移来增强氢气进化反应。","authors":"Zhihui Li, Xinyu Zhang, Yiran Teng, Hanming Zhang, Tongguang Xu, Fei Teng","doi":"10.1021/acsami.4c11560","DOIUrl":null,"url":null,"abstract":"<p><p>The high cost of hydrogen production by water electrolysis severely challenges its commercial application. It is highly desirable to develop efficient electrocatalysts and innovative electrolytic cells. Introducing additional metal nodes to form bimetallic metal-organic framework (MOF) is a simple, feasible strategy to overcome the poor electrocatalytic performance of single-metal MOF. In this study, the hydrothermal method is used to synthesize bimetallic Ni<i><sub>x</sub></i>Co<sub>y</sub>-BTC. It is found that for hydrogen evolution reaction (HER), Ni<sub>0.8</sub>Co<sub>0.2</sub>-BTC merely requires a potential of -0.203 V (vs reverse hydrogen electrode, RHE) to achieve 10 mA cm<sup>-2</sup>, which is significantly lower than that of Ni-BTC (-0.341 V vs RHE). Notably, electrochemical impedance spectroscopy (EIS) and distribution of relaxation time (DRT) analysis indicate that Ni<i><sub>x</sub></i>Co<i><sub>y</sub></i>-BTC has improved charge transfer and mass transfer process, compared with Ni-BTC. Electron paramagnetic resonance (EPR) confirms that Ni<sub>0.8</sub>Co<sub>0.2</sub>-BTC has more unpaired electrons than Ni-BTC. Density functional theory (DFT) calculations show that compared with Ni-BTC, Ni<i><sub>x</sub></i>Co<i><sub>y</sub></i>-BTC is more thermodynamically favorable for the adsorption of H<sup>+</sup>, OH<sup>-</sup>, and H<sub>2</sub>O. It demonstrates that the change of mass transfer caused by bimetallic nodes and the delicate variation of MOF surface play an important role in the electrochemical process. Moreover, a novel electrolytic cell was developed using a methanol oxidation reaction (MOR) to replace oxygen evolution reaction (OER). In this MOR-based electrolytic cell, a current density of 50 mA cm<sup>-2</sup> can be achieved at only a cell voltage of 1.85 V, which is lower than the 2.22 V of OER-based electrolytic cell, suggesting that 16.7% electric energy can be saved. At the same time, the Faraday efficiency (FE, 98.2%) of the MOR-based cell is higher than that (94.5%) of the OER-based cell. This research offers a promising strategy for low-cost hydrogen production.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":null,"pages":null},"PeriodicalIF":5.4000,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhancing Hydrogen Evolution Reaction through the Improved Mass Transfer and Charge Transfer by Bimetal Nodes.\",\"authors\":\"Zhihui Li, Xinyu Zhang, Yiran Teng, Hanming Zhang, Tongguang Xu, Fei Teng\",\"doi\":\"10.1021/acsami.4c11560\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The high cost of hydrogen production by water electrolysis severely challenges its commercial application. It is highly desirable to develop efficient electrocatalysts and innovative electrolytic cells. Introducing additional metal nodes to form bimetallic metal-organic framework (MOF) is a simple, feasible strategy to overcome the poor electrocatalytic performance of single-metal MOF. In this study, the hydrothermal method is used to synthesize bimetallic Ni<i><sub>x</sub></i>Co<sub>y</sub>-BTC. It is found that for hydrogen evolution reaction (HER), Ni<sub>0.8</sub>Co<sub>0.2</sub>-BTC merely requires a potential of -0.203 V (vs reverse hydrogen electrode, RHE) to achieve 10 mA cm<sup>-2</sup>, which is significantly lower than that of Ni-BTC (-0.341 V vs RHE). Notably, electrochemical impedance spectroscopy (EIS) and distribution of relaxation time (DRT) analysis indicate that Ni<i><sub>x</sub></i>Co<i><sub>y</sub></i>-BTC has improved charge transfer and mass transfer process, compared with Ni-BTC. Electron paramagnetic resonance (EPR) confirms that Ni<sub>0.8</sub>Co<sub>0.2</sub>-BTC has more unpaired electrons than Ni-BTC. Density functional theory (DFT) calculations show that compared with Ni-BTC, Ni<i><sub>x</sub></i>Co<i><sub>y</sub></i>-BTC is more thermodynamically favorable for the adsorption of H<sup>+</sup>, OH<sup>-</sup>, and H<sub>2</sub>O. It demonstrates that the change of mass transfer caused by bimetallic nodes and the delicate variation of MOF surface play an important role in the electrochemical process. Moreover, a novel electrolytic cell was developed using a methanol oxidation reaction (MOR) to replace oxygen evolution reaction (OER). In this MOR-based electrolytic cell, a current density of 50 mA cm<sup>-2</sup> can be achieved at only a cell voltage of 1.85 V, which is lower than the 2.22 V of OER-based electrolytic cell, suggesting that 16.7% electric energy can be saved. At the same time, the Faraday efficiency (FE, 98.2%) of the MOR-based cell is higher than that (94.5%) of the OER-based cell. This research offers a promising strategy for low-cost hydrogen production.</p>\",\"PeriodicalId\":8,\"journal\":{\"name\":\"ACS Biomaterials Science & Engineering\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.4000,\"publicationDate\":\"2024-11-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Biomaterials Science & Engineering\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1021/acsami.4c11560\",\"RegionNum\":2,\"RegionCategory\":\"医学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/10/30 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, BIOMATERIALS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Biomaterials Science & Engineering","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1021/acsami.4c11560","RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/10/30 0:00:00","PubModel":"Epub","JCR":"Q2","JCRName":"MATERIALS SCIENCE, BIOMATERIALS","Score":null,"Total":0}
引用次数: 0
摘要
水电解制氢的高成本对其商业应用构成了严重挑战。开发高效的电催化剂和创新的电解槽是非常可取的。引入额外的金属节点形成双金属金属有机框架（MOF）是克服单金属 MOF 电催化性能差的一种简单可行的策略。本研究采用水热法合成了双金属 NixCoy-BTC。研究发现，在氢进化反应（HER）中，Ni0.8Co0.2-BTC 只需要 -0.203 V 的电位（相对于反向氢电极，RHE）就能达到 10 mA cm-2，明显低于 Ni-BTC 的电位（相对于反向氢电极，-0.341 V）。值得注意的是，电化学阻抗谱（EIS）和弛豫时间分布（DRT）分析表明，与 Ni-BTC 相比，NixCoy-BTC 改善了电荷转移和质量转移过程。电子顺磁共振（EPR）证实，Ni0.8Co0.2-BTC 比 Ni-BTC 有更多的未成对电子。密度泛函理论（DFT）计算表明，与 Ni-BTC 相比，NixCoy-BTC 在热力学上更有利于 H+、OH- 和 H2O 的吸附。这表明，双金属节点引起的传质变化和 MOF 表面的微妙变化在电化学过程中发挥了重要作用。此外，研究人员还利用甲醇氧化反应（MOR）取代氧进化反应（OER），开发出一种新型电解池。在这种基于 MOR 的电解池中，只需 1.85 V 的电池电压就能达到 50 mA cm-2 的电流密度，低于基于 OER 的电解池的 2.22 V 电压，这表明可以节省 16.7% 的电能。同时，基于 MOR 的电池的法拉第效率（FE，98.2%）高于基于 OER 的电池（94.5%）。这项研究为低成本制氢提供了一种前景广阔的策略。
Enhancing Hydrogen Evolution Reaction through the Improved Mass Transfer and Charge Transfer by Bimetal Nodes.
The high cost of hydrogen production by water electrolysis severely challenges its commercial application. It is highly desirable to develop efficient electrocatalysts and innovative electrolytic cells. Introducing additional metal nodes to form bimetallic metal-organic framework (MOF) is a simple, feasible strategy to overcome the poor electrocatalytic performance of single-metal MOF. In this study, the hydrothermal method is used to synthesize bimetallic NixCoy-BTC. It is found that for hydrogen evolution reaction (HER), Ni0.8Co0.2-BTC merely requires a potential of -0.203 V (vs reverse hydrogen electrode, RHE) to achieve 10 mA cm-2, which is significantly lower than that of Ni-BTC (-0.341 V vs RHE). Notably, electrochemical impedance spectroscopy (EIS) and distribution of relaxation time (DRT) analysis indicate that NixCoy-BTC has improved charge transfer and mass transfer process, compared with Ni-BTC. Electron paramagnetic resonance (EPR) confirms that Ni0.8Co0.2-BTC has more unpaired electrons than Ni-BTC. Density functional theory (DFT) calculations show that compared with Ni-BTC, NixCoy-BTC is more thermodynamically favorable for the adsorption of H+, OH-, and H2O. It demonstrates that the change of mass transfer caused by bimetallic nodes and the delicate variation of MOF surface play an important role in the electrochemical process. Moreover, a novel electrolytic cell was developed using a methanol oxidation reaction (MOR) to replace oxygen evolution reaction (OER). In this MOR-based electrolytic cell, a current density of 50 mA cm-2 can be achieved at only a cell voltage of 1.85 V, which is lower than the 2.22 V of OER-based electrolytic cell, suggesting that 16.7% electric energy can be saved. At the same time, the Faraday efficiency (FE, 98.2%) of the MOR-based cell is higher than that (94.5%) of the OER-based cell. This research offers a promising strategy for low-cost hydrogen production.
期刊介绍：
ACS Biomaterials Science & Engineering is the leading journal in the field of biomaterials, serving as an international forum for publishing cutting-edge research and innovative ideas on a broad range of topics:
Applications and Health – implantable tissues and devices, prosthesis, health risks, toxicology
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Characterization, Synthesis, and Modification – new biomaterials, bioinspired and biomimetic approaches to biomaterials, exploiting structural hierarchy and architectural control, combinatorial strategies for biomaterials discovery, genetic biomaterials design, synthetic biology, new composite systems, bionics, polymer synthesis
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