Pub Date : 2024-06-13DOI: 10.1021/acsenergylett.4c01238
Thimo S. Jacobs, Sunghak Park, Marco Schönig, Bert M. Weckhuysen, Marc T.M. Koper, Ward van der Stam
Accurate determination of the temperature dynamics at the electrode surface is crucial for advancing electrocatalysis, particularly in the development of stable materials that aid energy conversion and storage technologies. Here, lanthanide-based in situ luminescence thermometry was used to probe local heat effects at the platinum electrode surface during alkaline water electrolysis. It is demonstrated that the oxygen evolution reaction (OER) induces a more significant temperature increase compared to the hydrogen evolution reaction (HER) under the same electrochemical conditions. This difference is attributed to variations in overpotential heating and local effects on Joule heating. Furthermore, local heat effects are not observed at increased electrolyte concentrations during the HER, whereas substantial temperature variations (up to 2 K) are detected for the OER at higher electrolyte concentrations. Our observations highlight the potential of in situ luminescence thermometry to measure interfacial temperature effects during electrocatalytic reactions.
准确测定电极表面的温度动态对于推进电催化技术，尤其是开发有助于能量转换和储存技术的稳定材料至关重要。在此，我们使用基于镧系元素的原位发光测温法来探测碱性水电解过程中铂电极表面的局部热效应。研究表明，在相同的电化学条件下，氧进化反应（OER）比氢进化反应（HER）引起的温度升高更为显著。这种差异归因于过电位加热的变化和焦耳加热的局部效应。此外，在 HER 反应过程中，电解质浓度增加时未观察到局部热效应，而在电解质浓度较高的 OER 反应中，则检测到了较大的温度变化（高达 2 K）。我们的观察结果凸显了原位发光测温法测量电催化反应过程中界面温度效应的潜力。
{"title":"Luminescence Thermometry Probes Local Heat Effects at the Platinum Electrode Surface during Alkaline Water Electrolysis","authors":"Thimo S. Jacobs, Sunghak Park, Marco Schönig, Bert M. Weckhuysen, Marc T.M. Koper, Ward van der Stam","doi":"10.1021/acsenergylett.4c01238","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01238","url":null,"abstract":"Accurate determination of the temperature dynamics at the electrode surface is crucial for advancing electrocatalysis, particularly in the development of stable materials that aid energy conversion and storage technologies. Here, lanthanide-based <i>in situ</i> luminescence thermometry was used to probe local heat effects at the platinum electrode surface during alkaline water electrolysis. It is demonstrated that the oxygen evolution reaction (OER) induces a more significant temperature increase compared to the hydrogen evolution reaction (HER) under the same electrochemical conditions. This difference is attributed to variations in overpotential heating and local effects on Joule heating. Furthermore, local heat effects are not observed at increased electrolyte concentrations during the HER, whereas substantial temperature variations (up to 2 K) are detected for the OER at higher electrolyte concentrations. Our observations highlight the potential of <i>in situ</i> luminescence thermometry to measure interfacial temperature effects during electrocatalytic reactions.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141329572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-12DOI: 10.1021/acsenergylett.4c01153
Yi-Chen Lan, Po-Hao Lai, Bryan D. Vogt, Enrique D. Gomez
All-solid-state batteries provide opportunities for safe and robust energy storage solutions. An emerging issue is the final disposal of spent batteries due to the required production scale, limited lifetime, and lack of recycling methods. Here, we propose an architectural design for recyclable all-solid-state lithium batteries based on interfacial layers at the electrodes. Flexible lithium bis(fluorosulfonyl)imide doped polypropylene carbonate (PPC-LiFSI) interfacial layers improve physical contacts at Li metal and Li7La3Zr2O12 (LLZO)-based composite electrolytes interfaces and serve as sacrificial layers to enable clean separation and direct recycling. Recovered components demonstrate the preservation of electrochemical properties through direct reintegration into batteries. Fully recovered full cells with Li-metal and LTO anodes show 92.5% and 93.8% of original discharge capacity at 0.05 C and room temperature. We demonstrate an approach for the design of recyclable all-solid-state lithium batteries to fulfill long-term goals for sustainable energy storage devices.
{"title":"Interfacial Layers to Enable Recyclability of All-Solid-State Lithium Batteries","authors":"Yi-Chen Lan, Po-Hao Lai, Bryan D. Vogt, Enrique D. Gomez","doi":"10.1021/acsenergylett.4c01153","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01153","url":null,"abstract":"All-solid-state batteries provide opportunities for safe and robust energy storage solutions. An emerging issue is the final disposal of spent batteries due to the required production scale, limited lifetime, and lack of recycling methods. Here, we propose an architectural design for recyclable all-solid-state lithium batteries based on interfacial layers at the electrodes. Flexible lithium bis(fluorosulfonyl)imide doped polypropylene carbonate (PPC-LiFSI) interfacial layers improve physical contacts at Li metal and Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (LLZO)-based composite electrolytes interfaces and serve as sacrificial layers to enable clean separation and direct recycling. Recovered components demonstrate the preservation of electrochemical properties through direct reintegration into batteries. Fully recovered full cells with Li-metal and LTO anodes show 92.5% and 93.8% of original discharge capacity at 0.05 C and room temperature. We demonstrate an approach for the design of recyclable all-solid-state lithium batteries to fulfill long-term goals for sustainable energy storage devices.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141329539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-11DOI: 10.1021/acsenergylett.4c01240
Qingjie Wang, Zeyuan Wang, Nan Liao, Salvador Montilla-Verdú, Maxime Contreras, Néstor Guijarro, Jingshan Luo
Altering the surface stoichiometry of semiconductor electrodes is known to affect the photoelectrochemical (PEC) response. To date, several reports have hinted at the influence of the surface Bi:V ratio on the solar water oxidation performance of BiVO4 photoanodes, but only a handful of strategies have been reported to afford tuning of such surface stoichiometry, while a comprehensive understanding at an atomic level of the role of the surface termination remains elusive. Herein, we report a new methodology that modulates the surface Bi:V ratio and maximizes the PEC performance toward the oxygen evolution reaction (OER). The presence of ammonium metavanadate drastically reduces the surface recombination while improving the charge separation. Detailed characterization revealed that this treatment filled the native surface vanadium vacancies, which usually act as recombination centers, while inducing a significant increase in the density of oxygen vacancies, which reinforced the built-in electric field that drives the charge separation. Interestingly, coating with NiFeOx improves, especially, the charge separation in surface V-modified BiVO4. Results suggest that the V-modified surface termination altered the surface energetics of BiVO4, leading to an improved band alignment across the interface. Overall, these results provide a new platform to modulate the surface stoichiometry of BiVO4 thin films while shedding new light on the mechanisms by which the surface termination governs the PEC response.
{"title":"Tailoring the Surface Termination of BiVO4 Photoanodes Using Ammonium Metavanadate Enhances the Solar Water Oxidation Performance","authors":"Qingjie Wang, Zeyuan Wang, Nan Liao, Salvador Montilla-Verdú, Maxime Contreras, Néstor Guijarro, Jingshan Luo","doi":"10.1021/acsenergylett.4c01240","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01240","url":null,"abstract":"Altering the surface stoichiometry of semiconductor electrodes is known to affect the photoelectrochemical (PEC) response. To date, several reports have hinted at the influence of the surface Bi:V ratio on the solar water oxidation performance of BiVO<sub>4</sub> photoanodes, but only a handful of strategies have been reported to afford tuning of such surface stoichiometry, while a comprehensive understanding at an atomic level of the role of the surface termination remains elusive. Herein, we report a new methodology that modulates the surface Bi:V ratio and maximizes the PEC performance toward the oxygen evolution reaction (OER). The presence of ammonium metavanadate drastically reduces the surface recombination while improving the charge separation. Detailed characterization revealed that this treatment filled the native surface vanadium vacancies, which usually act as recombination centers, while inducing a significant increase in the density of oxygen vacancies, which reinforced the built-in electric field that drives the charge separation. Interestingly, coating with NiFeO<sub><i>x</i></sub> improves, especially, the charge separation in surface V-modified BiVO<sub>4</sub>. Results suggest that the V-modified surface termination altered the surface energetics of BiVO<sub>4</sub>, leading to an improved band alignment across the interface. Overall, these results provide a new platform to modulate the surface stoichiometry of BiVO<sub>4</sub> thin films while shedding new light on the mechanisms by which the surface termination governs the PEC response.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141304650","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-11DOI: 10.1021/acsenergylett.4c01027
Zezhou Guo, Zehao Cui, Arumugam Manthiram
LiNiO2-based layered oxides are regarded as promising cathode candidates for high-energy-density lithium-ion batteries. However, the large initial capacity loss (ICL) and severe electrode–electrolyte interfacial reactions significantly compromise the discharge capacity and cycle life of high-Ni cathodes. Here, we present a systemic investigation of the ICL in high-Ni cathodes by controlling the upper cutoff voltage (UCV) and dopants. It is demonstrated that the elevated ICL due to an incomplete M–H1 phase transition during discharge can be reduced via an activation step to H2–H3 phase transition at high voltages. It is shown that performing formation cycles of LiNiO2 cells with a high UCV of 4.4 V offers significantly improved discharge capacity with minimal capacity retention penalty on cycling under a low UCV of 4.1 V. Furthermore, it is found that doping with Co reduces ICL, while other dopants, such as Mn, Al, and Mg, lead to an increase in ICL.
基于 LiNiO2 的层状氧化物被认为是高能量密度锂离子电池的理想正极候选材料。然而，较大的初始容量损失（ICL）和严重的电极-电解质界面反应严重影响了高镍正极的放电容量和循环寿命。在此，我们通过控制上限截止电压（UCV）和掺杂剂，对高镍阴极中的 ICL 进行了系统研究。研究表明，由于放电过程中 M-H1 相变不完全而导致的 ICL 升高，可以通过激活步骤在高电压下降低到 H2-H3 相变。研究表明，在 4.4 V 的高 UCV 下进行二氧化钛电池的形成循环，可显著提高放电容量，而在 4.1 V 的低 UCV 下进行循环时，对容量保持的影响最小。此外，研究还发现，掺入 Co 会降低 ICL，而其他掺杂剂（如锰、铝和镁）则会提高 ICL。
{"title":"Reducing the Initial Capacity Loss in High-Nickel Cathodes with a Higher Upper Cut-off Voltage Formation Cycle Protocol","authors":"Zezhou Guo, Zehao Cui, Arumugam Manthiram","doi":"10.1021/acsenergylett.4c01027","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01027","url":null,"abstract":"LiNiO<sub>2</sub>-based layered oxides are regarded as promising cathode candidates for high-energy-density lithium-ion batteries. However, the large initial capacity loss (ICL) and severe electrode–electrolyte interfacial reactions significantly compromise the discharge capacity and cycle life of high-Ni cathodes. Here, we present a systemic investigation of the ICL in high-Ni cathodes by controlling the upper cutoff voltage (UCV) and dopants. It is demonstrated that the elevated ICL due to an incomplete M–H1 phase transition during discharge can be reduced via an activation step to H2–H3 phase transition at high voltages. It is shown that performing formation cycles of LiNiO<sub>2</sub> cells with a high UCV of 4.4 V offers significantly improved discharge capacity with minimal capacity retention penalty on cycling under a low UCV of 4.1 V. Furthermore, it is found that doping with Co reduces ICL, while other dopants, such as Mn, Al, and Mg, lead to an increase in ICL.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141329496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aqueous zinc metal batteries (ZMBs) have attracted much attention in the field of grid-scale energy storage due to their high safety, low cost, and abundant resources. Zn powders exhibit the unique advantages of high specific surface area, mature scaled-up manufacturing ability, and structural tunability, which can meet the large-scale energy storage devices, and even the special-shaped devices. However, Zn powder-based anodes are at an early stage and far from the practical industrial application. With the pursuit of comprehensive electrochemical performances of Zn powder-based anodes, this review focus on the advances, issues, and optimized strategies, which are discussed systematically from the previous reports of Zn powder-based anodes. Meanwhile, we also added many supplementary discussions of some important strategies in relevant content but not yet reported. Finally, future prospects toward high performance and practicability of Zn powder-based anodes are proposed, which will provide scientific guidance for the practical application of ZMBs.
{"title":"Zn Powder-Based Anodes for Aqueous Zn Metal Batteries: Strategies, Structures, and Perspectives","authors":"Biao Fu, Guanqun Liu, Yajue Zhang, Zhexuan Liu, Xuefang Xie, Guozhao Fang, Shuquan Liang","doi":"10.1021/acsenergylett.4c00628","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c00628","url":null,"abstract":"Aqueous zinc metal batteries (ZMBs) have attracted much attention in the field of grid-scale energy storage due to their high safety, low cost, and abundant resources. Zn powders exhibit the unique advantages of high specific surface area, mature scaled-up manufacturing ability, and structural tunability, which can meet the large-scale energy storage devices, and even the special-shaped devices. However, Zn powder-based anodes are at an early stage and far from the practical industrial application. With the pursuit of comprehensive electrochemical performances of Zn powder-based anodes, this review focus on the advances, issues, and optimized strategies, which are discussed systematically from the previous reports of Zn powder-based anodes. Meanwhile, we also added many supplementary discussions of some important strategies in relevant content but not yet reported. Finally, future prospects toward high performance and practicability of Zn powder-based anodes are proposed, which will provide scientific guidance for the practical application of ZMBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141304675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-07DOI: 10.1021/acsenergylett.4c01123
Liyuan Li, Yushuang Zheng, Jie Xu, Bo Peng, Guoyin Zhu, Junxiong Wu, Lianbo Ma, Zhong Jin
Zinc metal batteries have emerged as promising candidates for next-generation energy storage devices due to their high capacities, high safety, and cost-effectiveness. However, the implementation of Zn metal anodes (ZMAs) faces significant challenges, including uncontrollable dendrite growth, pronounced corrosion, and notable side reactions. To address these issues, extensive research efforts are underway, focusing on tailored structures, compositions, and interfaces for ZMAs, supported by multi-level engineering approaches. Various efficient solutions have been proposed and verified, including homogenizing the ion flux/electric field, enriching the nucleation site number, reducing nucleation energy barriers, and providing sufficient space for Zn deposition. This Review provides a thorough summary of recent advancements in the innovative design of ZMAs, from the viewpoints of structural and interfacial engineering strategies. Key design concepts and functional mechanisms in resolving the aforementioned issues of ZMAs are highlighted. Furthermore, the remaining issues and challenges are discussed, and future research directions are also identified.
{"title":"Structural and Interfacial Engineering Strategies for Constructing Dendrite-Free Zinc Metal Anodes","authors":"Liyuan Li, Yushuang Zheng, Jie Xu, Bo Peng, Guoyin Zhu, Junxiong Wu, Lianbo Ma, Zhong Jin","doi":"10.1021/acsenergylett.4c01123","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01123","url":null,"abstract":"Zinc metal batteries have emerged as promising candidates for next-generation energy storage devices due to their high capacities, high safety, and cost-effectiveness. However, the implementation of Zn metal anodes (ZMAs) faces significant challenges, including uncontrollable dendrite growth, pronounced corrosion, and notable side reactions. To address these issues, extensive research efforts are underway, focusing on tailored structures, compositions, and interfaces for ZMAs, supported by multi-level engineering approaches. Various efficient solutions have been proposed and verified, including homogenizing the ion flux/electric field, enriching the nucleation site number, reducing nucleation energy barriers, and providing sufficient space for Zn deposition. This Review provides a thorough summary of recent advancements in the innovative design of ZMAs, from the viewpoints of structural and interfacial engineering strategies. Key design concepts and functional mechanisms in resolving the aforementioned issues of ZMAs are highlighted. Furthermore, the remaining issues and challenges are discussed, and future research directions are also identified.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141287301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-06-07DOI: 10.1021/acsenergylett.4c00881
Dongyu Li, Benzheng Lyu, Jiayun Sun, Qi Xiong, Hanwen Zhu, Zhengyan Jiang, Dezhong Zhang, Chunyu Liu, Wallace C. H. Choy
Mixed-chloride/bromide perovskite nanocrystals (PeNCs) possess unique advantages for pure blue emission but suffer from severe halogen segregation. While ligand exchange is a promising method to improve stability, there are limited studies on comparative evaluation of the ligand ion pair combinations. We conduct a comprehensive investigation of the ligand exchange process by combining different ion pairs. Surprisingly, changes of ligand ion combinations cause a deviation from pure blue emission of CsPbBrxCl3–x, even without intentional halogen alteration. This spectral shift is attributed to the halogen redistribution, which is dominated by the solubility principle in a nonpolar environment. With a detailed ligand-exchange study, we demonstrate pure-blue perovskite light-emitting diodes (PeLEDs) with an external quantum efficiency (EQE) of 7.45% and an operational half-lifetime (T50) of 61 min at an initial luminance of 100 cd m–2. Our findings provide a ligand selection guideline and promote mixed-halide, pure blue PeLEDs for practical applications.
{"title":"Ligands Optimization Governed by Solubility Principles for Pure Blue Emission in Mixed-Halide Perovskite LEDs","authors":"Dongyu Li, Benzheng Lyu, Jiayun Sun, Qi Xiong, Hanwen Zhu, Zhengyan Jiang, Dezhong Zhang, Chunyu Liu, Wallace C. H. Choy","doi":"10.1021/acsenergylett.4c00881","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c00881","url":null,"abstract":"Mixed-chloride/bromide perovskite nanocrystals (PeNCs) possess unique advantages for pure blue emission but suffer from severe halogen segregation. While ligand exchange is a promising method to improve stability, there are limited studies on comparative evaluation of the ligand ion pair combinations. We conduct a comprehensive investigation of the ligand exchange process by combining different ion pairs. Surprisingly, changes of ligand ion combinations cause a deviation from pure blue emission of CsPbBr<sub><i>x</i></sub>Cl<sub>3–<i>x</i></sub>, even without intentional halogen alteration. This spectral shift is attributed to the halogen redistribution, which is dominated by the solubility principle in a nonpolar environment. With a detailed ligand-exchange study, we demonstrate pure-blue perovskite light-emitting diodes (PeLEDs) with an external quantum efficiency (EQE) of 7.45% and an operational half-lifetime (<i>T</i><sub>50</sub>) of 61 min at an initial luminance of 100 cd m<sup>–2</sup>. Our findings provide a ligand selection guideline and promote mixed-halide, pure blue PeLEDs for practical applications.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141287304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Solar-to-chemical conversion is crucial, as it can form chemicals that are easy to store. Hydrogen peroxide (H2O2) represents a favorable chemical for energy storage and disinfection. Solar driven H2O2 photocatalysis is a promising method, as it could greatly reduce costs and provide on-demand production. The big challenge lies in achieving optimum production rate with reasonable materials cost. Herein, by precise control of synthetic conditions, tungsten (W)-based metal–organic-framework (MOF) with up to 28.64% undercoordinated W4/5+ is prepared. The H2O2 photoproduction rate up to 330,000 μmol g–1 h–1 L–1 is achieved, highest for non-noble metal-based catalysts. A multistage solar driven evaporation system further increases H2O2 concentration to 0.43 wt %, reaching application level for water treatment. Such an efficient production originates from ultrafast hole preservation, which enables a two-electron transfer reaction pathway for H2O2 production. Our work highlighted the potential of MOF-based photocatalyst for on-demand and large scale H2O2 production.
{"title":"Ultrafast Hole Preservation with Undercoordinated Tungsten for Efficient Solar-to-Chemical Conversion","authors":"Qiushi Hu, Shang Liu, Jingjing Liu, Meng Lin, Ruquan Ye, Xihan Chen","doi":"10.1021/acsenergylett.4c01336","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01336","url":null,"abstract":"Solar-to-chemical conversion is crucial, as it can form chemicals that are easy to store. Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) represents a favorable chemical for energy storage and disinfection. Solar driven H<sub>2</sub>O<sub>2</sub> photocatalysis is a promising method, as it could greatly reduce costs and provide on-demand production. The big challenge lies in achieving optimum production rate with reasonable materials cost. Herein, by precise control of synthetic conditions, tungsten (W)-based metal–organic-framework (MOF) with up to 28.64% undercoordinated W<sup>4/5+</sup> is prepared. The H<sub>2</sub>O<sub>2</sub> photoproduction rate up to 330,000 μmol g<sup>–1</sup> h<sup>–1</sup> L<sup>–1</sup> is achieved, highest for non-noble metal-based catalysts. A multistage solar driven evaporation system further increases H<sub>2</sub>O<sub>2</sub> concentration to 0.43 wt %, reaching application level for water treatment. Such an efficient production originates from ultrafast hole preservation, which enables a two-electron transfer reaction pathway for H<sub>2</sub>O<sub>2</sub> production. Our work highlighted the potential of MOF-based photocatalyst for on-demand and large scale H<sub>2</sub>O<sub>2</sub> production.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141287318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Vanadium-based fluoride phosphate polyanionic compounds are the most competitive candidates for cathode materials in potassium-ion batteries (PIBs). However, they have faced the long-standing obstacle of poor intrinsic kinetics that has yet to be overcome, ascribed to the unique electron transfer pattern in the covalently bonded structures. Herein, by adjusting the coordinated circumstance of the V octahedron via the introduction of a large-sized and weak-field ligand Cl–, we synthesized KVPO4F0.9Cl0.1 (KVPFCl) with fast kinetics. A distorted octahedral symmetry with the larger Cl– expands the lattice structure, facilitating K+ ion diffusion in the KVPFCl material. Furthermore, accelerated electronic kinetics is achieved via the stronger electron donor Cl–, which stimulates the hybridization of the V 3d orbital and the 2p/3p orbitals of the ligands and narrows the crystal field splitting energy. Therefore, the as-prepared KVPFCl has a high rate capability and capacity retention. Our results provide prospective insights into achieving fast kinetics in vanadium fluorophosphate polyanionic materials for PIBs.
钒基氟化物磷酸多阴离子化合物是钾离子电池（PIB）阴极材料中最具竞争力的候选材料。然而，由于共价键结构中独特的电子传递模式，它们长期以来一直面临着内在动力学性能不佳的障碍，至今仍有待克服。在此，我们通过引入大尺寸弱场配体 Cl- 来调整 V 八面体的配位情况，合成了具有快速动力学特性的 KVPO4F0.9Cl0.1 （KVPFCl）。大尺寸 Cl- 的扭曲八面体对称性扩展了晶格结构，促进了 K+ 离子在 KVPFCl 材料中的扩散。此外，较强的电子供体 Cl- 可加速电子动力学，从而刺激配体的 V 3d 轨道和 2p/3p 轨道杂化，缩小晶场分裂能。因此，制备的 KVPFCl 具有较高的速率能力和容量保持能力。我们的研究结果为实现用于 PIB 的氟磷酸钒多阴离子材料的快速动力学提供了前瞻性见解。
{"title":"Ligand Engineering Enables Fast Kinetics of KVPO4F Cathode for Potassium-Ion Batteries","authors":"Yixin Zhu, Boning Ou, Chongwei Gao, Yueteng Gao, Biao Zhang, Feiyu Kang, Dengyun Zhai","doi":"10.1021/acsenergylett.4c01052","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01052","url":null,"abstract":"Vanadium-based fluoride phosphate polyanionic compounds are the most competitive candidates for cathode materials in potassium-ion batteries (PIBs). However, they have faced the long-standing obstacle of poor intrinsic kinetics that has yet to be overcome, ascribed to the unique electron transfer pattern in the covalently bonded structures. Herein, by adjusting the coordinated circumstance of the V octahedron via the introduction of a large-sized and weak-field ligand Cl<sup>–</sup>, we synthesized KVPO<sub>4</sub>F<sub>0.9</sub>Cl<sub>0.1</sub> (KVPFCl) with fast kinetics. A distorted octahedral symmetry with the larger Cl<sup>–</sup> expands the lattice structure, facilitating K<sup>+</sup> ion diffusion in the KVPFCl material. Furthermore, accelerated electronic kinetics is achieved via the stronger electron donor Cl<sup>–</sup>, which stimulates the hybridization of the V 3d orbital and the 2p/3p orbitals of the ligands and narrows the crystal field splitting energy. Therefore, the as-prepared KVPFCl has a high rate capability and capacity retention. Our results provide prospective insights into achieving fast kinetics in vanadium fluorophosphate polyanionic materials for PIBs.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141265048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The local pH drop caused by water oxidation inevitably leads to photoanode corrosion and deactivation. As a well-studied photoanode, the stability of BiVO4 restricts its application, despite the state-of-the-art efficiency approaching the theoretical limit. Herein, we demonstrate a facile strategy to improve the stability by sequentially coating bilayer ionomers of the anion exchange ionomer and proton exchange ionomer on a classic photoanode, NiFe/BiVO4. This strategy creates a buffer layer that regulates the local pH near the photoanode surface. By modulating water dissociation and subsequent transfer of protons and hydroxyls, bilayer ionomers decouple the reaction-associated local pH changes from water oxidation, mitigating the inherently acidic corrosion toward photoanodes. An extended stability of 200 h is obtained, compared to less than 10 h without ionomer modification. This work provides a general strategy for stabilizing acid-sensitive photoanodes and offers insights in fabricating long-term stable systems related to photocatalysis and electrocatalysis.
{"title":"Decoupling Inherent Corrosion from Water Oxidation by Coating Bilayer Ionomers on Photoanodes","authors":"Yizhou Wu, Chen Tao, Linqin Wang, Shuo Sun, Qinglu Liu, Biaobiao Zhang, Licheng Sun","doi":"10.1021/acsenergylett.4c01169","DOIUrl":"https://doi.org/10.1021/acsenergylett.4c01169","url":null,"abstract":"The local pH drop caused by water oxidation inevitably leads to photoanode corrosion and deactivation. As a well-studied photoanode, the stability of BiVO<sub>4</sub> restricts its application, despite the state-of-the-art efficiency approaching the theoretical limit. Herein, we demonstrate a facile strategy to improve the stability by sequentially coating bilayer ionomers of the anion exchange ionomer and proton exchange ionomer on a classic photoanode, NiFe/BiVO<sub>4</sub>. This strategy creates a buffer layer that regulates the local pH near the photoanode surface. By modulating water dissociation and subsequent transfer of protons and hydroxyls, bilayer ionomers decouple the reaction-associated local pH changes from water oxidation, mitigating the inherently acidic corrosion toward photoanodes. An extended stability of 200 h is obtained, compared to less than 10 h without ionomer modification. This work provides a general strategy for stabilizing acid-sensitive photoanodes and offers insights in fabricating long-term stable systems related to photocatalysis and electrocatalysis.","PeriodicalId":16,"journal":{"name":"ACS Energy Letters ","volume":null,"pages":null},"PeriodicalIF":22.0,"publicationDate":"2024-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141265126","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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