Journal of the American Chemical Society最新文献_第6页

Sorbent Mediated Electrocatalytic Reduction of Dilute CO2 to Methane 吸附剂介导的稀CO2电催化还原制甲烷研究

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-06 DOI: 10.1021/jacs.4c18303

Jared S. Stanley, Hunter N. Pauker, Erin Kuker, Vy Dong, Robert J. Nielsen, Jenny Y. Yang

{"title":"Sorbent Mediated Electrocatalytic Reduction of Dilute CO2 to Methane","authors":"Jared S. Stanley, Hunter N. Pauker, Erin Kuker, Vy Dong, Robert J. Nielsen, Jenny Y. Yang","doi":"10.1021/jacs.4c18303","DOIUrl":"https://doi.org/10.1021/jacs.4c18303","url":null,"abstract":"Efficient CO2 utilization is a critical component of closing the anthropogenic carbon cycle. Most studies have focused on the use of pure streams of CO2. However, CO2 is generally available only in dilute streams, which requires capture by sorbents followed by energy-intensive regeneration to release concentrated CO2. Direct utilization of sorbed-CO2 avoids the costly regeneration step, and the sorbent-CO2 interaction can kinetically activate CO2 to tune its reactivity toward products that could otherwise be inaccessible with direct CO2 reduction. We demonstrate that an N-heterocyclic carbene, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (DPIy), quantitatively reacts with CO2 from dilute streams (0.04 and 10%) to form the sorbent-CO2 substrate 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (DPICx). Electrocatalyst iron tetraphenylporphyrin chloride (Fe(TPP)Cl) typically reduces CO2 to CO; however, with DPICx as the substrate, the eight-electron reduced product methane (CH4) is produced with a high Faradaic efficiency (>85%) and regeneration of the sorbent DPIy. In addition to the overall energy and capital advantages of integrated CO2 capture and conversion, this result illustrates how sorbents can serve a dual purpose for both CO2 capture and chemical auxiliary purposes to access unique products. CO2 has a spectrum of reactivity with different types of sorbents; thus, these studies demonstrate how sorbent-CO2 interactions can be leveraged for integrated capture and utilization platforms to access a wider range of CO2-derived products.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Conformational Plasticity in dsRNA-Binding Domains Drives Functional Divergence in RNA Recognition dsrna结合域的构象可塑性驱动RNA识别的功能分化

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-06 DOI: 10.1021/jacs.5c02057

Debadutta Patra, Jaydeep Paul, Upasana Rai, Aravind P. S., Mandar V. Deshmukh

{"title":"Conformational Plasticity in dsRNA-Binding Domains Drives Functional Divergence in RNA Recognition","authors":"Debadutta Patra, Jaydeep Paul, Upasana Rai, Aravind P. S., Mandar V. Deshmukh","doi":"10.1021/jacs.5c02057","DOIUrl":"https://doi.org/10.1021/jacs.5c02057","url":null,"abstract":"The functional specificity of proteins is often attributed to their sequence and structural homology while frequently neglecting the underlying conformational dynamics occurring at different time scales that can profoundly impact biological consequences. Using 15N-CEST NMR and RDC-corrected metainference molecular dynamics simulations, here, we reveal differential substrate recognition mechanisms in two dsRNA-binding domain (dsRBD) paralogs, DRB2D1 and DRB3D1. Despite their nearly identical solution structures and conserved dsRNA interaction interfaces, DRB3D1 demonstrates structural plasticity that enables it to recognize conformationally flexible dsRNA, a feature notably absent in the more rigid DRB2D1. We present the pivotal role of intrinsic structural dynamics in driving functional divergence and provide insights into the mechanisms that govern specificity in dsRBD:dsRNA interactions. Importantly, our combined experimental and computational approach captures a cluster of intermediate conformations, complementing conventional methods to resolve the dominant ground state and sparsely populated excited states.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"31 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Measuring Nanometer Distances in Proteins and Rigid Rulers between 19F and Gd3+ by Integration of 19F-ENDOR Signal Intensities 用19F- endor信号强度积分测量19F和Gd3+之间蛋白质和刚性尺的纳米距离

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-06 DOI: 10.1021/jacs.4c13530

Martyna Judd, Mian Qi, Elwy H. Abdelkader, Haocheng Qianzhu, Anton Savitsky, Thomas Huber, Jeffrey R. Harmer, Adelheid Godt, Gottfried Otting, Nicholas Cox

引用次数: 0

Lipid Scrambling Pathways in the Sec61 Translocon Complex Sec61易位复合体中的脂质抢夺途径

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-05 DOI: 10.1021/jacs.4c11142

Matti Javanainen, Jan Šimek, Dale Tranter, Sarah O’Keefe, Sudeep Karki, Denys Biriukov, Radek Šachl, Ville O. Paavilainen

{"title":"Lipid Scrambling Pathways in the Sec61 Translocon Complex","authors":"Matti Javanainen, Jan Šimek, Dale Tranter, Sarah O’Keefe, Sudeep Karki, Denys Biriukov, Radek Šachl, Ville O. Paavilainen","doi":"10.1021/jacs.4c11142","DOIUrl":"https://doi.org/10.1021/jacs.4c11142","url":null,"abstract":"Cellular homeostasis depends on the rapid, ATP-independent translocation of newly synthesized lipids across the endoplasmic reticulum (ER) membrane. Lipid translocation is facilitated by membrane proteins known as scramblases, a few of which have recently been identified in the ER. Our previous structure of the translocon-associated protein (TRAP) bound to the Sec61 translocation channel revealed local membrane thinning, suggesting that the Sec61/TRAP complex might be involved in lipid scrambling. Using complementary fluorescence spectroscopy assays, we detected nonselective scrambling by reconstituted translocon complexes. This activity was unaffected by Sec61 inhibitors that block its lateral gate, suggesting a second lipid scrambling pathway within the complex. Molecular dynamics simulations indicate that the trimeric TRAP subunit forms this alternative route, facilitating lipid translocation via a “credit card” mechanism, using a crevice lined with polar residues to shield lipid head groups from the hydrophobic membrane interior. Kinetic and thermodynamic analyses confirmed that local membrane thinning enhances scrambling efficiency and that both Sec61 and TRAP scramble phosphatidylcholine faster than phosphatidylethanolamine and phosphatidylserine, reflecting the intrinsic lipid flip–flop tendencies of these lipid species. As the Sec61 scrambling site lies in the lateral gate region, it is likely inaccessible during protein translocation, in line with our experiments on Sec61-inhibited samples. Hence, our findings suggest that the metazoan-specific trimeric TRAP bundle is a viable candidate for lipid scrambling activity that is insensitive to the functional state of the translocon.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"43 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Deciphering Catalyst–Support Interaction via Doping for Highly Active and Durable Oxygen Evolution Catalysis 高活性和持久的析氧催化通过掺杂破译催化剂-载体相互作用

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-05 DOI: 10.1021/jacs.5c02001

Jinyeop Kim, Jinglong Guo, Nannan Shan, Jimun Yoo, Pedro Farinazzo Bergamo Dias Martins, Jongsu Noh, Moonjung Jung, Peter Zapol, Bongjin Simon Mun, Robert Klie, Pietro Papa Lopes, Nenad M. Markovic, Dong Young Chung

{"title":"Deciphering Catalyst–Support Interaction via Doping for Highly Active and Durable Oxygen Evolution Catalysis","authors":"Jinyeop Kim, Jinglong Guo, Nannan Shan, Jimun Yoo, Pedro Farinazzo Bergamo Dias Martins, Jongsu Noh, Moonjung Jung, Peter Zapol, Bongjin Simon Mun, Robert Klie, Pietro Papa Lopes, Nenad M. Markovic, Dong Young Chung","doi":"10.1021/jacs.5c02001","DOIUrl":"https://doi.org/10.1021/jacs.5c02001","url":null,"abstract":"The design of oxygen evolution reaction (OER) electrocatalysts demands a delicate balance between activity and stability. In this study, we present a rational design approach that leverages catalyst–support interactions to enhance both the intrinsic activity and durability of Ir-based catalysts. Our study reveals that while Mo doping energetically promotes the formation of high-valent Ir species, enhancing intrinsic catalytic activity, it also leads to a reduction in electrical conductivity. These findings emphasize that supporting doping can introduce both beneficial and limiting effects, highlighting the need for a carefully balanced design strategy to optimize the overall OER performance. Simultaneously, in situ analytical techniques and comparative evaluation reveal the crucial role of oxide supports in stabilizing the catalyst. These findings highlight the pivotal role of interface engineering in maintaining catalyst integrity and the need for support materials that balance dopant-driven electronic promotion with structural and electrochemical robustness. These interconnected degradation pathways highlight the need to move beyond a catalyst-centric view and instead adopt a system-level understanding of the stability. Our approach offers a strong foundation for the rational design and evaluation of high-performance OER electrocatalysts for electrochemical energy applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"118 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Designing Highly Conductive Anion Exchange Membranes: Tuning Domain Continuity with ABC Block Copolymer Self-Assembly 设计高导电性阴离子交换膜：ABC嵌段共聚物自组装调域连续性

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-05 DOI: 10.1021/jacs.5c03175

Alexandra J. Macbeth, Danielle Markovich, Abigail L. Taylor, Ethan B. Flanagan, Julia E. Borowski, Jesse H. Hsu, Cheyenne R. Peltier, David A. Muller, Brett P. Fors, Kevin J. T. Noonan, Geoffrey W. Coates

{"title":"Designing Highly Conductive Anion Exchange Membranes: Tuning Domain Continuity with ABC Block Copolymer Self-Assembly","authors":"Alexandra J. Macbeth, Danielle Markovich, Abigail L. Taylor, Ethan B. Flanagan, Julia E. Borowski, Jesse H. Hsu, Cheyenne R. Peltier, David A. Muller, Brett P. Fors, Kevin J. T. Noonan, Geoffrey W. Coates","doi":"10.1021/jacs.5c03175","DOIUrl":"https://doi.org/10.1021/jacs.5c03175","url":null,"abstract":"Anion exchange membranes (AEMs) play a critical role in clean energy devices, and optimizing their performance requires a deeper understanding of morphology–performance relationships. This study investigates ABC triblock terpolymer AEMs to explore how domain continuity influences hydroxide conductivity, water uptake, and dimensional stability. High molecular weight ABC triblock terpolymers were synthesized through the controlled vinyl-addition polymerization of norbornene monomers functionalized with alkyl, benzyl, or bromobutyl substituents. Morphology was systematically varied across the series without significantly changing the molecular weight or ion exchange capacity (IEC) of the polymer by adjusting the alkyl/benzyl block length ratio. Solution-cast films exhibited either 2D-continuous lamellar or 3D-co-continuous network phase morphologies, with domain continuity largely retained after cationic functionalization. AEMs with 3D-co-continuous domains demonstrated superior performance, including enhanced dimensional stability and competitive hydroxide conductivities of up to 84 mS/cm at 25 °C and 131 mS/cm at 80 °C. This work highlights how the self-assembly of ABC triblock terpolymers can be leveraged to investigate morphology–performance relationships and achieve highly conductive, durable AEMs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"56 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

X-ray-Induced Photodegradation of Hydrogels by the Incorporation of X-ray-Activated Long Persistent Luminescent Nanoparticles x射线激活的长持久发光纳米粒子对水凝胶的x射线诱导光降解

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-05 DOI: 10.1021/jacs.4c14477

Shanshan Li, Hailei Zhang, Jiaying Zhong, Bo Zhang, Kaiming Zhang, Yuangong Zhang, Leipeng Li, Yanmin Yang, Yonggang Wu, Richard Hoogenboom

{"title":"X-ray-Induced Photodegradation of Hydrogels by the Incorporation of X-ray-Activated Long Persistent Luminescent Nanoparticles","authors":"Shanshan Li, Hailei Zhang, Jiaying Zhong, Bo Zhang, Kaiming Zhang, Yuangong Zhang, Leipeng Li, Yanmin Yang, Yonggang Wu, Richard Hoogenboom","doi":"10.1021/jacs.4c14477","DOIUrl":"https://doi.org/10.1021/jacs.4c14477","url":null,"abstract":"The development of on-demand degradable hydrogels remains an important challenge. Even though photodegradable hydrogels offer spatiotemporal control over degradation, it is difficult to use ultraviolet, visible, or near-infrared light as a tool for noninvasive triggering in vivo due to the poor tissue-penetration capacity. In contrast, X-ray irradiation can penetrate deep tissue and has virtually no penetration limitations for biological soft tissues. In this study, we propose an X-ray-photodegradation cascade system for hydrogel degradation by incorporating X-ray-activated persistent luminescence nanoparticles (X-PLNPs) into photodegradable hydrogels. A photodegradable 9,10-dialkoxyanthracene-based cross-linker was synthesized and used to prepare photodegradable hydrogels, of which the degradation behavior can be triggered by visible green light. Next, Tb3+-doped β-NaLuF4 was introduced as an X-PLNP that can convert X-rays into visible light centered at 544 nm. The afterglow can even be detected for 4 × 103 s after switching off the X-ray irradiation. The X-ray-induced green light emission was demonstrated to trigger photodegradation of the hydrogel. This proof-of-concept system for X-ray irradiation-induced on-demand hydrogel degradation was used to demonstrate X-ray-sensitive drug delivery inside a chicken breast as the in vitro tissue model. As this X-ray-induced cascade degradation of hydrogels can penetrate deep tissues, it is a promising platform for future in vivo applications requiring on-demand triggered hydrogel degradation, such as drug delivery or removal of hydrogel patches, hydrogel adhesives, or hydrogel tissue engineering scaffolds. It should, however, be noted that the hydrogel’s X-ray and photoresponsiveness should be further improved to enable future in vivo use.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"70 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

From Reagent to Catalyst: Dispersion-Driven Design of a General Asymmetric Transfer Hydrogenation Catalyst 从试剂到催化剂：一种通用的不对称转移加氢催化剂的分散驱动设计

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-05 DOI: 10.1021/jacs.5c00641

Wencke Leinung, Benjamin Mitschke, Markus Leutzsch, Vijay N. Wakchaure, Rajat Maji, Benjamin List

{"title":"From Reagent to Catalyst: Dispersion-Driven Design of a General Asymmetric Transfer Hydrogenation Catalyst","authors":"Wencke Leinung, Benjamin Mitschke, Markus Leutzsch, Vijay N. Wakchaure, Rajat Maji, Benjamin List","doi":"10.1021/jacs.5c00641","DOIUrl":"https://doi.org/10.1021/jacs.5c00641","url":null,"abstract":"Even though chemists have long underappreciated the role of London dispersion in catalysis, its importance in determining a reaction course is now well recognized. Dispersion interactions have been shown to stabilize transition states and govern the stereoselectivity. In this context, the transfer hydrogenation of α,β-unsaturated aldehydes reported by our group via asymmetric counteranion-directed catalysis (ACDC) was revisited mechanistically. Previously, the use of an engineered Hantzsch ester featuring an isopropyl group was crucial for high enantioselectivity, suggesting London dispersion as an important stereocontrolling factor. Based on this hypothesis and the method’s drawbacks (commercially unavailable Hantzsch ester, limited substrate scope, high catalyst loadings), we designed a broadly applicable second-generation catalyst system by introducing dispersion energy donors into the catalyst instead of the Hantzsch ester reagent. With the help of computational analysis, noncovalent interactions contributing to stereocontrol in the two systems were elucidated.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"47 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910909","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Coordination Chemistry toward Advanced Zn–I2 Batteries with Four-Electron I–/I0/I+ Conversion 四电子I - /I0/I+转换先进锌- i2电池的配位化学研究

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-05 DOI: 10.1021/jacs.5c02085

Shao-Jian Zhang, Junnan Hao, Han Wu, Qianru Chen, Yiyang Hu, Xun Zhao, Shi-Zhang Qiao

{"title":"Coordination Chemistry toward Advanced Zn–I2 Batteries with Four-Electron I–/I0/I+ Conversion","authors":"Shao-Jian Zhang, Junnan Hao, Han Wu, Qianru Chen, Yiyang Hu, Xun Zhao, Shi-Zhang Qiao","doi":"10.1021/jacs.5c02085","DOIUrl":"https://doi.org/10.1021/jacs.5c02085","url":null,"abstract":"Aqueous zinc–iodine (Zn–I2) batteries with four-electron (4e) I–/I0/I+ conversion (4eZIBs) offer high energy density but face significant challenges for application, including the polyiodide shuttle effect and I+ hydrolysis for the I2 cathodes and poor reversibility for the Zn anodes. Here, we report a coordination chemistry strategy to address these issues simultaneously by introducing hexamethylenetetramine (HMTA) as an electrolyte additive. In aqueous electrolytes, HMTA undergoes protonation to form positively charged nitrogen moieties that effectively precipitate the polyiodides and I+ species (ICl2–) to mitigate the polyiodides shuttle and I+ hydrolysis. This strategy enables 4eZIBs to achieve a near-theoretical specific capacity of 425 mA h g–1 (based on the mass of iodine) and a Coulombic efficiency (CE) exceeding 99%. On the Zn anode, HMTA preferentially adsorbs onto its surface, inhibiting competitive water adsorption to suppress both Zn dendrite formation and hydrogen evolution. As a result, for the first time, we achieve durable 4eZIB performance in pouch-cell configurations with limited Zn supply. A 0.5 A h pouch cell with 15% Zn utilization exhibits a high energy density of 113.0 W h kg–1 (based on the mass of cathodes and anodes) and excellent cycling stability for over 1400 cycles, highlighting the potential of 4eZIBs for next-generation energy storage systems.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Heterogeneous Interfaces of Ni3Se4 Nanoclusters Decorated on a Ni3N Surface Enhance Efficient and Durable Hydrogen Evolution Reactions in Alkaline Electrolyte 在Ni3N表面修饰Ni3Se4纳米簇的非均相界面增强了碱性电解质中高效持久的析氢反应

IF 15 1区化学

Journal of the American Chemical Society Pub Date : 2025-05-05 DOI: 10.1021/jacs.4c17747

Dessalew Dagnew Alemayehu, Meng-Che Tsai, Meng-Hsuan Tsai, Chueh-Cheng Yang, Chun-Chi Chang, Chia-Yu Chang, Endalkachew Asefa Moges, Keseven Lakshmanan, Yosef Nikodimos, Wei-Nien Su, Chia-Hsin Wang, Bing Joe Hwang

{"title":"Heterogeneous Interfaces of Ni3Se4 Nanoclusters Decorated on a Ni3N Surface Enhance Efficient and Durable Hydrogen Evolution Reactions in Alkaline Electrolyte","authors":"Dessalew Dagnew Alemayehu, Meng-Che Tsai, Meng-Hsuan Tsai, Chueh-Cheng Yang, Chun-Chi Chang, Chia-Yu Chang, Endalkachew Asefa Moges, Keseven Lakshmanan, Yosef Nikodimos, Wei-Nien Su, Chia-Hsin Wang, Bing Joe Hwang","doi":"10.1021/jacs.4c17747","DOIUrl":"https://doi.org/10.1021/jacs.4c17747","url":null,"abstract":"Transition metal selenides (TMSes) have been identified as cost-efficient alternatives to platinum (Pt) for the alkaline hydrogen evolution reaction (HER) owing to their distinct electronic properties and excellent conductivity. However, they encounter challenges such as sluggish water dissociation and severe oxidative degradation, requiring further optimizations. In this study, we developed a dual-site heterogeneous catalyst, Ni3Se4–Ni3N, by decorating Ni3Se4 nanoclusters on a Ni3N substrate. This catalyst design promoted significant interfacial electronic interactions, modulated electronic structures, and enhanced the adsorption of the intermediates. Various spectroscopic analyses and theoretical calculations revealed that the nitride surfaces improved water adsorption and dissociation, enriching the surface with adsorbed hydrogen (H*) atoms, while the Se sites facilitated hydrogen coupling and subsequent release of H2. Following a hydrogen spillover mechanism, the surface-adsorbed hydrogen atoms were transferred to nearby electron-dense selenide sites for H2 formation and release. Consequently, the optimized catalyst demonstrated improved HER activity, requiring only an ∼60 mV overpotential at 10 mA cm–2 current density and maintained stability under higher potential conditions.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"13 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-05-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0