Pub Date : 2025-12-23DOI: 10.1016/j.jechem.2025.12.033
Wenli Li , Xiangyi Gu , Jie Zhang , Xu Wang , Yujia Cai , Guohua Gao , Qinghong Wang , Jianguo Lu
Rechargeable aqueous zinc-ion batteries (ZIBs) represent a promising energy storage technology due to their intrinsic safety, low cost, and environmental compatibility. However, the practical application of vanadium-based cathodes is hindered by structural instability and rapid capacity decay during cycling. Herein, we develop an Al3+ doping strategy to engineer the VO2 cathode with remarkably enhanced stability. The introduction of Al3+ not only induces favorable oxygen vacancies but also reinforces the host structure, effectively mitigating lattice strain and minimizing vanadium dissolution. The resulting Al2-VO2 cathode exhibits a high specific capacity of 452 mAh g−1 at 0.1 A g−1 and exceptional long-term cyclability, retaining ∼70% capacity after 10,000 cycles at 10 A g−1. Kinetics studies further reveal capacitive-dominated storage behavior and facilitated Zn2+ diffusion, underscoring the role of defect engineering in boosting electrochemical performance. This work provides a feasible cation-doping approach to realize highly stable VO2-based cathodes for sustainable energy storage applications.
可充电水锌离子电池具有安全、低成本、环保等优点，是一种极具发展前景的储能技术。然而，钒基阴极的实际应用受到结构不稳定和循环过程中容量快速衰减的阻碍。在此，我们开发了一种Al3+掺杂策略来设计具有显著增强稳定性的VO2阴极。Al3+的引入不仅产生了有利的氧空位，而且强化了基体结构，有效地减轻了晶格应变，减少了钒的溶解。所得的Al2-VO2阴极在0.1 a g−1下具有452 mAh g−1的高比容量和优异的长期可循环性，在10 a g−1下循环10,000次后仍保持70%的容量。动力学研究进一步揭示了电容主导的存储行为和促进Zn2+扩散，强调了缺陷工程在提高电化学性能方面的作用。这项工作提供了一种可行的阳离子掺杂方法来实现高稳定的vo2基阴极，用于可持续储能应用。
{"title":"Engineering vanadium dioxide cathodes toward ultrastable zinc ion batteries","authors":"Wenli Li , Xiangyi Gu , Jie Zhang , Xu Wang , Yujia Cai , Guohua Gao , Qinghong Wang , Jianguo Lu","doi":"10.1016/j.jechem.2025.12.033","DOIUrl":"10.1016/j.jechem.2025.12.033","url":null,"abstract":"<div><div>Rechargeable aqueous zinc-ion batteries (ZIBs) represent a promising energy storage technology due to their intrinsic safety, low cost, and environmental compatibility. However, the practical application of vanadium-based cathodes is hindered by structural instability and rapid capacity decay during cycling. Herein, we develop an Al<sup>3+</sup> doping strategy to engineer the VO<sub>2</sub> cathode with remarkably enhanced stability. The introduction of Al<sup>3+</sup> not only induces favorable oxygen vacancies but also reinforces the host structure, effectively mitigating lattice strain and minimizing vanadium dissolution. The resulting Al2-VO<sub>2</sub> cathode exhibits a high specific capacity of 452 mAh g<sup>−1</sup> at 0.1 A g<sup>−1</sup> and exceptional long-term cyclability, retaining ∼70% capacity after 10,000 cycles at 10 A g<sup>−1</sup>. Kinetics studies further reveal capacitive-dominated storage behavior and facilitated Zn<sup>2+</sup> diffusion, underscoring the role of defect engineering in boosting electrochemical performance. This work provides a feasible cation-doping approach to realize highly stable VO<sub>2</sub>-based cathodes for sustainable energy storage applications.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 801-810"},"PeriodicalIF":14.9,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976999","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}
Pub Date : 2025-12-23DOI: 10.1016/j.jechem.2025.12.030
Yuxuan Gao , Huan Liu , Xiaopeng Liu , Yida Zhang , Tianyu Zhang , Jie Bai
Hydrofuroin (HDF), a key precursor of fuel, can be produced by electrocatalytic furfural (FF) hydrodimerization, offering a promising way to generate value-added products. However, this process is hindered by sluggish C–C coupling and hydrogenation steps, resulting in low Faradaic efficiency (FE). Herein, atomically dispersed Ru sites anchored on lattice vacancies of La0.9NiO3 (Ru-La0.9NiO3) electrocatalysts were demonstrated as an efficient electrocatalyst for FF hydrodimerization, where an intermediate spillover strategy significantly enhances the FE. Mechanistic investigations reveal that Ru single atoms serve as active sites for the initial hydrogenation to form the FF-CHOH* intermediate with almost 100% selectivity, thereby suppressing the side reaction of hydrogen evolution. Subsequently, the increased FE-CHOH* intermediate undergoes spillover to adjacent Ni sites, decreasing the energy barrier for the subsequent C–C coupling step to HDF (ΔG = 0.63 eV). As a result, the Ru-La0.9NiO3 catalyst displays a high FE of 74% and a production rate of 3.95 mmol cm−2 h−1 toward electrocatalytic FF hydrodimerization to HDF product. This work provides an efficient intermediate spillover approach, offering mechanistic insights into Ru-Ni synergism in Ru-La0.9NiO3 and providing a sensible method for electrocatalytic hydrodimerization of furfural to produce high-value products.
{"title":"Spillover of intermediates from Ru single atoms to La0.9NiO3 for boosting electrocatalytic furfural C–C coupling into jet fuel precursors","authors":"Yuxuan Gao , Huan Liu , Xiaopeng Liu , Yida Zhang , Tianyu Zhang , Jie Bai","doi":"10.1016/j.jechem.2025.12.030","DOIUrl":"10.1016/j.jechem.2025.12.030","url":null,"abstract":"<div><div>Hydrofuroin (HDF), a key precursor of fuel, can be produced by electrocatalytic furfural (FF) hydrodimerization, offering a promising way to generate value-added products. However, this process is hindered by sluggish C–C coupling and hydrogenation steps, resulting in low Faradaic efficiency (FE). Herein, atomically dispersed Ru sites anchored on lattice vacancies of La<sub>0.9</sub>NiO<sub>3</sub> (Ru-La<sub>0.9</sub>NiO<sub>3</sub>) electrocatalysts were demonstrated as an efficient electrocatalyst for FF hydrodimerization, where an intermediate spillover strategy significantly enhances the FE. Mechanistic investigations reveal that Ru single atoms serve as active sites for the initial hydrogenation to form the FF-CHOH* intermediate with almost 100% selectivity, thereby suppressing the side reaction of hydrogen evolution. Subsequently, the increased FE-CHOH* intermediate undergoes spillover to adjacent Ni sites, decreasing the energy barrier for the subsequent C–C coupling step to HDF (Δ<em>G</em> = 0.63 eV). As a result, the Ru-La<sub>0.9</sub>NiO<sub>3</sub> catalyst displays a high FE of 74% and a production rate of 3.95 mmol cm<sup>−2</sup> h<sup>−1</sup> toward electrocatalytic FF hydrodimerization to HDF product. This work provides an efficient intermediate spillover approach, offering mechanistic insights into Ru-Ni synergism in Ru-La<sub>0.9</sub>NiO<sub>3</sub> and providing a sensible method for electrocatalytic hydrodimerization of furfural to produce high-value products.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 769-777"},"PeriodicalIF":14.9,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977582","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}
Pub Date : 2025-12-23DOI: 10.1016/j.jechem.2025.12.032
Stijn Van Rompaey , Eduardo Morais , Mikhail Gromov , Anton Nikiforov , Annemie Bogaerts
CH4 valorisation into H2 and value-added hydrocarbons is a promising route towards sustainable chemistry and energy production. However, the fundamental plasma-chemical pathways leading to H2, olefins, and soot precursors remain insufficiently understood. This study addresses these knowledge gaps by investigating CH4 conversion in a nanosecond pulsed discharge through a combined experimental and modelling approach. A zero-dimensional kinetic model is developed, incorporating excitation, ionisation, dissociation, and radical recombination reactions to capture the plasma-chemical dynamics. The model predictions were validated by gas chromatography measurements across a pressure range of 0.5–2.0 bar. The CH4 conversion averaged ∼17%, with H2 and C2H2 as the main products. The best performance was obtained at 2.0 bar, yielding an energy cost of 272 kJ mol−1. The simulations and experiments consistently revealed that both power density and gas temperature critically influence species formation, highlighting the interplay between plasma-induced and thermal (pyrolysis) processes during the nanosecond pulse and in the afterglow, respectively. The reaction mechanism clarifies the relative importance of electron impact processes versus thermally driven chemistry, as well as the growth routes toward solid carbon and soot precursors. By correlating kinetic modelling with time-resolved plasma conditions, this work provides new insights into the elementary steps governing CH4 decomposition in nanosecond pulsed plasmas. Overall, this study advances our understanding of plasma-driven CH4 valorisation and establishes a framework for distinguishing plasma-specific effects from conventional thermal pyrolysis.
{"title":"CH4 conversion in nanosecond pulsed plasma: Is it pyrolysis?","authors":"Stijn Van Rompaey , Eduardo Morais , Mikhail Gromov , Anton Nikiforov , Annemie Bogaerts","doi":"10.1016/j.jechem.2025.12.032","DOIUrl":"10.1016/j.jechem.2025.12.032","url":null,"abstract":"<div><div>CH<sub>4</sub> valorisation into H<sub>2</sub> and value-added hydrocarbons is a promising route towards sustainable chemistry and energy production. However, the fundamental plasma-chemical pathways leading to H<sub>2</sub>, olefins, and soot precursors remain insufficiently understood. This study addresses these knowledge gaps by investigating CH<sub>4</sub> conversion in a nanosecond pulsed discharge through a combined experimental and modelling approach. A zero-dimensional kinetic model is developed, incorporating excitation, ionisation, dissociation, and radical recombination reactions to capture the plasma-chemical dynamics. The model predictions were validated by gas chromatography measurements across a pressure range of 0.5–2.0 bar. The CH<sub>4</sub> conversion averaged ∼17%, with H<sub>2</sub> and C<sub>2</sub>H<sub>2</sub> as the main products. The best performance was obtained at 2.0 bar, yielding an energy cost of 272 kJ mol<sup>−1</sup>. The simulations and experiments consistently revealed that both power density and gas temperature critically influence species formation, highlighting the interplay between plasma-induced and thermal (pyrolysis) processes during the nanosecond pulse and in the afterglow, respectively. The reaction mechanism clarifies the relative importance of electron impact processes versus thermally driven chemistry, as well as the growth routes toward solid carbon and soot precursors. By correlating kinetic modelling with time-resolved plasma conditions, this work provides new insights into the elementary steps governing CH<sub>4</sub> decomposition in nanosecond pulsed plasmas. Overall, this study advances our understanding of plasma-driven CH<sub>4</sub> valorisation and establishes a framework for distinguishing plasma-specific effects from conventional thermal pyrolysis.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 811-823"},"PeriodicalIF":14.9,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977581","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}
Pub Date : 2025-12-23DOI: 10.1016/j.jechem.2025.12.029
Zongyu Guan , Meng Li , Ao Chen , Jihuan Xie , Aoci Yang , Yang Gu , Guoyao Pang , Kuan Wang , Weidong Zhuang , Jiangtao Hu , Biwei Xiao
Sodium-ion batteries (SIBs) are regarded as a promising alternative to lithium-ion batteries for grid-scale energy storage owing to their low cost and sustainability; however, their competitiveness is still limited by relatively low energy density. Here, we report a scalable Mn-Fe-Ni layered oxide with a compositional-structural dual-gradient (DG) architecture synthesized via a three-step co-precipitation method. By exploiting the opposite roles of high-ionic-potential Mn and low-ionic-potential Fe in stabilizing the P2 and O3 frameworks, respectively, a pure compositional Mn/Fe gradient is translated into a structural P2/O3 gradient with precisely guided synthesis conditions. The Fe-deficient surface effectively suppressed Fe4+-induced side reactions, while the stable P2-type shell and the enlarged R value of the O3 core further enhanced cycling stability during structural evolution. The optimized cathode delivered an energy density of 478 Wh kg−1 at 4.2 V, with 82% capacity retention after 200 cycles in half cells and 91% retention after 1600 cycles in full cells. This study demonstrates a viable pathway for developing high-energy-density and long-lifetime cathodes for sodium-ion batteries.
{"title":"Ionic potential mediated compositional-structural dual gradient engineering in P2/O3 cathodes for high-energy sodium storage","authors":"Zongyu Guan , Meng Li , Ao Chen , Jihuan Xie , Aoci Yang , Yang Gu , Guoyao Pang , Kuan Wang , Weidong Zhuang , Jiangtao Hu , Biwei Xiao","doi":"10.1016/j.jechem.2025.12.029","DOIUrl":"10.1016/j.jechem.2025.12.029","url":null,"abstract":"<div><div>Sodium-ion batteries (SIBs) are regarded as a promising alternative to lithium-ion batteries for grid-scale energy storage owing to their low cost and sustainability; however, their competitiveness is still limited by relatively low energy density. Here, we report a scalable Mn-Fe-Ni layered oxide with a compositional-structural dual-gradient (DG) architecture synthesized via a three-step co-precipitation method. By exploiting the opposite roles of high-ionic-potential Mn and low-ionic-potential Fe in stabilizing the P2 and O3 frameworks, respectively, a pure compositional Mn/Fe gradient is translated into a structural P2/O3 gradient with precisely guided synthesis conditions. The Fe-deficient surface effectively suppressed Fe<sup>4+</sup>-induced side reactions, while the stable P2-type shell and the enlarged <em>R</em> value of the O3 core further enhanced cycling stability during structural evolution. The optimized cathode delivered an energy density of 478 Wh kg<sup>−1</sup> at 4.2 V, with 82% capacity retention after 200 cycles in half cells and 91% retention after 1600 cycles in full cells. This study demonstrates a viable pathway for developing high-energy-density and long-lifetime cathodes for sodium-ion batteries.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 791-800"},"PeriodicalIF":14.9,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977583","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}
Pub Date : 2025-12-23DOI: 10.1016/j.jechem.2025.12.031
Muhammad Pramaditya Garry Hanantyo , Lakshya Mathur , Junghyun Park , Saron Park , Sejong Shin , Sun-Ju Song
The development of high-performance electrolyte-supported reversible solid oxide cells (RSOCs) is significantly hindered by the limitations of existing electrolyte materials, particularly in achieving high ionic conductivity and long-term stability under targeted operating conditions. While scandia stabilized zirconia (ScSZ) exhibits the highest ionic conductivity among zirconia-based electrolytes, ScSZ rapid conductivity degradation during prolonged operation remains a significant obstacle to commercialization. To address this pressing challenge, both binary and ternary co-doping were explored, incorporating Mg2+, In3+, Yb3+, and Sm3+ into the base composition of (Sc2O3)0.11(ZrO2)0.89 (11ScSZ). Among these, the optimized ternary co-doped composition, (In2O3)0.0025(Yb2O3)0.0025(Sc2O3)0.11(ZrO2)0.885 (0.25In0.25Yb11ScSZ), demonstrates significant enhancements in both ionic conductivity and stability. This ternary co-doped electrolyte exhibits superior conductivity and nearly double the stability of undoped 11ScSZ. In addition, it exhibits an enhanced flexural strength even higher than state-of-the-art electrolytes (161 MPa) and respectably wide electrolytic domain (1016–10−27 atm at 800 °C). When implemented in 200 µm-thick electrolyte-supported RSOC devices, the 0.25In0.25Yb11ScSZ electrolyte enables record-breaking performance, achieving a peak power density (PPD) of 1.02 W cm−2 in fuel cell (FC) mode and a current density of 1.05 A cm−2 at 1.3 V in electrolysis cell (EC) mode at 800 °C, both representing two- to three-fold improvement over state-of-the-art systems. These exceptional performance metrics, combined with excellent long-term durability, rank among the highest reported for electrolyte-supported cells, highlighting the potential of this novel ternary co-doped electrolyte for high-performance RSOC technologies capable of meeting the demanding requirements of next-generation energy systems.
高性能电解质支持的可逆固体氧化物电池（rsoc）的发展受到现有电解质材料的限制，特别是在实现高离子电导率和目标操作条件下的长期稳定性方面。虽然钪稳定氧化锆（ScSZ）在锆基电解质中具有最高的离子电导率，但ScSZ在长时间使用过程中电导率的快速下降仍然是商业化的重大障碍。为了解决这一紧迫的挑战，研究人员探索了二元和三元共掺杂，将Mg2+， In3+， Yb3+和Sm3+掺入（Sc2O3）0.11(ZrO2)0.89 （11ScSZ）的碱组成中。其中，优化后的三元共掺杂组合物（In2O3）0.0025(Yb2O3)0.0025(Sc2O3)0.11(ZrO2)0.885 （0.25In0.25Yb11ScSZ）的离子电导率和稳定性均有显著提高。这种三元共掺杂电解质具有优异的导电性，稳定性几乎是未掺杂11ScSZ的两倍。此外，它具有更高的抗弯强度，甚至高于最先进的电解质（161 MPa）和相当宽的电解域（800°C时1016-10−27 atm）。当在200 μ m厚的电解质支持的RSOC器件中实施时，0.25In0.25Yb11ScSZ电解质实现了破纪录的性能，在燃料电池（FC）模式下实现了1.02 W cm - 2的峰值功率密度（PPD），在电解电池（EC）模式下在800°C下实现了1.3 V下的1.05 a cm - 2的电流密度，两者都比最先进的系统提高了两到三倍。这些卓越的性能指标，加上出色的长期耐用性，是电解质支持电池的最高报告之一，突出了这种新型三元共掺杂电解质在高性能RSOC技术方面的潜力，能够满足下一代能源系统的苛刻要求。
{"title":"High performance and stability of electrolyte-supported reversible solid oxide cells with ternary co-doped scandia-stabilized zirconia","authors":"Muhammad Pramaditya Garry Hanantyo , Lakshya Mathur , Junghyun Park , Saron Park , Sejong Shin , Sun-Ju Song","doi":"10.1016/j.jechem.2025.12.031","DOIUrl":"10.1016/j.jechem.2025.12.031","url":null,"abstract":"<div><div>The development of high-performance electrolyte-supported reversible solid oxide cells (RSOCs) is significantly hindered by the limitations of existing electrolyte materials, particularly in achieving high ionic conductivity and long-term stability under targeted operating conditions. While scandia stabilized zirconia (ScSZ) exhibits the highest ionic conductivity among zirconia-based electrolytes, ScSZ rapid conductivity degradation during prolonged operation remains a significant obstacle to commercialization. To address this pressing challenge, both binary and ternary co-doping were explored, incorporating Mg<sup>2+</sup>, In<sup>3+</sup>, Yb<sup>3+</sup>, and Sm<sup>3+</sup> into the base composition of (Sc<sub>2</sub>O<sub>3</sub>)<sub>0.11</sub>(ZrO<sub>2</sub>)<sub>0.89</sub> (11ScSZ). Among these, the optimized ternary co-doped composition, (In<sub>2</sub>O<sub>3</sub>)<sub>0.0025</sub>(Yb<sub>2</sub>O<sub>3</sub>)<sub>0.0025</sub>(Sc<sub>2</sub>O<sub>3</sub>)<sub>0.11</sub>(ZrO<sub>2</sub>)<sub>0.885</sub> (0.25In0.25Yb11ScSZ), demonstrates significant enhancements in both ionic conductivity and stability. This ternary co-doped electrolyte exhibits superior conductivity and nearly double the stability of undoped 11ScSZ. In addition, it exhibits an enhanced flexural strength even higher than state-of-the-art electrolytes (161 MPa) and respectably wide electrolytic domain (10<sup>16</sup>–10<sup>−27</sup> atm at 800 °C). When implemented in 200 µm-thick electrolyte-supported RSOC devices, the 0.25In0.25Yb11ScSZ electrolyte enables record-breaking performance, achieving a peak power density (PPD) of 1.02 W cm<sup>−2</sup> in fuel cell (FC) mode and a current density of 1.05 A cm<sup>−2</sup> at 1.3 V in electrolysis cell (EC) mode at 800 °C, both representing two- to three-fold improvement over state-of-the-art systems. These exceptional performance metrics, combined with excellent long-term durability, rank among the highest reported for electrolyte-supported cells, highlighting the potential of this novel ternary co-doped electrolyte for high-performance RSOC technologies capable of meeting the demanding requirements of next-generation energy systems.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 868-879"},"PeriodicalIF":14.9,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977539","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}
Pub Date : 2025-12-22DOI: 10.1016/j.jechem.2025.12.028
Guiyang Yu , Fatong Yang , Jinghao Zhu , Xinying Zhao , Xiang Li , Ke Gong , Yanchao Wang , Haibin Huang
Solar energy-driven direct-transformation of alcohol into two or multi-carbon compounds via controlled carbon-carbon coupling is highly attractive but concomitant with low efficiency and byproducts. In this study, it is firstly reported that bismuth-based composite (BOB*/BOB*I) highly catalyzes dehydrogenative coupling of aromatic alcohol to hydrobenzoin under visible light irradiation without any sacrificial reagent or oxidants. The apparent quantum yield for aromatic alcohol conversion reaches 3.34% at 420 nm with >98% hydrobenzoin yield within 4 h, along with proton reduction with a H2 evolution rate of 2.49 mmol/g/h. Theoretical calculation and a series of spectral characterizations demonstrate that the interfacial charge transfer-separation between BOB* and BOB*I abides by the Z-scheme mechanism, which ensures faster kinetics and preserves the strong redox capability of photogenerated electrons and holes. Mechanistic studies reveal that the BOB*/BOB*I heterojunction preferentially activates the Cα–H bond in aromatic alcohol instead of the O–H bond, which is further oxidized by photogenerated holes to form a carbon-centered radical intermediate. Subsequent C–C coupling process results in the hydrobenzoin product. This work not only expands photoredox application for designing multifunctional bismuth-based photocatalyst but also offers an economic and ecological route for the synthesis of hydrobenzoin.
{"title":"Cooperatively boosting C–C coupling and proton reduction upon bismuth-based Z-scheme dual-functional photocatalyst","authors":"Guiyang Yu , Fatong Yang , Jinghao Zhu , Xinying Zhao , Xiang Li , Ke Gong , Yanchao Wang , Haibin Huang","doi":"10.1016/j.jechem.2025.12.028","DOIUrl":"10.1016/j.jechem.2025.12.028","url":null,"abstract":"<div><div>Solar energy-driven direct-transformation of alcohol into two or multi-carbon compounds via controlled carbon-carbon coupling is highly attractive but concomitant with low efficiency and byproducts. In this study, it is firstly reported that bismuth-based composite (BOB*/BOB*I) highly catalyzes dehydrogenative coupling of aromatic alcohol to hydrobenzoin under visible light irradiation without any sacrificial reagent or oxidants. The apparent quantum yield for aromatic alcohol conversion reaches 3.34% at 420 nm with >98% hydrobenzoin yield within 4 h, along with proton reduction with a H<sub>2</sub> evolution rate of 2.49 mmol/g/h. Theoretical calculation and a series of spectral characterizations demonstrate that the interfacial charge transfer-separation between BOB* and BOB*I abides by the Z-scheme mechanism, which ensures faster kinetics and preserves the strong redox capability of photogenerated electrons and holes. Mechanistic studies reveal that the BOB*/BOB*I heterojunction preferentially activates the C<sub>α</sub>–H bond in aromatic alcohol instead of the O–H bond, which is further oxidized by photogenerated holes to form a carbon-centered radical intermediate. Subsequent C–C coupling process results in the hydrobenzoin product. This work not only expands photoredox application for designing multifunctional bismuth-based photocatalyst but also offers an economic and ecological route for the synthesis of hydrobenzoin.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 778-790"},"PeriodicalIF":14.9,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977535","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}
Pub Date : 2025-12-19DOI: 10.1016/j.jechem.2025.12.023
Yifan Wu , Zhongyong Zhang , Shangquan Zhao , Bin Huang , Neng Li , Naigen Zhou
Grain boundaries (GBs), particularly Σ7 coincidence site lattice (CSL) defects experimentally observed in MXenes, significantly influence their performance as lithium-ion battery (LIB) anodes. This work systematically investigates the impact of Σ7 GBs on MXene electrochemical properties, with a focus on rate capability. The results indicated that Σ7 GB formation is thermodynamically favored in Ti2C, Nb2C, and Mo2C MXenes compared to other M2C compositions, with stability further enhanced by oxygen and sulfur surface functionalization. These GBs induce substantial geometric distortions that reduce surface charge localization while enhancing electrical conductivity in Ti2CO2. The altered electronic structure at GB sites weakens lithium adsorption strength without promoting lithium dendrite formation. Furthermore, diffusion kinetics calculations reveal significantly reduced lithium diffusion barriers at Σ7 GBs in Ti2C, Mo2C, and Mo2CS2 compared to pristine materials. Mechanistic analysis attributes this enhancement to diminished charge localization at GB regions, which generates a “charge pool” effect—a zone of uniformly distributed free charge observed in Ti2C and Mo2C. This charge pool not only facilitates ultra-low lithium diffusion barriers (as low as 11 meV in M2C at 0.1 V vs. Li+/Li) but also enhances potential responsiveness of diffusion kinetics. Our findings establish the intentional introduction of Σ7 GBs as an effective strategy for designing high-rate MXene anodes. This work provides fundamental insights into GB-enhanced electrochemical mechanisms in 2D materials, offering crucial theoretical guidance for the design of high-rate anode materials.
{"title":"Unlocking high-rate MXenes as lithium-ion battery anodes via Σ7 coincidence site lattice grain boundaries","authors":"Yifan Wu , Zhongyong Zhang , Shangquan Zhao , Bin Huang , Neng Li , Naigen Zhou","doi":"10.1016/j.jechem.2025.12.023","DOIUrl":"10.1016/j.jechem.2025.12.023","url":null,"abstract":"<div><div>Grain boundaries (GBs), particularly Σ7 coincidence site lattice (CSL) defects experimentally observed in MXenes, significantly influence their performance as lithium-ion battery (LIB) anodes. This work systematically investigates the impact of Σ7 GBs on MXene electrochemical properties, with a focus on rate capability. The results indicated that Σ7 GB formation is thermodynamically favored in Ti<sub>2</sub>C, Nb<sub>2</sub>C, and Mo<sub>2</sub>C MXenes compared to other M<sub>2</sub>C compositions, with stability further enhanced by oxygen and sulfur surface functionalization. These GBs induce substantial geometric distortions that reduce surface charge localization while enhancing electrical conductivity in Ti<sub>2</sub>CO<sub>2</sub>. The altered electronic structure at GB sites weakens lithium adsorption strength without promoting lithium dendrite formation. Furthermore, diffusion kinetics calculations reveal significantly reduced lithium diffusion barriers at Σ7 GBs in Ti<sub>2</sub>C, Mo<sub>2</sub>C, and Mo<sub>2</sub>CS<sub>2</sub> compared to pristine materials. Mechanistic analysis attributes this enhancement to diminished charge localization at GB regions, which generates a “charge pool” effect—a zone of uniformly distributed free charge observed in Ti<sub>2</sub>C and Mo<sub>2</sub>C. This charge pool not only facilitates ultra-low lithium diffusion barriers (as low as 11 meV in M<sub>2</sub>C at 0.1 V vs. Li<sup>+</sup>/Li) but also enhances potential responsiveness of diffusion kinetics. Our findings establish the intentional introduction of Σ7 GBs as an effective strategy for designing high-rate MXene anodes. This work provides fundamental insights into GB-enhanced electrochemical mechanisms in 2D materials, offering crucial theoretical guidance for the design of high-rate anode materials.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"116 ","pages":"Pages 31-37"},"PeriodicalIF":14.9,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145981988","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}
Pub Date : 2025-12-19DOI: 10.1016/j.jechem.2025.12.025
Feng Sun , Anjun Hu , Junmei Han , Shenghai Xin , Zhihui Ma , Youwei Wang , Jianbin Li , Qi Wan , Ruidie Tang , Shaofei Wu , Xuanhui Qu , Ping Li
Silicon dioxide (SiO) is regarded as a promising anode candidate for high-energy-density lithium-ion batteries (LIBs) owing to its superior theoretical specific capacity. However, SiO anodes encounter substantial challenges, including substantial volume expansion and persistent growth of a thick solid electrolyte interphase (SEI). In this work, a composite conductive network with dual pinning and piezoelectric effects is proposed, which is cleverly designed to improve the electrochemical reaction kinetics of the electrode. Within the proposed network architecture, single-walled carbon nanotubes (CNTs) serve as fast electronic conductors and structural protective layers, forming a three-dimensional (3D) coating network on the surface of SiO particles. Barium titanate (BTO) nanoparticles are anchored at the nodes of the CNT network through the formation of rigid anchor points, dispersing stress throughout the network. Concurrently, mechanical stress induced by electrochemical reactions prompts BTO to generate a local electric field, facilitating Li+ transport. Consequently, the developed anode (SiO@PCB) demonstrates remarkable electrochemical performance in LIBs, exhibiting a capacity retention rate of 94% even after 500 cycles at 1 A g−1. Furthermore, a capacity retention of 71.6% is demonstrated by SiO@PCB anode after 1000 cycles at 5 C in sulfide-based all-solid-state LIBs using an NCM83 cathode. This composite conductive network structure provides an effective guidance plan for achieving interface stability and long-term lithium storage of Si-based anodes.
二氧化硅（SiO）由于其优越的理论比容量，被认为是高能量密度锂离子电池（LIBs）极有前途的阳极候选材料。然而，SiO阳极面临着巨大的挑战，包括大量的体积膨胀和厚固体电解质界面（SEI）的持续生长。在这项工作中，提出了一种具有双钉钉和压电效应的复合导电网络，该网络的设计巧妙地改善了电极的电化学反应动力学。在提出的网络结构中，单壁碳纳米管（CNTs）作为快速电子导体和结构保护层，在SiO颗粒表面形成三维（3D）涂层网络。钛酸钡（BTO）纳米颗粒通过形成刚性锚点锚定在碳纳米管网络的节点上，在整个网络中分散应力。同时，电化学反应引起的机械应力促使BTO产生局部电场，有利于Li+的输运。因此，开发的阳极（SiO@PCB）在锂离子电池中表现出卓越的电化学性能，即使在1 a g−1下循环500次后，其容量保持率仍为94%。此外，在使用NCM83阴极的硫化物基全固态锂电池中，SiO@PCB阳极在5℃下循环1000次后，其容量保持率为71.6%。这种复合导电网络结构为实现硅基阳极的界面稳定性和锂的长期存储提供了有效的指导方案。
{"title":"Synergistic pinning and piezoelectric effects in CNT/BaTiO3 network for SiO-based anodes toward ultra-stable lithium batteries","authors":"Feng Sun , Anjun Hu , Junmei Han , Shenghai Xin , Zhihui Ma , Youwei Wang , Jianbin Li , Qi Wan , Ruidie Tang , Shaofei Wu , Xuanhui Qu , Ping Li","doi":"10.1016/j.jechem.2025.12.025","DOIUrl":"10.1016/j.jechem.2025.12.025","url":null,"abstract":"<div><div>Silicon dioxide (SiO) is regarded as a promising anode candidate for high-energy-density lithium-ion batteries (LIBs) owing to its superior theoretical specific capacity. However, SiO anodes encounter substantial challenges, including substantial volume expansion and persistent growth of a thick solid electrolyte interphase (SEI). In this work, a composite conductive network with dual pinning and piezoelectric effects is proposed, which is cleverly designed to improve the electrochemical reaction kinetics of the electrode. Within the proposed network architecture, single-walled carbon nanotubes (CNTs) serve as fast electronic conductors and structural protective layers, forming a three-dimensional (3D) coating network on the surface of SiO particles. Barium titanate (BTO) nanoparticles are anchored at the nodes of the CNT network through the formation of rigid anchor points, dispersing stress throughout the network. Concurrently, mechanical stress induced by electrochemical reactions prompts BTO to generate a local electric field, facilitating Li<sup>+</sup> transport. Consequently, the developed anode (SiO@PCB) demonstrates remarkable electrochemical performance in LIBs, exhibiting a capacity retention rate of 94% even after 500 cycles at 1 A g<sup>−1</sup>. Furthermore, a capacity retention of 71.6% is demonstrated by SiO@PCB anode after 1000 cycles at 5 C in sulfide-based all-solid-state LIBs using an NCM83 cathode. This composite conductive network structure provides an effective guidance plan for achieving interface stability and long-term lithium storage of Si-based anodes.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 748-758"},"PeriodicalIF":14.9,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977543","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}
Pub Date : 2025-12-19DOI: 10.1016/j.jechem.2025.12.022
Wenjun Zhang , Takehisa Mimbu , Dae-Yeong Kim , Shinya Furukawa , Hyun-Ha Kim , Tomohiro Nozaki
Methanation of CO2 in biogas offers an efficient and sustainable pathway compared to the carbon sources from carbon capture and utilization/storage (CCU/CCS) technologies, as it avoids a separate CO2 capture step. Moreover, CO2 from biogas combustion does not need to be recycled, owing to the carbon-neutral nature of biogas as a renewable energy source. Herein, we report biogas methanation using plasma catalysis for the first time in a packed-bed dielectric barrier discharge (DBD) reactor over 6 wt%-Ni/γ-Al2O3. The total gas flow rate reached up to 3000 mL min−1 (CH4/CO2 = 60/40, CO2/H2 = 1/4), representing a large-scale study. The respective contributions of nonthermal plasma and methanation reaction heat were clarified. We observed that plasma-generated reactive species—vibrationally excited CO2 and plasma-derived atomic hydrogen (PDAH)—play a crucial role. These species enhance CH4 yield at low temperature and decrease reaction onset temperature (TON) compared to thermal catalysis. Also, pseudo-autonomous operation was confirmed at a total gas flow of 3000 mL min−1 and DBD power of 11 W with CO2 conversion of 77%, CH4 selectivity >98%, and energy efficiency of 75%. Moreover, pulsed CH4 injection experiments demonstrated that they endow the reaction system with the ability to withstand external disturbances, such as fluctuation of CH4 content in biogas. These results demonstrate the feasibility and high efficiency of plasma-catalyzed biogas methanation. Moreover, a high flexibility of DBD makes it particularly suitable for upgrading decentralized or stranded biogas resources.
与碳捕集与利用/封存（CCU/CCS）技术相比，沼气中二氧化碳的甲烷化提供了一种高效和可持续的途径，因为它避免了单独的二氧化碳捕集步骤。此外，由于沼气作为可再生能源的碳中性特性，沼气燃烧产生的二氧化碳不需要再循环利用。在此，我们首次报道了等离子体催化沼气甲烷化在填充床介质阻挡放电（DBD）反应器中使用6 wt%-Ni/γ-Al2O3。总气量高达3000 mL min - 1 (CH4/CO2 = 60/40, CO2/H2 = 1/4)，为大规模研究。澄清了非热等离子体和甲烷化反应热各自的贡献。我们观察到等离子体产生的反应物质-振动激发CO2和等离子体衍生的原子氢(PDAH) -起着至关重要的作用。与热催化相比，这些物质提高了低温下CH4的产率，降低了反应起始温度。同时，在总气量为3000 mL min - 1、DBD功率为11 W、CO2转化率为77%、CH4选择性为98%、能效为75%的条件下，模拟自主运行。此外，脉冲CH4注入实验表明，它们赋予反应体系抵御外部干扰的能力，如沼气中CH4含量的波动。这些结果证明了等离子体催化沼气甲烷化的可行性和高效性。此外，DBD的高度灵活性使其特别适合于升级分散或搁浅的沼气资源。
{"title":"Plasma promotion of CO2 methanation at low temperature: Validation of nonthermal effect on large-scale biogas upgrading","authors":"Wenjun Zhang , Takehisa Mimbu , Dae-Yeong Kim , Shinya Furukawa , Hyun-Ha Kim , Tomohiro Nozaki","doi":"10.1016/j.jechem.2025.12.022","DOIUrl":"10.1016/j.jechem.2025.12.022","url":null,"abstract":"<div><div>Methanation of CO<sub>2</sub> in biogas offers an efficient and sustainable pathway compared to the carbon sources from carbon capture and utilization/storage (CCU/CCS) technologies, as it avoids a separate CO<sub>2</sub> capture step. Moreover, CO<sub>2</sub> from biogas combustion does not need to be recycled, owing to the carbon-neutral nature of biogas as a renewable energy source. Herein, we report biogas methanation using plasma catalysis for the first time in a packed-bed dielectric barrier discharge (DBD) reactor over 6 wt%-Ni/γ-Al<sub>2</sub>O<sub>3</sub>. The total gas flow rate reached up to 3000 mL min<sup>−1</sup> (CH<sub>4</sub>/CO<sub>2</sub> = 60/40, CO<sub>2</sub>/H<sub>2</sub> = 1/4), representing a large-scale study. The respective contributions of nonthermal plasma and methanation reaction heat were clarified. We observed that plasma-generated reactive species—vibrationally excited CO<sub>2</sub> and plasma-derived atomic hydrogen (PDAH)—play a crucial role. These species enhance CH<sub>4</sub> yield at low temperature and decrease reaction onset temperature (<em>T</em><sub>ON</sub>) compared to thermal catalysis. Also, pseudo-autonomous operation was confirmed at a total gas flow of 3000 mL min<sup>−1</sup> and DBD power of 11 W with CO<sub>2</sub> conversion of 77%, CH<sub>4</sub> selectivity >98%, and energy efficiency of 75%. Moreover, pulsed CH<sub>4</sub> injection experiments demonstrated that they endow the reaction system with the ability to withstand external disturbances, such as fluctuation of CH<sub>4</sub> content in biogas. These results demonstrate the feasibility and high efficiency of plasma-catalyzed biogas methanation. Moreover, a high flexibility of DBD makes it particularly suitable for upgrading decentralized or stranded biogas resources.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 858-867"},"PeriodicalIF":14.9,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977540","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}
Pub Date : 2025-12-17DOI: 10.1016/j.jechem.2025.12.021
Yu Huang , Gui Chu , Mao Wang , Kehan Li , Tongen Lin , Lili Wang , Yongqi Sun , Kui Li , Xiaobo Zhu
P2-type layered oxides are promising cathodes for sodium-ion batteries, yet their practical application is hindered by structural instability and parasitic interfacial reactions. Conventional surface coatings face a fundamental trade-off, where protective layers inevitably introduce additional Na+ transport paths and barriers. Here, we overcome this limitation by designing a multifunctional Nd-rich nano-island heterostructure on the P2-type cathode surface. Driven by a large lattice mismatch, this non-continuous architecture creates a thermodynamically stable interface where chemically rooted, electronically conductive nano-islands enhance charge transfer, while inter-island channels maintain open pathways for rapid Na+ diffusion. Theoretical calculations reveal that the heterostructure improves surface conductivity and anchors lattice oxygen via strong Nd–O bonds. Experimentally, in situ XRD confirms the mitigation of the detrimental P2-O2 phase transition by a buffering Z-phase and the recovery of lattice parameters upon discharge, while depth-resolved ToF-SIMS validates the formation of a thin, compact, and inorganic-rich cathode-electrolyte interphase that reduces interfacial side reactions. Consequently, the engineered cathode demonstrates exceptional rate performance (90 mA h g−1 at 20 C), outstanding cycling stability (85.8 % retention over 200 cycles), and demonstrated potential in practical pouch cell configurations.
p2型层状氧化物是一种很有前途的钠离子电池阴极材料，但其实际应用受到结构不稳定性和寄生界面反应的阻碍。传统的表面涂层面临着一个基本的权衡，其中保护层不可避免地引入额外的Na+传输路径和屏障。在这里，我们通过在p2型阴极表面设计多功能富nd纳米岛异质结构来克服这一限制。在大晶格失配的驱动下，这种非连续结构创造了一个热力学稳定的界面，其中化学扎根的电子导电纳米岛增强了电荷转移，而岛间通道保持了Na+快速扩散的开放途径。理论计算表明，异质结构提高了表面导电性，并通过强Nd-O键锚定晶格氧。实验中，原位XRD证实了缓冲z相减缓了有害的P2-O2相变，并在放电时恢复了晶格参数，而深度分辨ToF-SIMS证实了薄、致密、富无机的阴极电解质界面相的形成，减少了界面副反应。因此，该工程阴极表现出优异的倍率性能（20℃下90 mA h g−1），出色的循环稳定性（200次循环保持率85.8%），并在实际的袋状电池配置中显示出潜力。
{"title":"A nano-island surface architecture that unlocks synergistic kinetic and stability enhancements in P2-type sodium-ion battery cathodes","authors":"Yu Huang , Gui Chu , Mao Wang , Kehan Li , Tongen Lin , Lili Wang , Yongqi Sun , Kui Li , Xiaobo Zhu","doi":"10.1016/j.jechem.2025.12.021","DOIUrl":"10.1016/j.jechem.2025.12.021","url":null,"abstract":"<div><div>P2-type layered oxides are promising cathodes for sodium-ion batteries, yet their practical application is hindered by structural instability and parasitic interfacial reactions. Conventional surface coatings face a fundamental trade-off, where protective layers inevitably introduce additional Na<sup>+</sup> transport paths and barriers. Here, we overcome this limitation by designing a multifunctional Nd-rich nano-island heterostructure on the P2-type cathode surface. Driven by a large lattice mismatch, this non-continuous architecture creates a thermodynamically stable interface where chemically rooted, electronically conductive nano-islands enhance charge transfer, while inter-island channels maintain open pathways for rapid Na<sup>+</sup> diffusion. Theoretical calculations reveal that the heterostructure improves surface conductivity and anchors lattice oxygen via strong Nd–O bonds. Experimentally, in situ XRD confirms the mitigation of the detrimental P2-O2 phase transition by a buffering Z-phase and the recovery of lattice parameters upon discharge, while depth-resolved ToF-SIMS validates the formation of a thin, compact, and inorganic-rich cathode-electrolyte interphase that reduces interfacial side reactions. Consequently, the engineered cathode demonstrates exceptional rate performance (90 mA h g<sup>−1</sup> at 20 C), outstanding cycling stability (85.8 % retention over 200 cycles), and demonstrated potential in practical pouch cell configurations.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"115 ","pages":"Pages 737-747"},"PeriodicalIF":14.9,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145977536","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}
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