Rational design of inorganic materials with targeted elastic properties requires understanding the physical mechanisms governing shear modulus (G) and bulk modulus (K). However, current machine learning approaches suffer from model opacity and neglect of feature interactions. Herein, we develop an interpretable machine learning framework that identifies 34 key physical descriptors from 5272 initial features (<1%), achieving R2 = 0.892 for G and 0.949 for K with robustness confirmed across diverse model architectures, while revealing their distinct physical origins through comprehensive interpretability analysis integrating ANOVA, SHAP, and partial dependence methods. Our analysis demonstrates that K is primarily governed by geometric and density features reflecting resistance to uniform compression, whereas G is controlled by electronic structure features encoding directional bonding characteristics. Volume per atom (vpa) emerges as the dominant descriptor, with fermi energy (efermi) exhibiting differential sensitivity between moduli (117% relative change for G versus 47% for K). Notably, systematic investigation of feature interactions uncovers synergistic and compensatory effects: low vpa provides the geometric prerequisite for effective orbital overlap, while high efermi ensures sufficient bonding electrons; the density-volume compensation offers alternative pathways to equivalent bulk modulus. These insights are translated into design strategies: high-toughness materials benefit from high-density constituents with moderate Fermi energy, whereas superhard materials demand minimized vpa coupled with maximized efermi. This framework bridges data-driven predictions with solid-state physics, providing a physically interpretable basis for tailoring elastic properties of inorganic materials.
{"title":"Decoding physical mechanisms governing elastic moduli in inorganic materials through interpretable machine learning","authors":"Xinglu Zhang, Hongwei Yang, Wenxia Li, Juan Du","doi":"10.1039/d6ta00098c","DOIUrl":"https://doi.org/10.1039/d6ta00098c","url":null,"abstract":"Rational design of inorganic materials with targeted elastic properties requires understanding the physical mechanisms governing shear modulus (<em>G</em>) and bulk modulus (<em>K</em>). However, current machine learning approaches suffer from model opacity and neglect of feature interactions. Herein, we develop an interpretable machine learning framework that identifies 34 key physical descriptors from 5272 initial features (<1%), achieving <em>R</em><small><sup>2</sup></small> = 0.892 for <em>G</em> and 0.949 for <em>K</em> with robustness confirmed across diverse model architectures, while revealing their distinct physical origins through comprehensive interpretability analysis integrating ANOVA, SHAP, and partial dependence methods. Our analysis demonstrates that <em>K</em> is primarily governed by geometric and density features reflecting resistance to uniform compression, whereas <em>G</em> is controlled by electronic structure features encoding directional bonding characteristics. Volume per atom (<em>vpa</em>) emerges as the dominant descriptor, with fermi energy (<em>efermi</em>) exhibiting differential sensitivity between moduli (117% relative change for <em>G versus</em> 47% for <em>K</em>). Notably, systematic investigation of feature interactions uncovers synergistic and compensatory effects: low <em>vpa</em> provides the geometric prerequisite for effective orbital overlap, while high <em>efermi</em> ensures sufficient bonding electrons; the density-volume compensation offers alternative pathways to equivalent bulk modulus. These insights are translated into design strategies: high-toughness materials benefit from high-density constituents with moderate Fermi energy, whereas superhard materials demand minimized <em>vpa</em> coupled with maximized <em>efermi</em>. This framework bridges data-driven predictions with solid-state physics, providing a physically interpretable basis for tailoring elastic properties of inorganic materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"31 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High-entropy oxides (HEOs) show great potential in supercapacitor due to their unique structural and electronic properties, but precise control of microstructure within these systems still remains a crucial challenge. Herein, a MOF gel synthesis strategy based on gelation kinetics engineering is proposed to tailor the architecture and pore characteristics of high-entropy spinel oxides by tuning the synthesis concentration of the precursor. The influence of gelation kinetics on the microstructure of MOF gel precursors, along with its impact on the morphology, specific surface area, and pore size distribution of the resulting pyrolysis products, was investigated. It was found that MOF gels formed under low-concentration conditions can derive HEOs with more densely packed particles and a hierarchically distributed pore structure. This unique architecture facilitates the establishment of an efficient electron conduction network and ion diffusion pathways, thereby significantly optimizing the electrode kinetics. The optimally structured HEO ((Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 ) 3 O 4 ) delivers a specific capacitance of 636.4 F g -1 at a current density of 1 A g -1 . When assembled as a cathode with activated carbon in a solid-state lithium-ion hybrid capacitor, the device exhibits a broad aqueous voltage window of 1.5 V and a high energy density of 36.6 W h kg -1 at a power density of 750 W kg -1 . This work highlights the potential of gelation kinetics engineering as a promising strategy for developing advanced porous HEOs.
高熵氧化物（HEOs）由于其独特的结构和电子特性在超级电容器中显示出巨大的潜力，但在这些系统中精确控制微观结构仍然是一个关键的挑战。本文提出了一种基于凝胶动力学工程的MOF凝胶合成策略，通过调整前驱体的合成浓度来调整高熵尖晶石氧化物的结构和孔隙特征。研究了凝胶动力学对MOF凝胶前驱体微观结构的影响，以及对热解产物形貌、比表面积和孔径分布的影响。研究发现，在低浓度条件下形成的MOF凝胶可以得到颗粒密度更大、孔隙结构分层分布的HEOs。这种独特的结构有助于建立有效的电子传导网络和离子扩散途径，从而显着优化电极动力学。优化结构的HEO （(Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2) 3o 4）在电流密度为1 a g -1时的比电容为636.4 F g -1。当在固态锂离子混合电容器中作为阴极与活性炭组装时，该器件表现出1.5 V的宽水电压窗和在750 W kg -1的功率密度下36.6 Wh kg -1的高能量密度。这项工作强调了凝胶动力学工程作为开发先进多孔heo的有前途的策略的潜力。
{"title":"Densely Packed High-Entropy Spinel Nanoparticles Derived from Concentration-Driven MOF Gel for Lithium-Ion Hybrid Capacitors","authors":"Yidong Zhang, Hui Cao, Jiale Liu, Jianfei Ding, Qirui Guo, Shixin Sun, Yuan Wang","doi":"10.1039/d6ta00353b","DOIUrl":"https://doi.org/10.1039/d6ta00353b","url":null,"abstract":"High-entropy oxides (HEOs) show great potential in supercapacitor due to their unique structural and electronic properties, but precise control of microstructure within these systems still remains a crucial challenge. Herein, a MOF gel synthesis strategy based on gelation kinetics engineering is proposed to tailor the architecture and pore characteristics of high-entropy spinel oxides by tuning the synthesis concentration of the precursor. The influence of gelation kinetics on the microstructure of MOF gel precursors, along with its impact on the morphology, specific surface area, and pore size distribution of the resulting pyrolysis products, was investigated. It was found that MOF gels formed under low-concentration conditions can derive HEOs with more densely packed particles and a hierarchically distributed pore structure. This unique architecture facilitates the establishment of an efficient electron conduction network and ion diffusion pathways, thereby significantly optimizing the electrode kinetics. The optimally structured HEO ((Cr 0.2 Mn 0.2 Fe 0.2 Co 0.2 Ni 0.2 ) 3 O 4 ) delivers a specific capacitance of 636.4 F g -1 at a current density of 1 A g -1 . When assembled as a cathode with activated carbon in a solid-state lithium-ion hybrid capacitor, the device exhibits a broad aqueous voltage window of 1.5 V and a high energy density of 36.6 W h kg -1 at a power density of 750 W kg -1 . This work highlights the potential of gelation kinetics engineering as a promising strategy for developing advanced porous HEOs.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"25 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The hydrogen evolution reaction (HER) is a cornerstone of water electrolysis technologies for sustainable hydrogen production. Nickel-based catalysts have emerged as leading non-precious alternatives to platinum due to their abundance, electrochemical stability in alkaline environments, and tunable physicochemical properties. This review critically examines recent advances in the synthesis, surface/interface modification, and performance optimization of monometallic Ni HER electrodes, emphasizing how rational engineering can elevate their reactivity toward state-of-theart levels. A comprehensive overview of fabrication techniques, including electrodeposition, hydrothermal synthesis, pulsed laser deposition (PLD), physical vapor deposition (PVD), laser nanomachining, and chemical vapor deposition (CVD), is presented with a focus on how these methods tailor microstructure, active-site density, and interfacial chemistry. Special attention is given to engineering strategies such as defect induction (e.g., oxygen vacancies), interface engineering, and hierarchical nanostructuring, which regulate surface reactivity, charge-transfer behavior, and catalytic efficiency. Across the literature, these approaches have produced monometallic Ni electrodes with overpotentials as low as ~ 40-50 mV at 10 mA cm -2 , and Tafel slopes in the range of 55-65 mV dec -1 , values that approach or, in some cases, rival those of multicomponent Ni-based electrocatalysts (e.g., Ni-Mo, Ni-Fe) and significantly narrow the performance gap to Pt-group materials under alkaline conditions. By systematically correlating synthesis routes, structural descriptors, and HER metrics, this review demonstrates how monometallic Ni can achieve high intrinsic activity, robust durability, and industrially relevant current densities without relying on noble metals or complex alloying. Furthermore, by outlining a strategic roadmap to translate these lab-scale advances into scalable manufacturing processes, these insights establish monometallic nickel not only as a benchmark model system for mechanistic studies but also as a technologically viable catalyst platform for next-generation alkaline hydrogen production.
析氢反应（HER）是水电解可持续制氢技术的基石。镍基催化剂由于其丰富度、在碱性环境中的电化学稳定性和可调的物理化学性质而成为铂的主要非贵重替代品。本文综述了单金属Ni HER电极的合成、表面/界面改性和性能优化方面的最新进展，强调了合理的工程设计如何将其反应性提升到最先进的水平。全面概述了包括电沉积、水热合成、脉冲激光沉积（PLD）、物理气相沉积（PVD）、激光纳米加工和化学气相沉积（CVD）在内的制造技术，重点介绍了这些方法如何定制微观结构、活性位点密度和界面化学。特别关注工程策略，如缺陷诱导（如氧空位）、界面工程和分层纳米结构，它们调节表面反应性、电荷转移行为和催化效率。在文献中，这些方法已经生产出了过电位低至~ 40-50 mV （10 mA cm -2）的单金属Ni电极，Tafel斜率在55-65 mV（12 -1）范围内，这些值接近或在某些情况下与多组分Ni基电催化剂（例如Ni- mo， Ni- fe）相当，并且在碱性条件下显着缩小了与pt基材料的性能差距。通过系统地关联合成路线、结构描述符和HER指标，本综述展示了单金属Ni如何在不依赖贵金属或复杂合金的情况下实现高内在活性、耐用性和工业相关电流密度。此外，通过概述将这些实验室规模的进展转化为可扩展的制造工艺的战略路线图，这些见解确立了单金属镍不仅是机械研究的基准模型系统，而且是下一代碱性氢生产技术上可行的催化剂平台。
{"title":"Monometallic Nickel as a Tunable Electrocatalyst for Alkaline Hydrogen Evolution: A Critical Review","authors":"Ioannis Poimenidis, Michalis Konsolakis","doi":"10.1039/d6ta00813e","DOIUrl":"https://doi.org/10.1039/d6ta00813e","url":null,"abstract":"The hydrogen evolution reaction (HER) is a cornerstone of water electrolysis technologies for sustainable hydrogen production. Nickel-based catalysts have emerged as leading non-precious alternatives to platinum due to their abundance, electrochemical stability in alkaline environments, and tunable physicochemical properties. This review critically examines recent advances in the synthesis, surface/interface modification, and performance optimization of monometallic Ni HER electrodes, emphasizing how rational engineering can elevate their reactivity toward state-of-theart levels. A comprehensive overview of fabrication techniques, including electrodeposition, hydrothermal synthesis, pulsed laser deposition (PLD), physical vapor deposition (PVD), laser nanomachining, and chemical vapor deposition (CVD), is presented with a focus on how these methods tailor microstructure, active-site density, and interfacial chemistry. Special attention is given to engineering strategies such as defect induction (e.g., oxygen vacancies), interface engineering, and hierarchical nanostructuring, which regulate surface reactivity, charge-transfer behavior, and catalytic efficiency. Across the literature, these approaches have produced monometallic Ni electrodes with overpotentials as low as ~ 40-50 mV at 10 mA cm -2 , and Tafel slopes in the range of 55-65 mV dec -1 , values that approach or, in some cases, rival those of multicomponent Ni-based electrocatalysts (e.g., Ni-Mo, Ni-Fe) and significantly narrow the performance gap to Pt-group materials under alkaline conditions. By systematically correlating synthesis routes, structural descriptors, and HER metrics, this review demonstrates how monometallic Ni can achieve high intrinsic activity, robust durability, and industrially relevant current densities without relying on noble metals or complex alloying. Furthermore, by outlining a strategic roadmap to translate these lab-scale advances into scalable manufacturing processes, these insights establish monometallic nickel not only as a benchmark model system for mechanistic studies but also as a technologically viable catalyst platform for next-generation alkaline hydrogen production.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"229 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mehmet E. Bayat, Edgar R. Nandayapa, Carlo Tiebe, Eva L. Unger, Emil J. W. List-Kratochvil
Controlling trace humidity is vital for both the fabrication and long-term stability of metal halide perovskite (MHP) solar cells. Relevant humidity levels are typically below 10 ppmV, especially in glovebox-based processing and in well-encapsulated devices. Even minute amounts during fabrication can influence crystallization, introducing defects and lowering efficiency. Over time, humidity accelerates degradation of the perovskite layer and internal interfaces, ultimately reducing operational lifetime. Probing these effects at low concentrations under operando conditions is therefore essential for advancing device performance and durability. In this work, we employed a high-precision transfer standard dew point hygrometer to investigate humidity levels between 5 and 35 ppmV in non-encapsulated MHP solar cells. To permit unobstructed water migration during operation, we fabricated interdigital back contact devices. Operando measurements revealed water transport through the perovskite layer and enabled quantification of outgassing. Under trace-humidified conditions, devices exhibited initial charge-carrier quenching, followed by gradual recovery. Notably, the photocurrent response to humidified nitrogen demonstrated that the MHP layer behaves fully reversibly within the explored timescale and across the investigated humidity levels and conditions. These findings establish a systematic operando framework for examining extrinsic stressors in perovskites and highlight opportunities for assessing passivation strategies.
{"title":"An operando spectroscopic examination of the influence of trace humidity on interdigital back contact metal halide perovskite solar cells","authors":"Mehmet E. Bayat, Edgar R. Nandayapa, Carlo Tiebe, Eva L. Unger, Emil J. W. List-Kratochvil","doi":"10.1039/d6ta01295g","DOIUrl":"https://doi.org/10.1039/d6ta01295g","url":null,"abstract":"Controlling trace humidity is vital for both the fabrication and long-term stability of metal halide perovskite (MHP) solar cells. Relevant humidity levels are typically below 10 ppm<small><sub>V</sub></small>, especially in glovebox-based processing and in well-encapsulated devices. Even minute amounts during fabrication can influence crystallization, introducing defects and lowering efficiency. Over time, humidity accelerates degradation of the perovskite layer and internal interfaces, ultimately reducing operational lifetime. Probing these effects at low concentrations under <em>operando</em> conditions is therefore essential for advancing device performance and durability. In this work, we employed a high-precision transfer standard dew point hygrometer to investigate humidity levels between 5 and 35 ppm<small><sub>V</sub></small> in non-encapsulated MHP solar cells. To permit unobstructed water migration during operation, we fabricated interdigital back contact devices. <em>Operando</em> measurements revealed water transport through the perovskite layer and enabled quantification of outgassing. Under trace-humidified conditions, devices exhibited initial charge-carrier quenching, followed by gradual recovery. Notably, the photocurrent response to humidified nitrogen demonstrated that the MHP layer behaves fully reversibly within the explored timescale and across the investigated humidity levels and conditions. These findings establish a systematic <em>operando</em> framework for examining extrinsic stressors in perovskites and highlight opportunities for assessing passivation strategies.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"58 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519176","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhiyu Jin, Lei Chen, Jiayu Li, Xiang Chen, Pengxiang Gao, jiuxiang sun, Chong Zhang, Bingcheng Hu
Substituent effects play a pivotal role in modulating the properties of organic ionic compounds through the synergistic electronic and steric effects. It is one of the core theoretical foundations for studying structure-property relationships in materials science and organic chemistry. However, in-depth examination of the substituent effects on significant cyclo-pentazolate anion (cyclo-N5−) salts has not been studied. Herein, to explore how different substituents (R) in 4-R-1,5-diaminotetrazolium cations affect the properties of their cyclo-N5− salts, four types of cyclo-N5− salts bearing distinct substituents (−CH3, −CH2COCH3, −CH2CONH2, and −CH2COOCH3) were designed and synthesized. Analysis of using X-ray single-crystal diffraction indicates that the crystal structures of these salts vary significantly based on the substituents. Among them, the cyclo-N5− salt with the −CH3 substituent exhibits optimal crystal density and stability. The −CH2CONH2 group improves crystal stability via increased hydrogen-bonding capacity. In contrast, −CH2COCH3 and −CH2COOCH3 lead to reduced stability and crystal density due to larger steric bulk and lack of hydrogen-bonding interactions. Additionally, Hirshfeld surface analysis and fingerprint plots were employed to investigate interionic interaction regions, revealing extensive van der Waals interactions and the formation of N–H···N hydrogen bonds. The cyclo-N5− salt with the −CH3 substituent displays the highest detonation performance (D: 8811.47 m·s−1; P: 26.94 GPa), which benefits from a higher enthalpy of formation.
{"title":"Modulating the 4-R-1,5-diaminotetrazole pentazolate salts properties by substituent effects","authors":"Zhiyu Jin, Lei Chen, Jiayu Li, Xiang Chen, Pengxiang Gao, jiuxiang sun, Chong Zhang, Bingcheng Hu","doi":"10.1039/d6ta00419a","DOIUrl":"https://doi.org/10.1039/d6ta00419a","url":null,"abstract":"Substituent effects play a pivotal role in modulating the properties of organic ionic compounds through the synergistic electronic and steric effects. It is one of the core theoretical foundations for studying structure-property relationships in materials science and organic chemistry. However, in-depth examination of the substituent effects on significant cyclo-pentazolate anion (cyclo-N5−) salts has not been studied. Herein, to explore how different substituents (R) in 4-R-1,5-diaminotetrazolium cations affect the properties of their cyclo-N5− salts, four types of cyclo-N5− salts bearing distinct substituents (−CH3, −CH2COCH3, −CH2CONH2, and −CH2COOCH3) were designed and synthesized. Analysis of using X-ray single-crystal diffraction indicates that the crystal structures of these salts vary significantly based on the substituents. Among them, the cyclo-N5− salt with the −CH3 substituent exhibits optimal crystal density and stability. The −CH2CONH2 group improves crystal stability via increased hydrogen-bonding capacity. In contrast, −CH2COCH3 and −CH2COOCH3 lead to reduced stability and crystal density due to larger steric bulk and lack of hydrogen-bonding interactions. Additionally, Hirshfeld surface analysis and fingerprint plots were employed to investigate interionic interaction regions, revealing extensive van der Waals interactions and the formation of N–H···N hydrogen bonds. The cyclo-N5− salt with the −CH3 substituent displays the highest detonation performance (D: 8811.47 m·s−1; P: 26.94 GPa), which benefits from a higher enthalpy of formation.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"90 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507487","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The metal–support interface and metal electronic properties critically govern CO2 adsorption configurations, hydrogen activation efficiency, and subsequent hydrogenation pathways, which significantly affect CO2 activation efficiency and product distribution. We engineered a Ni/SrTiNbO3 catalyst through Nb substitution at the B-site of SrTiO3, which induced electron transfer from Nb to Ni, thereby optimizing the Ni electronic structure and enhancing H2 activation with efficient hydrogen spillover. This specific Nb–Ni interface facilitated exclusive CO2 activation via the formate pathway, achieving highly selective CH4 production. DFT calculations revealed a significantly reduced energy barrier for hydrogen-assisted CO2 dissociation and a lower rate-determining step barrier compared to Ni/SrTiO3. The optimized catalyst demonstrated exceptional performance with a CH4 selectivity of 94.7% and CO2 conversion of 75.6%, maintaining stability over 200 hours. This work establishes a rational design strategy for selective CO2 hydrogenation catalysts through precise modulation of interfacial electronic structures and adsorption configurations.
{"title":"Selective CO2 methanation over Ni catalysts on Nb-doped SrTiO3 via interfacial electronic engineering","authors":"Haocheng Li, Chenwei Wang, Yuchen Yan, Yiming Li, Haotian Li, Hongbo Yu, Hongfeng Yin","doi":"10.1039/d6ta00345a","DOIUrl":"https://doi.org/10.1039/d6ta00345a","url":null,"abstract":"The metal–support interface and metal electronic properties critically govern CO<small><sub>2</sub></small> adsorption configurations, hydrogen activation efficiency, and subsequent hydrogenation pathways, which significantly affect CO<small><sub>2</sub></small> activation efficiency and product distribution. We engineered a Ni/SrTiNbO<small><sub>3</sub></small> catalyst through Nb substitution at the B-site of SrTiO<small><sub>3</sub></small>, which induced electron transfer from Nb to Ni, thereby optimizing the Ni electronic structure and enhancing H<small><sub>2</sub></small> activation with efficient hydrogen spillover. This specific Nb–Ni interface facilitated exclusive CO<small><sub>2</sub></small> activation <em>via</em> the formate pathway, achieving highly selective CH<small><sub>4</sub></small> production. DFT calculations revealed a significantly reduced energy barrier for hydrogen-assisted CO<small><sub>2</sub></small> dissociation and a lower rate-determining step barrier compared to Ni/SrTiO<small><sub>3</sub></small>. The optimized catalyst demonstrated exceptional performance with a CH<small><sub>4</sub></small> selectivity of 94.7% and CO<small><sub>2</sub></small> conversion of 75.6%, maintaining stability over 200 hours. This work establishes a rational design strategy for selective CO<small><sub>2</sub></small> hydrogenation catalysts through precise modulation of interfacial electronic structures and adsorption configurations.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"19 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147519175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic–inorganic hybrid perovskites exhibit outstanding properties, including long carrier diffusion lengths, strong visible light absorption, and high extinction coefficients. In these materials, organic cations (MA+) play a critical role in the development of perovskite devices. However, the inherent thermal instability and moisture sensitivity of organic cations are the core reasons leading to material degradation and decreased device stability, which greatly limit the practical application of organic–inorganic hybrid perovskites. To enhance the stability of perovskites, inspired by the stronger hydrogen bonds in heavy water, we replaced the methylammonium cation (CH3NH3+, MA+) in the perovskite with its deuterated form, CH3ND3+, anticipating that this would strengthen the hydrogen bonding with the inorganic framework, thereby effectively improving the material's structural stability and device lifetime. We found that this molecular-level reinforcement leads to multi-faceted macroscopic performance improvements. Firstly, it increases the initial decomposition temperature of the perovskite. This enhancement in thermal stability directly translates into the reliable operation capability of perovskite devices under harsher environmental conditions. Secondly, the stronger hydrogen bond network effectively suppresses the formation of hydrogen vacancies, thereby reducing non-radiative recombination losses. The enhanced hydrogen bonding strengthens the lattice structure, significantly improving the stability of the perovskite material in ambient air.
{"title":"Deuterium-induced hydrogen bond strengthening: a novel strategy for high stability in hybrid perovskites","authors":"Zhuoyue Li, Mengke Yang, Siqi Zhou, Yundong Ma, Guozong Zheng, Ziyu Hu","doi":"10.1039/d5ta09136e","DOIUrl":"https://doi.org/10.1039/d5ta09136e","url":null,"abstract":"Organic–inorganic hybrid perovskites exhibit outstanding properties, including long carrier diffusion lengths, strong visible light absorption, and high extinction coefficients. In these materials, organic cations (MA<small><sup>+</sup></small>) play a critical role in the development of perovskite devices. However, the inherent thermal instability and moisture sensitivity of organic cations are the core reasons leading to material degradation and decreased device stability, which greatly limit the practical application of organic–inorganic hybrid perovskites. To enhance the stability of perovskites, inspired by the stronger hydrogen bonds in heavy water, we replaced the methylammonium cation (CH<small><sub>3</sub></small>NH<small><sub>3</sub></small><small><sup>+</sup></small>, MA<small><sup>+</sup></small>) in the perovskite with its deuterated form, CH<small><sub>3</sub></small>ND<small><sub>3</sub></small><small><sup>+</sup></small>, anticipating that this would strengthen the hydrogen bonding with the inorganic framework, thereby effectively improving the material's structural stability and device lifetime. We found that this molecular-level reinforcement leads to multi-faceted macroscopic performance improvements. Firstly, it increases the initial decomposition temperature of the perovskite. This enhancement in thermal stability directly translates into the reliable operation capability of perovskite devices under harsher environmental conditions. Secondly, the stronger hydrogen bond network effectively suppresses the formation of hydrogen vacancies, thereby reducing non-radiative recombination losses. The enhanced hydrogen bonding strengthens the lattice structure, significantly improving the stability of the perovskite material in ambient air.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"26 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507486","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This review presents an overview of recent progress on conductive metallogels and their applications in fabrication of various electronic devices. It highlights the metallogel classification, synthesis strategies, gelation methods along with the role of metal ions and gelators in integration of ionic/electronic conductance. It also emphasize on the method of fabrication of various devices using conductive metallogels for the targeted applications in wearable electronics, sensors, energy storage and conversion. The imporatance of design of gelator, the selection of metal ions, and its metallogel matrix in driving the electronic and ionic conductivity have also been highlighted with appropriate examples. Further, the dependence of metallogel conductivity on rheological properties has been drawn to highlight the importance of gel-phase soft materials in the fabrication of soft electronic devices. The critical review on current challenges and potential future advancements of conductive metallogels has also been addressed to inspire researchers to investigate new avenues in the field of conductive soft materials.
{"title":"Conductive Metallogels for Electronic Device Fabrication","authors":"Bharat Kumar Sahu, Sakshi Tiwari, Mrigendra Dubey","doi":"10.1039/d5ta10470j","DOIUrl":"https://doi.org/10.1039/d5ta10470j","url":null,"abstract":"This review presents an overview of recent progress on conductive metallogels and their applications in fabrication of various electronic devices. It highlights the metallogel classification, synthesis strategies, gelation methods along with the role of metal ions and gelators in integration of ionic/electronic conductance. It also emphasize on the method of fabrication of various devices using conductive metallogels for the targeted applications in wearable electronics, sensors, energy storage and conversion. The imporatance of design of gelator, the selection of metal ions, and its metallogel matrix in driving the electronic and ionic conductivity have also been highlighted with appropriate examples. Further, the dependence of metallogel conductivity on rheological properties has been drawn to highlight the importance of gel-phase soft materials in the fabrication of soft electronic devices. The critical review on current challenges and potential future advancements of conductive metallogels has also been addressed to inspire researchers to investigate new avenues in the field of conductive soft materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"12 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuan Yang, Xinwei Wang, Jinhai Zhang, Cai Qi, Yi Ke, Can Qian, Zhuang Ji, Tao Wang, Yuan Ma, Faxing Wang, Zhi Zhu, Jiarui He, Xin-Bing Cheng, Yiren Zhong, Yuping Wu
Lithium metal batteries (LMBs) promise the next generation of energy storage technology due to their ultra-high theoretical specific capacity and energy density. The realization of LMBs heavily relies on stable, high-capacity, and fast charging/discharging Li metal anodes (LMAs). However, plating/stripping of Li metal at the widely-used "hostless" Li foil is subjected to severe dendrite growth and low reversibility, challenging the practical application of LMAs. Unlike the conventional Li foil, LMAs with delicately-designed bulk structures, denoted as structured LMAs, regulate Li deposition behavior through the incorporated framework, providing an effective way of containing the inherent defects of LMAs, such as infinite volume expansion, uncontrollable growth of Li dendrites, and excessive side reactions with electrolyte. Despite much progress, the design of structured LMAs lacks a systematic summary and deep insight into the structure-property relationship. This review underlines the challenges in the design and preparation of structured LMAs and then categorizes and summarizes the current progress of research on structured LMAs in detail, highlighting the interplay of framework components in regulating the deposition behavior of Li metal. We also discuss the existing hurdles and possible design criteria of structured LMAs, and provide an outlook on some promising directions for future research. The aim of this review is to provide guidance for the rational design of LMAs with unique structures for the next generation of high-energy-density batteries.
{"title":"Design Principle of Structured Lithium Metal Anodes for High-Energy Batteries","authors":"Yuan Yang, Xinwei Wang, Jinhai Zhang, Cai Qi, Yi Ke, Can Qian, Zhuang Ji, Tao Wang, Yuan Ma, Faxing Wang, Zhi Zhu, Jiarui He, Xin-Bing Cheng, Yiren Zhong, Yuping Wu","doi":"10.1039/d6ta00509h","DOIUrl":"https://doi.org/10.1039/d6ta00509h","url":null,"abstract":"Lithium metal batteries (LMBs) promise the next generation of energy storage technology due to their ultra-high theoretical specific capacity and energy density. The realization of LMBs heavily relies on stable, high-capacity, and fast charging/discharging Li metal anodes (LMAs). However, plating/stripping of Li metal at the widely-used \"hostless\" Li foil is subjected to severe dendrite growth and low reversibility, challenging the practical application of LMAs. Unlike the conventional Li foil, LMAs with delicately-designed bulk structures, denoted as structured LMAs, regulate Li deposition behavior through the incorporated framework, providing an effective way of containing the inherent defects of LMAs, such as infinite volume expansion, uncontrollable growth of Li dendrites, and excessive side reactions with electrolyte. Despite much progress, the design of structured LMAs lacks a systematic summary and deep insight into the structure-property relationship. This review underlines the challenges in the design and preparation of structured LMAs and then categorizes and summarizes the current progress of research on structured LMAs in detail, highlighting the interplay of framework components in regulating the deposition behavior of Li metal. We also discuss the existing hurdles and possible design criteria of structured LMAs, and provide an outlook on some promising directions for future research. The aim of this review is to provide guidance for the rational design of LMAs with unique structures for the next generation of high-energy-density batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"60 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507091","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yajun Yue, Fengjin Qu, Aleksandra Dzięgielewska, Anucha Koedtruad, Qifeng Zheng, Wang Hay Kan, Stephen Hull, Marcin Malys, Marcin Krynski, Franciszek Krok, Takashi Honda, Shuki Torii, Vaclav Petricek, Isaac Abrahams, Ping Miao
Incommensurate structural modulation is a defining yet poorly understood feature of several functional solids, particularly regarding its impact on defect dynamics in fast-ion conductors. Here, using the model oxide-ion conductor Bi2V0.9Cu0.1O5.35 (BICUVOX.10), we achieve the first full determination of a (3 + 2)D incommensurately modulated structure in the well-known γ-type BIMEVOX family. Combined single-crystal and powder X-ray diffraction, neutron total scattering with reverse Monte Carlo modelling, and ab initio molecular dynamics (AIMD) reveal that the γ′-phase exhibits short-range oxygen-vacancy ordering that intrinsically causes its modulation behavior. Upon heating, this vacancy ordering transforms into the dynamically disordered γ-phase, establishing the structural origin of fast-ion conduction. The modulation waves strongly constrain oxygen motion within the vanadate layers, elevating the activation energy, while the coupled apical–equatorial positional modulations generate versatile V/Cu coordination geometries and a zig-zag oxide-ion diffusion network. In addition, Cu atoms were found to act as local vacancy traps. These findings identify vacancy-driven modulation as the mechanism governing the reversible γ′ ↔ γ transition and establish a general framework linking incommensurate structural modulation, defect organization, and ionic transport in complex solid-state conductors.
{"title":"(3 + 2)D modulation governs vacancy ordering and oxide-ion transport in γ-type BIMEVOX conductors","authors":"Yajun Yue, Fengjin Qu, Aleksandra Dzięgielewska, Anucha Koedtruad, Qifeng Zheng, Wang Hay Kan, Stephen Hull, Marcin Malys, Marcin Krynski, Franciszek Krok, Takashi Honda, Shuki Torii, Vaclav Petricek, Isaac Abrahams, Ping Miao","doi":"10.1039/d6ta00458j","DOIUrl":"https://doi.org/10.1039/d6ta00458j","url":null,"abstract":"Incommensurate structural modulation is a defining yet poorly understood feature of several functional solids, particularly regarding its impact on defect dynamics in fast-ion conductors. Here, using the model oxide-ion conductor Bi<small><sub>2</sub></small>V<small><sub>0.9</sub></small>Cu<small><sub>0.1</sub></small>O<small><sub>5.35</sub></small> (BICUVOX.10), we achieve the first full determination of a (3 + 2)D incommensurately modulated structure in the well-known γ-type BIMEVOX family. Combined single-crystal and powder X-ray diffraction, neutron total scattering with reverse Monte Carlo modelling, and <em>ab initio</em> molecular dynamics (AIMD) reveal that the γ′-phase exhibits short-range oxygen-vacancy ordering that intrinsically causes its modulation behavior. Upon heating, this vacancy ordering transforms into the dynamically disordered γ-phase, establishing the structural origin of fast-ion conduction. The modulation waves strongly constrain oxygen motion within the vanadate layers, elevating the activation energy, while the coupled apical–equatorial positional modulations generate versatile V/Cu coordination geometries and a zig-zag oxide-ion diffusion network. In addition, Cu atoms were found to act as local vacancy traps. These findings identify vacancy-driven modulation as the mechanism governing the reversible γ′ ↔ γ transition and establish a general framework linking incommensurate structural modulation, defect organization, and ionic transport in complex solid-state conductors.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"86 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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