Maximizing iridium utilization while maintaining high oxygen evolution reaction (OER) performance remains a persistent challenge in acidic water electrolysis. Immobilizing Ir on conductive, acid-stable supports is promising, yet simultaneously achieving sub-nanometer size, high areal coverage, and strong electronic coupling is difficult. Here, we report a sequential surface-synthesis on titanium nitride (TiN) that yields uniformly distributed sub-nanometer Ir arrays (~0.7 nm). Our method uses ethylenediaminetetraacetic acid (EDTA) as a temporal scaffold: it chemisorbs to TiN to install dense chelating sites, captures Ir 3+ ions, and confines Ir cluster growth. A subsequent thermal treatment at 500°C in a reducing atmosphere removes the ligand shell while preserving ultrasmall particle size and establishing direct Ir-TiN electronic coupling.The optimized catalyst exhibits mixed Ir⁰/Ir x+ coordination with low Ohmic resistance (19 Ω), delivering a mass activity of 342 A g⁻¹_Ir at 1.54 V in acidic electrolyte. In-situ X-ray absorption spectroscopy reveals irreversible surface oxidation as the primary stability-limiting factor. This stepwise strategy provides a general framework for supported catalysts that maximize precious metal utilization via sub-nanometer dispersion.
在保持高析氧反应性能的同时最大限度地提高铱的利用率，是酸性电解领域面临的一个长期挑战。将Ir固定在导电的、酸稳定的载体上是很有前途的，但同时实现亚纳米尺寸、高面积覆盖和强电子耦合是很困难的。在这里，我们报道了氮化钛（TiN）的连续表面合成，产生了均匀分布的亚纳米Ir阵列（~0.7 nm）。我们的方法使用乙二胺四乙酸（EDTA）作为时间支架：它与TiN化学吸附以安装密集的螯合位点，捕获Ir 3+离子，并限制Ir簇的生长。随后在500°C的还原气氛中进行热处理，去除配体壳，同时保持超小颗粒尺寸并建立直接的Ir-TiN电子耦合。优化的催化剂表现出混合Ir⁰/Ir x+配位和低欧米电阻（19 Ω），在酸性电解质中在1.54 V时提供342 a g⁻¹_Ir的质量活性。原位x射线吸收光谱显示不可逆的表面氧化是主要的稳定性限制因素。这种循序渐进的策略为支持催化剂提供了一个总体框架，通过亚纳米分散最大化贵金属的利用。
{"title":"Sequential Surface Synthesis of Dispersed Sub-Nanometer Iridium on Titanium Nitride for Acidic Water Oxidation","authors":"Wenhao Liu, Zhenhua Xie, Lihua Zhang, Jingguang G. Chen, Fang Lu, Yugang Zhang","doi":"10.1039/d5ta09528j","DOIUrl":"https://doi.org/10.1039/d5ta09528j","url":null,"abstract":"Maximizing iridium utilization while maintaining high oxygen evolution reaction (OER) performance remains a persistent challenge in acidic water electrolysis. Immobilizing Ir on conductive, acid-stable supports is promising, yet simultaneously achieving sub-nanometer size, high areal coverage, and strong electronic coupling is difficult. Here, we report a sequential surface-synthesis on titanium nitride (TiN) that yields uniformly distributed sub-nanometer Ir arrays (~0.7 nm). Our method uses ethylenediaminetetraacetic acid (EDTA) as a temporal scaffold: it chemisorbs to TiN to install dense chelating sites, captures Ir 3+ ions, and confines Ir cluster growth. A subsequent thermal treatment at 500°C in a reducing atmosphere removes the ligand shell while preserving ultrasmall particle size and establishing direct Ir-TiN electronic coupling.The optimized catalyst exhibits mixed Ir⁰/Ir x+ coordination with low Ohmic resistance (19 Ω), delivering a mass activity of 342 A g⁻¹_Ir at 1.54 V in acidic electrolyte. In-situ X-ray absorption spectroscopy reveals irreversible surface oxidation as the primary stability-limiting factor. This stepwise strategy provides a general framework for supported catalysts that maximize precious metal utilization via sub-nanometer dispersion.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"47 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122359","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}
Fujun Tao, Zeyi Yao, Jiahui Hou, Zexin Wang, Zhenzhen Yang, Yan Wang
Lithium replenishment separators (LRS) integrating the pre-lithiation agents can regenerate degraded lithium cathodes via facile reassembly with a fresh anode and the LRS. A persistent challenge is the formation of gas or solid residues during pre-lithiation. To address this, for the first time, we develop an LRS based on a molecularly engineered dilithium salt of tetrafluorohydroquinone, which compensates for lithium loss while generating decomposition products that dissolve in the electrolyte as a favorable additive, without forming gas or solid residues, thus offering a green route for lithium compensation. A pristine LiFePO4‖graphite full cell with the LRS exhibits 9.3% higher overall capacity than a polypropylene separator (PPS) cell after 50 cycles at 0.5C, and the degraded LiFePO4‖graphite full cell incorporating this LRS achieves a 44.9% higher capacity than the PPS-based cell after 200 cycles at 0.5C. Our LRS demonstrates strong potential for high-performance lithium-ion batteries and spent battery regeneration.
{"title":"Molecularly Engineered Li Compensation Agent-Integrated Separator Enabling Regeneration of Degraded LiFePO4","authors":"Fujun Tao, Zeyi Yao, Jiahui Hou, Zexin Wang, Zhenzhen Yang, Yan Wang","doi":"10.1039/d5ta09041e","DOIUrl":"https://doi.org/10.1039/d5ta09041e","url":null,"abstract":"Lithium replenishment separators (LRS) integrating the pre-lithiation agents can regenerate degraded lithium cathodes via facile reassembly with a fresh anode and the LRS. A persistent challenge is the formation of gas or solid residues during pre-lithiation. To address this, for the first time, we develop an LRS based on a molecularly engineered dilithium salt of tetrafluorohydroquinone, which compensates for lithium loss while generating decomposition products that dissolve in the electrolyte as a favorable additive, without forming gas or solid residues, thus offering a green route for lithium compensation. A pristine LiFePO4‖graphite full cell with the LRS exhibits 9.3% higher overall capacity than a polypropylene separator (PPS) cell after 50 cycles at 0.5C, and the degraded LiFePO4‖graphite full cell incorporating this LRS achieves a 44.9% higher capacity than the PPS-based cell after 200 cycles at 0.5C. Our LRS demonstrates strong potential for high-performance lithium-ion batteries and spent battery regeneration.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"51 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122360","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}
In the field of photoelectrocatalytic (PEC) water splitting research, BiVO4/WO3 photoanodes exhibit excellent performance in facilitating the separation and transport of photogenerated electron-hole pairs. However, further improving charge transfer efficiency at the heterojunction interface and optimizing the kinetics of water oxidation reactions remain critical challenges. In this study, a Co-BiVO4-Mo/WO3 photoanode was successfully constructed by selectively introducing Mo at the interface and doping Co on the surface of the BiVO4/WO3 heterojunction, enabling precise control over the spatially graded distribution of the two dopants. The resulting photoanode achieved a photocurrent density of 3.423 mA/cm2 at 1.23 V vs. RHE, representing an approximately 1.6 times enhancement compared to the unmodified BiVO4/WO3 heterojunction (2.157 mA/cm2), a 2.3 times higher than relative to pristine BiVO4 (1.508 mA/cm2), and a nearly 3.8 times improvement over pristine WO3 (0.916 mA/cm2). The results demonstrate that the reversible interconversion between Mo4+/Mo6+ at the heterojunction interface effectively promotes interfacial charge transfer. Meanwhile, the formed CoOOH on the photoanode surface significantly enhances surface reaction kinetics and improves photoanode stability. The gradient co-doping of Co and Mo at the interface and surface effectively enhances interfacial charge transfer kinetics and significantly improves structural stability. This well-designed gradient doping strategy provides a viable technical pathway for the rational design and controllable fabrication of high-performance PEC photoanodes for water oxidation.
{"title":"Enhancing Charge Transfer and Photoelectrochemical Performance of BiVO4/WO3 Heterojunction via Gradient Surface/Interface Co-Mo Doping","authors":"Faqi Zhan, Jiahao Qi, Guochang Wen, Bing Wang, Yisi Liu, Chenchen Feng, Yanchun Zhao, Peiqing La","doi":"10.1039/d5ta09911k","DOIUrl":"https://doi.org/10.1039/d5ta09911k","url":null,"abstract":"In the field of photoelectrocatalytic (PEC) water splitting research, BiVO4/WO3 photoanodes exhibit excellent performance in facilitating the separation and transport of photogenerated electron-hole pairs. However, further improving charge transfer efficiency at the heterojunction interface and optimizing the kinetics of water oxidation reactions remain critical challenges. In this study, a Co-BiVO4-Mo/WO3 photoanode was successfully constructed by selectively introducing Mo at the interface and doping Co on the surface of the BiVO4/WO3 heterojunction, enabling precise control over the spatially graded distribution of the two dopants. The resulting photoanode achieved a photocurrent density of 3.423 mA/cm2 at 1.23 V vs. RHE, representing an approximately 1.6 times enhancement compared to the unmodified BiVO4/WO3 heterojunction (2.157 mA/cm2), a 2.3 times higher than relative to pristine BiVO4 (1.508 mA/cm2), and a nearly 3.8 times improvement over pristine WO3 (0.916 mA/cm2). The results demonstrate that the reversible interconversion between Mo4+/Mo6+ at the heterojunction interface effectively promotes interfacial charge transfer. Meanwhile, the formed CoOOH on the photoanode surface significantly enhances surface reaction kinetics and improves photoanode stability. The gradient co-doping of Co and Mo at the interface and surface effectively enhances interfacial charge transfer kinetics and significantly improves structural stability. This well-designed gradient doping strategy provides a viable technical pathway for the rational design and controllable fabrication of high-performance PEC photoanodes for water oxidation.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"89 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122364","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}
Gi Hyo Sim, Chanyong Lee, Janghan Na, Hyeyeon Jung, Changsoo Lee, Minjoong Kim, Ju Hun Park, Young Woo Choi, Jong Hak Kim, Sungyeon Heo, Jae Hun Lee
Colloidal metal oxide nanocrystals offer advantages such as controllable size, shape, and doping, along with excellent solution dispersion, making them promising fillers for anion exchange membranes (AEMs). However, as-synthesized nanocrystals are typically capped with hydrophobic ligands, which limit water uptake and ion conductivity. Here, we address this challenge by employing in situ ligand stripping of highly dispersed CeO2 nanocrystals within a polymer matrix. The ligandcapped nanocrystals are homogeneously distributed in quaternized poly(styrene-b-(ethylene-co-butylene)-b-styrene) (QSEBS) AEMs. Under alkaline conditions (1 M KOH), the ligands are removed in situ within the polymer matrix, transforming the nanocrystals from hydrophobic to hydrophilic. A 6 wt% loading of nanocrystals yields the highest OH -conductivity (139.5 mS cm -1 at 80 ℃) and water electrolysis performance (2.52 A cm -2 at 2.0 V at 50 ℃). The composite membranes also exhibit enhanced alkaline/oxidation stability and mechanical properties, attributed to the stripped CeO2 nanocrystals. Our study provides new insights into the design of mixed matrix AEMs through in situ ligand stripping of highly dispersed nanocrystals.
胶体金属氧化物纳米晶体具有尺寸、形状可控、掺杂可控、溶液分散性好等优点，是极有前景的阴离子交换膜（AEMs）填料。然而，合成的纳米晶体通常被疏水配体覆盖，这限制了水的吸收和离子的电导率。在这里，我们通过在聚合物基质中采用高度分散的CeO2纳米晶体的原位配体剥离来解决这一挑战。配体包盖纳米晶体均匀分布在季铵盐化聚苯乙烯-b-（乙烯-共丁烯）-b-苯乙烯（QSEBS） AEMs中。在碱性条件下（1 M KOH），配体在聚合物基体中被原位去除，使纳米晶体从疏水性转变为亲水性。负载6 wt%的纳米晶体可获得最高的OH -电导率（80℃时为139.5 mS cm -1）和水电解性能（50℃时为2.0 V时为2.52 A cm -2）。由于剥离的CeO2纳米晶体，复合膜还表现出增强的碱性/氧化稳定性和机械性能。我们的研究为通过原位剥离高度分散的纳米晶体配体来设计混合基质AEMs提供了新的见解。
{"title":"In Situ Ligand Stripping of CeO2 Nanocrystals in Anion Exchange Membranes for Enhanced Water Electrolysis","authors":"Gi Hyo Sim, Chanyong Lee, Janghan Na, Hyeyeon Jung, Changsoo Lee, Minjoong Kim, Ju Hun Park, Young Woo Choi, Jong Hak Kim, Sungyeon Heo, Jae Hun Lee","doi":"10.1039/d5ta10039a","DOIUrl":"https://doi.org/10.1039/d5ta10039a","url":null,"abstract":"Colloidal metal oxide nanocrystals offer advantages such as controllable size, shape, and doping, along with excellent solution dispersion, making them promising fillers for anion exchange membranes (AEMs). However, as-synthesized nanocrystals are typically capped with hydrophobic ligands, which limit water uptake and ion conductivity. Here, we address this challenge by employing in situ ligand stripping of highly dispersed CeO2 nanocrystals within a polymer matrix. The ligandcapped nanocrystals are homogeneously distributed in quaternized poly(styrene-b-(ethylene-co-butylene)-b-styrene) (QSEBS) AEMs. Under alkaline conditions (1 M KOH), the ligands are removed in situ within the polymer matrix, transforming the nanocrystals from hydrophobic to hydrophilic. A 6 wt% loading of nanocrystals yields the highest OH -conductivity (139.5 mS cm -1 at 80 ℃) and water electrolysis performance (2.52 A cm -2 at 2.0 V at 50 ℃). The composite membranes also exhibit enhanced alkaline/oxidation stability and mechanical properties, attributed to the stripped CeO2 nanocrystals. Our study provides new insights into the design of mixed matrix AEMs through in situ ligand stripping of highly dispersed nanocrystals.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"9 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122365","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}
Sung Heo, Myung-Jin Lee, Dongwook Lee, Jaehan Lee, Jucheol Park, Seontae Park, Seongyoung Park, Ju Sik Kim
Garnet-type solid electrolytes, such as Li7La3Zr2O12 (LLZO), are promising candidates for next-generation solid-state batteries due to their high ionic conductivity, mechanical stability, and excellent compatibility with lithium metal anodes. However, a major safety concern remains: internal short-circuits caused by lithium dendrite penetration, a mechanism that is not yet fully understood. To address this, we employed a suite of in-situ techniques-including conductive atomic force microscopy (C-AFM), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM) to directly observe the mechanism of lithium plating and propagation in Ta-doped Li6.5La3Zr1.5Ta0.5O12 (LLZTO) solid electrolytes. Our findings reveal that non-uniform current distribution within the LLZTO is the primary driver for lithium dendrite formation. We observed that lithium crystals initially nucleate and grow as discrete islands along the grain boundaries where current is concentrated. These isolated crystals subsequently merge, forming continuous dendritic pathways that lead to shortcircuiting. The growth of these lithium crystals was further confirmed by in-situ electron beam induced current (EBIC) experiments. Based on these insights, we developed a novel C-AFM-based technique to artificially induce lithium dendrite growth from the LLZTO surface, which serves as a powerful diagnostic tool for identifying regions of non-uniform current flow. This work elucidates the fundamental mechanism of lithium dendrite formation and provides a valuable method for assessing the safety and performance of solid-state electrolytes.
{"title":"In-situ investigation of Li permeation through grain boundaries in garnet-based solid electrolyte","authors":"Sung Heo, Myung-Jin Lee, Dongwook Lee, Jaehan Lee, Jucheol Park, Seontae Park, Seongyoung Park, Ju Sik Kim","doi":"10.1039/d5ta09003b","DOIUrl":"https://doi.org/10.1039/d5ta09003b","url":null,"abstract":"Garnet-type solid electrolytes, such as Li7La3Zr2O12 (LLZO), are promising candidates for next-generation solid-state batteries due to their high ionic conductivity, mechanical stability, and excellent compatibility with lithium metal anodes. However, a major safety concern remains: internal short-circuits caused by lithium dendrite penetration, a mechanism that is not yet fully understood. To address this, we employed a suite of in-situ techniques-including conductive atomic force microscopy (C-AFM), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM) to directly observe the mechanism of lithium plating and propagation in Ta-doped Li6.5La3Zr1.5Ta0.5O12 (LLZTO) solid electrolytes. Our findings reveal that non-uniform current distribution within the LLZTO is the primary driver for lithium dendrite formation. We observed that lithium crystals initially nucleate and grow as discrete islands along the grain boundaries where current is concentrated. These isolated crystals subsequently merge, forming continuous dendritic pathways that lead to shortcircuiting. The growth of these lithium crystals was further confirmed by in-situ electron beam induced current (EBIC) experiments. Based on these insights, we developed a novel C-AFM-based technique to artificially induce lithium dendrite growth from the LLZTO surface, which serves as a powerful diagnostic tool for identifying regions of non-uniform current flow. This work elucidates the fundamental mechanism of lithium dendrite formation and provides a valuable method for assessing the safety and performance of solid-state electrolytes.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"76 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129441","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}
Hydrogen is gaining momentum as a clean, high-energy-density alternative to fossil fuels, with green hydrogen production offering a pathway to zero-carbon energy systems. Conventional water splitting, comprising the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode, suffers from the intrinsic sluggishness of the OER a kinetically demanding four-electron process requiring a high overpotential (1.23 V vs. RHE). Replacing the OER with the hydrazine oxidation reaction (HzOR), a thermodynamically favourable process with faster kinetics, can markedly improve energy efficiency in electrolytic hydrogen production. This review focuses on carbon-based electrocatalysts as a sustainable platform for HzOR, with particular attention to their coordination chemistry features. Strategies such as heteroatom doping (N, S, P, B) and incorporation of transition-metal centres (Fe, Co, Ni, Cu) into carbon lattices generate well-defined coordination environments most notably M-N x sites that modulate the electronic structure, enhance hydrazine adsorption, and lower activation barriers. The influence of coordination geometry, ligand field effects, and metalligand orbital interactions on reaction pathways is discussed alongside synthetic approaches, including MOF-derived carbons, which allow atomic-level control over active site distribution. Furthermore, we examine the interplay between interfacial charge transfer and catalytic stability, and highlight the use of theoretical modelling and machine learning to predict and optimise coordination environments. By integrating fundamental coordination chemistry with materials engineering, this review underscores the potential of rationally designed carbonbased catalysts to drive HzOR efficiently, paving the way for scalable, sustainable green hydrogen generation.
{"title":"Carbon-Based Catalysts for Hydrazine Oxidation Reaction: A Promising Low-Energy Route for Hydrogen Generation Beyond Conventional Water Splitting","authors":"Manish Chauhan, Abinaya Shri, Ankita Chaurasiya, Yashmeen Budania, K. Karthikeyan, Shiv Singh","doi":"10.1039/d5ta08656f","DOIUrl":"https://doi.org/10.1039/d5ta08656f","url":null,"abstract":"Hydrogen is gaining momentum as a clean, high-energy-density alternative to fossil fuels, with green hydrogen production offering a pathway to zero-carbon energy systems. Conventional water splitting, comprising the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode, suffers from the intrinsic sluggishness of the OER a kinetically demanding four-electron process requiring a high overpotential (1.23 V vs. RHE). Replacing the OER with the hydrazine oxidation reaction (HzOR), a thermodynamically favourable process with faster kinetics, can markedly improve energy efficiency in electrolytic hydrogen production. This review focuses on carbon-based electrocatalysts as a sustainable platform for HzOR, with particular attention to their coordination chemistry features. Strategies such as heteroatom doping (N, S, P, B) and incorporation of transition-metal centres (Fe, Co, Ni, Cu) into carbon lattices generate well-defined coordination environments most notably M-N x sites that modulate the electronic structure, enhance hydrazine adsorption, and lower activation barriers. The influence of coordination geometry, ligand field effects, and metalligand orbital interactions on reaction pathways is discussed alongside synthetic approaches, including MOF-derived carbons, which allow atomic-level control over active site distribution. Furthermore, we examine the interplay between interfacial charge transfer and catalytic stability, and highlight the use of theoretical modelling and machine learning to predict and optimise coordination environments. By integrating fundamental coordination chemistry with materials engineering, this review underscores the potential of rationally designed carbonbased catalysts to drive HzOR efficiently, paving the way for scalable, sustainable green hydrogen generation.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"51 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146116","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}
Huang-Chin Lin, Yi Chen, Tzu-Hao Hung, Ding-Huei Tsai, Lu-Yu Chueh, Chun-I Chou, Kun-Han Lin, Yung-Tin Pan
Chemical looping integrated with CO2 utilization is an attractive chemical process that can contribute greatly to on-site carbon capture and utilization. To reduce the excess energy consumption, the kinetics of the CO2-splitting half reaction has been revisited on pure iron oxygen carriers. High CO2-splitting rate at a very low temperature of 350 °C is discovered with unambiguous relation to the presence FeO. Through controlled reduction, a nanoporous oxygen carrier enriched with active FeO, capable of 2-dimensional oxide growth with fast kinetics is formed and can be regenerated under cycling conditions of chemical looping reverse water-gas shift model reaction at 500 °C. Over-reduction leads to the formation of low activity metallic Fe that requires additional 100 °C or more to conduct CO2-splitting which deactivates rapidly due to severe sintering. Density functional theory calculations reveal the minimum energy pathway having the dissociation of adsorbed CO2 on Fe surface followed by the spillover of CO to FeO surface for desorption. The findings provide guidance to the design of a reactive iron-based oxygen carrier for low temperature CO2-splitting for all chemical looping carbon capture utilization processes.
{"title":"FeO-Enabled Low-Temperature CO2 -Splitting for Chemical Looping Carbon Utilization","authors":"Huang-Chin Lin, Yi Chen, Tzu-Hao Hung, Ding-Huei Tsai, Lu-Yu Chueh, Chun-I Chou, Kun-Han Lin, Yung-Tin Pan","doi":"10.1039/d5ta07934a","DOIUrl":"https://doi.org/10.1039/d5ta07934a","url":null,"abstract":"Chemical looping integrated with CO<small><sub>2</sub></small> utilization is an attractive chemical process that can contribute greatly to on-site carbon capture and utilization. To reduce the excess energy consumption, the kinetics of the CO<small><sub>2-</sub></small>splitting half reaction has been revisited on pure iron oxygen carriers. High CO<small><sub>2</sub></small>-splitting rate at a very low temperature of 350 °C is discovered with unambiguous relation to the presence FeO. Through controlled reduction, a nanoporous oxygen carrier enriched with active FeO, capable of 2-dimensional oxide growth with fast kinetics is formed and can be regenerated under cycling conditions of chemical looping reverse water-gas shift model reaction at 500 °C. Over-reduction leads to the formation of low activity metallic Fe that requires additional 100 °C or more to conduct CO<small><sub>2</sub></small>-splitting which deactivates rapidly due to severe sintering. Density functional theory calculations reveal the minimum energy pathway having the dissociation of adsorbed CO<small><sub>2</sub></small> on Fe surface followed by the spillover of CO to FeO surface for desorption. The findings provide guidance to the design of a reactive iron-based oxygen carrier for low temperature CO<small><sub>2</sub></small>-splitting for all chemical looping carbon capture utilization processes.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"94 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135486","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}
Haotong Chen, Zilong Han, Zhiyuan Zhang, Yan Li, Lili Yu, Zhilong Zhang, Li Li
Electrochemical nitrate reduction (NO3RR) presents a promising alternative to the conventional Haber-Bosch process for ammonia production. However, developing highly active and stable catalysts that function effectively in a wide pH range remains a challenge. Copper (Cu) is a high-potential electrocatalyst, but still suffers from low activity and instability across wide pH range, especially in acidic conditions, hindering practical applications. Herein, we developed an acid-base dual-immune Cu electrocatalyst by in situ decorating cationic quaternized chitosan (QCS) on Cu nanoparticles, which exhibits outstanding NO3RR activity across a broad pH range, with NH3 yield rate of 1.4, 0.1 and 0.54 mmol h–1 cm–2, selectivity of 96.4%, 86.4% and 91.4%, FE of 96.3%, 95.8% and 96.1%, in acid, neutral, and alkaline condition, respectively. Moreover, it demonstrates high NH3 selectivity and FE over a wide range of NO3– concentrations and good stability across a wide pH range, e.g., >80% FE after ~550 h reaction in strong acid. The experimental results reveal that QCS plays a pluripotent role for the enhanced NO3RR, consisting of promoting the adsorption of NOx– by the positively charged ions, protecting Cu from corrosion, and possessing high stability in highly acidic and alkaline electrolyte. Furthermore, the co-production of NH3 and adipic acid system shows high combined electron efficiency.
{"title":"Acid-Base Dual-Immune Cu Electrocatalyst via Quaternized Chitosan Buffering for pH Universal Nitrate Reduction to Ammonia","authors":"Haotong Chen, Zilong Han, Zhiyuan Zhang, Yan Li, Lili Yu, Zhilong Zhang, Li Li","doi":"10.1039/d5ta09605g","DOIUrl":"https://doi.org/10.1039/d5ta09605g","url":null,"abstract":"Electrochemical nitrate reduction (NO3RR) presents a promising alternative to the conventional Haber-Bosch process for ammonia production. However, developing highly active and stable catalysts that function effectively in a wide pH range remains a challenge. Copper (Cu) is a high-potential electrocatalyst, but still suffers from low activity and instability across wide pH range, especially in acidic conditions, hindering practical applications. Herein, we developed an acid-base dual-immune Cu electrocatalyst by in situ decorating cationic quaternized chitosan (QCS) on Cu nanoparticles, which exhibits outstanding NO3RR activity across a broad pH range, with NH3 yield rate of 1.4, 0.1 and 0.54 mmol h–1 cm–2, selectivity of 96.4%, 86.4% and 91.4%, FE of 96.3%, 95.8% and 96.1%, in acid, neutral, and alkaline condition, respectively. Moreover, it demonstrates high NH3 selectivity and FE over a wide range of NO3– concentrations and good stability across a wide pH range, e.g., >80% FE after ~550 h reaction in strong acid. The experimental results reveal that QCS plays a pluripotent role for the enhanced NO3RR, consisting of promoting the adsorption of NOx– by the positively charged ions, protecting Cu from corrosion, and possessing high stability in highly acidic and alkaline electrolyte. Furthermore, the co-production of NH3 and adipic acid system shows high combined electron efficiency.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"69 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122363","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}
Low-cost, high-activity multifunctional Pt electrocatalysts remain elusive. Under the guidance of a data–knowledge dual-driven approach, Ni, Co, Fe (X), Mn, Cr (Y), and Ga (Z) are quickly determined in a PtXYZ high-entropy alloy system. Ga doping significantly enhances its order at 873 K, while its unit cell undergoes a notable anisotropic lattice strain. Precise Ga doping enables Pt40Ni9Co7Fe10Mn8Cr12Ga14/CNT to achieve trifunctional catalysis with an HER overpotential of 13.6 mV, an OER overpotential of 260 mV, an ORR half-wave potential of 0.94 V, and a bifunctional oxygen potential difference of 0.552 V. In actual devices, it achieves 1 A cm−2 at 2.43 V (stability for 236 h) in overall water splitting, and peak power densities of 123.88 mW cm−2 (for 260 h) and 149.58 mW cm−2 are reached in aqueous/flexible rechargeable zinc–air batteries, respectively. Density functional theory calculations reveal that Ga doping precisely modulates lattice constants and the d-band center, thereby tailoring intermediate adsorption energetics. This design strategy offers a fresh route to high-performance multifunctional PtXYZ high-entropy alloy catalysts.
低成本、高活性的多功能Pt电催化剂仍然难以捉摸。在数据知识双驱动方法的指导下，在PtXYZ高熵合金体系中快速测定了Ni， Co, Fe (X), Mn, Cr (Y)和Ga (Z)。在873 K时，Ga掺杂显著提高了其有序度，同时其晶胞发生了显著的各向异性晶格应变。精确的Ga掺杂使Pt40Ni9Co7Fe10Mn8Cr12Ga14/CNT实现了HER过电位13.6 mV、OER过电位260 mV、ORR半波电位0.94 V、双功能氧电位差0.552 V的三功能催化。在实际设备中，它在2.43 V （236 h的稳定性）下实现了1 A cm - 2的整体水分解，在水/柔性可充电锌-空气电池中分别达到了123.88 mW cm - 2 （260 h）和149.58 mW cm - 2的峰值功率密度。密度泛函理论计算表明，Ga掺杂可以精确地调节晶格常数和d带中心，从而调整中间吸附能量。该设计策略为开发高性能多功能PtXYZ高熵合金催化剂提供了一条新的途径。
{"title":"Data–knowledge dual-driven design of a lattice-strain-controlled L10-PtNiCoFeMnCrGa/CNT multifunctional catalyst","authors":"Xinhui Cao, Zeqi Song, Zhengzheng Bai, Xirui Duan, Liuxiong Luo, Shen Gong, Bing Liu","doi":"10.1039/d5ta09904h","DOIUrl":"https://doi.org/10.1039/d5ta09904h","url":null,"abstract":"Low-cost, high-activity multifunctional Pt electrocatalysts remain elusive. Under the guidance of a data–knowledge dual-driven approach, Ni, Co, Fe (X), Mn, Cr (Y), and Ga (Z) are quickly determined in a PtXYZ high-entropy alloy system. Ga doping significantly enhances its order at 873 K, while its unit cell undergoes a notable anisotropic lattice strain. Precise Ga doping enables Pt<small><sub>40</sub></small>Ni<small><sub>9</sub></small>Co<small><sub>7</sub></small>Fe<small><sub>10</sub></small>Mn<small><sub>8</sub></small>Cr<small><sub>12</sub></small>Ga<small><sub>14</sub></small>/CNT to achieve trifunctional catalysis with an HER overpotential of 13.6 mV, an OER overpotential of 260 mV, an ORR half-wave potential of 0.94 V, and a bifunctional oxygen potential difference of 0.552 V. In actual devices, it achieves 1 A cm<small><sup>−2</sup></small> at 2.43 V (stability for 236 h) in overall water splitting, and peak power densities of 123.88 mW cm<small><sup>−2</sup></small> (for 260 h) and 149.58 mW cm<small><sup>−2</sup></small> are reached in aqueous/flexible rechargeable zinc–air batteries, respectively. Density functional theory calculations reveal that Ga doping precisely modulates lattice constants and the d-band center, thereby tailoring intermediate adsorption energetics. This design strategy offers a fresh route to high-performance multifunctional PtXYZ high-entropy alloy catalysts.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"30 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122362","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}
Per-and polyfluoroalkyl substances (PFAS) persist in water systems due to their extreme chemical stability and weak degradability, demanding treatment approaches that extend beyond simple capture.This review delineates the molecular-to-system framework governing PFAS adsorption, regeneration, and destruction on carbon-based materials under realistic conditions. Mechanistic insights reveal that hydrophobic partitioning, electrostatic steering, and fluorophilic affinity jointly control adsorption, while pore blocking, dissolved organics, and temperature govern short-chain breakthrough and desorption. Advances in nitrogen/fluorine-doped carbons, hierarchical porosity, and hybrid magnetic or electroactive scaffolds enable rapid, selective uptake and multi-cycle regeneration. Coupled destructive pathways-electrochemical, supercritical CO 2 , mechanochemical, and sonochemicalachieve near-complete mineralization and fluoride recovery, paving the way toward circular PFAS management. Integrating adsorption with regeneration and life-cycle evaluation establishes a sustainable, low-carbon paradigm that transforms PFAS remediation from single-use removal to capture-regenerate-destroy-reuse circularity.
{"title":"From capture to circularity: Carbon-based adsorbents bridging adsorption, regeneration, and destruction pathways for sustainable PFAS remediation","authors":"Huawen Hu, Jin Liu, Xuejun Xu, Xiaowen Wang","doi":"10.1039/d5ta09440b","DOIUrl":"https://doi.org/10.1039/d5ta09440b","url":null,"abstract":"Per-and polyfluoroalkyl substances (PFAS) persist in water systems due to their extreme chemical stability and weak degradability, demanding treatment approaches that extend beyond simple capture.This review delineates the molecular-to-system framework governing PFAS adsorption, regeneration, and destruction on carbon-based materials under realistic conditions. Mechanistic insights reveal that hydrophobic partitioning, electrostatic steering, and fluorophilic affinity jointly control adsorption, while pore blocking, dissolved organics, and temperature govern short-chain breakthrough and desorption. Advances in nitrogen/fluorine-doped carbons, hierarchical porosity, and hybrid magnetic or electroactive scaffolds enable rapid, selective uptake and multi-cycle regeneration. Coupled destructive pathways-electrochemical, supercritical CO 2 , mechanochemical, and sonochemicalachieve near-complete mineralization and fluoride recovery, paving the way toward circular PFAS management. Integrating adsorption with regeneration and life-cycle evaluation establishes a sustainable, low-carbon paradigm that transforms PFAS remediation from single-use removal to capture-regenerate-destroy-reuse circularity.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"58 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129439","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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