Ramon Manzorro, Jose M. Montes-Monroy, Carmen Mora Moreno, Lidia E Chinchilla, Ana Belén Belén Hungría Hernandez, José Juan Calvino, Jose Antonio Perez-Omil
Achieving the full potential of ceria-based catalysts relies on maximizing the utilization of the Ce4+/Ce3+ redox couple. This study presents a strategy to synthesize highly efficient catalysts by epitaxially dispersing cerium oxide onto strontium titanate (SrTiO3) nanocubes. Leveraging the structural compatibility between the fluorite (CeO2) and perovskite (SrTiO3) structures, revealed by atomic resolution Scanning Transmission Electron Microscopy, reductive thermal treatments are used to generate two-dimensional (2D) ceria-perovskite nano-overlayers-precisely one unit-cell thick-that uniformly cover the SrTiO3 support. This atomic-scale control results in a catalyst system that achieves 100% cerium redox utilization, exhibiting significantly enhanced reducibility and a stabilized surface compared to bulk ceria. The experimental evidences are corroborated by Density Functional Theory calculations. This work establishes a robust foundation for designing lanthanide-lean catalysts with superior chemical properties by exploring analogous fluorite-perovskite support interfaces.
{"title":"Nanoengineering 2D Ceria-Perovskite Monolayers on SrTiO3 Nanocubes: Structure-Redox Property Relationship","authors":"Ramon Manzorro, Jose M. Montes-Monroy, Carmen Mora Moreno, Lidia E Chinchilla, Ana Belén Belén Hungría Hernandez, José Juan Calvino, Jose Antonio Perez-Omil","doi":"10.1039/d5ta08625f","DOIUrl":"https://doi.org/10.1039/d5ta08625f","url":null,"abstract":"Achieving the full potential of ceria-based catalysts relies on maximizing the utilization of the Ce<small><sup>4+</sup></small>/Ce<small><sup>3+</sup></small> redox couple. This study presents a strategy to synthesize highly efficient catalysts by epitaxially dispersing cerium oxide onto strontium titanate (SrTiO<small><sub>3</sub></small>) nanocubes. Leveraging the structural compatibility between the fluorite (CeO<small><sub>2</sub></small>) and perovskite (SrTiO<small><sub>3</sub></small>) structures, revealed by atomic resolution Scanning Transmission Electron Microscopy, reductive thermal treatments are used to generate two-dimensional (2D) ceria-perovskite nano-overlayers-precisely one unit-cell thick-that uniformly cover the SrTiO<small><sub>3</sub></small> support. This atomic-scale control results in a catalyst system that achieves 100% cerium redox utilization, exhibiting significantly enhanced reducibility and a stabilized surface compared to bulk ceria. The experimental evidences are corroborated by Density Functional Theory calculations. This work establishes a robust foundation for designing lanthanide-lean catalysts with superior chemical properties by exploring analogous fluorite-perovskite support interfaces.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"5 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138970","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}
Lane E. Schultz, Nickolas Gantzler, N. Scott Bobbitt, Dorina F. Sava Gallis, Rémi Dingreville
Metal–organic frameworks (MOFs) are porous crystalline materials with applications in gas capture, drug delivery, and molecular separations. While high-throughput computational screening has traditionally identified promising MOFs, recent advances increasingly harness machine learning to accelerate discovery and screening. Existing optimization methods such as Bayesian optimization (BO) and genetic algorithms often overlook the detailed structure–property relationships critical to MOF performance. Here, we present an optimization workflow that couples graph neural networks (GNNs) with multi-objective BO to enhance MOF discovery and screening. By representing MOFs as graphs embedding atomic- and structural-level features, GNNs capture intricate structure–property correlations, enabling more accurate property predictions than traditional methods relying solely on macroscopic descriptors. Our integrated framework efficiently identifies Pareto-optimal MOF candidates tailored for improved separation of alkanes, alkenes, alcohols, and aromatics, demonstrating the significant advantage of graph-based models in materials optimization workflows.
{"title":"Graph neural network-based multi-objective Bayesian optimization for enhanced screening of metal–organic frameworks with optimal separation performance","authors":"Lane E. Schultz, Nickolas Gantzler, N. Scott Bobbitt, Dorina F. Sava Gallis, Rémi Dingreville","doi":"10.1039/d5ta09133k","DOIUrl":"https://doi.org/10.1039/d5ta09133k","url":null,"abstract":"Metal–organic frameworks (MOFs) are porous crystalline materials with applications in gas capture, drug delivery, and molecular separations. While high-throughput computational screening has traditionally identified promising MOFs, recent advances increasingly harness machine learning to accelerate discovery and screening. Existing optimization methods such as Bayesian optimization (BO) and genetic algorithms often overlook the detailed structure–property relationships critical to MOF performance. Here, we present an optimization workflow that couples graph neural networks (GNNs) with multi-objective BO to enhance MOF discovery and screening. By representing MOFs as graphs embedding atomic- and structural-level features, GNNs capture intricate structure–property correlations, enabling more accurate property predictions than traditional methods relying solely on macroscopic descriptors. Our integrated framework efficiently identifies Pareto-optimal MOF candidates tailored for improved separation of alkanes, alkenes, alcohols, and aromatics, demonstrating the significant advantage of graph-based models in materials optimization workflows.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"45 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139007","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}
Beatrice Ricci, Felix-Cosmin Mocanu, Dimitrios Chatzogiannakis, Victor Fuentes, Ashley Phillip Black-Serra, Benoît Cluzeau, Cécile Tessier, Patrick Bernard, Saiful Islam, M. Rosa Palacín
Olivine-type phosphates LiMnxFe1–xPO4 are attracting increasing interest as positive electrode materials for lithium-ion batteries due to their low cost and good electrochemical performance. However, the effects of the mixed Mn/Fe composition on lithium intercalation and ion transport are not fully characterised, especially in Mn-rich compositions. In this study, the electrochemical, structural and ion transport properties of Mn-rich LiMnxFe1–xPO4 (x = 0.6, 0.7, 0.8) (LMFP) are investigated using a combination of experimental and materials modelling techniques. Considerable asymmetry in charge/discharge profiles is found, which highlights the complexity of the mixed-metal system. An intricate lithium intercalation mechanism is observed, including both solid solution and two-phase regions. While the Fe/Mn cation disorder causes the oxidation to proceed mostly via a solid solution mechanism, the Mn plateau remains associated with a two-phase process. Ab initio simulations indicate that Li-ion diffusion occurs along one-dimensional channels parallel to the crystallographic b-axis following a curved trajectory and find favourable Li/Fe and Li/Mn anti-site defect formation. Analysing the band gaps of the lithiated and delithiated phases revealed that Mn substitution of Fe can improve the electronic conductivity, suggesting asymmetric electronic behaviour.
{"title":"Investigating the asymmetric electrochemical, structural and electronic properties of Mn-rich Li(Mn,Fe)PO4 electrode materials","authors":"Beatrice Ricci, Felix-Cosmin Mocanu, Dimitrios Chatzogiannakis, Victor Fuentes, Ashley Phillip Black-Serra, Benoît Cluzeau, Cécile Tessier, Patrick Bernard, Saiful Islam, M. Rosa Palacín","doi":"10.1039/d5ta10330d","DOIUrl":"https://doi.org/10.1039/d5ta10330d","url":null,"abstract":"Olivine-type phosphates LiMn<small><sub>x</sub></small>Fe<small><sub>1–x</sub></small>PO<small><sub>4</sub></small> are attracting increasing interest as positive electrode materials for lithium-ion batteries due to their low cost and good electrochemical performance. However, the effects of the mixed Mn/Fe composition on lithium intercalation and ion transport are not fully characterised, especially in Mn-rich compositions. In this study, the electrochemical, structural and ion transport properties of Mn-rich LiMn<small><sub>x</sub></small>Fe<small><sub>1–x</sub></small>PO<small><sub>4</sub></small> (x = 0.6, 0.7, 0.8) (LMFP) are investigated using a combination of experimental and materials modelling techniques. Considerable asymmetry in charge/discharge profiles is found, which highlights the complexity of the mixed-metal system. An intricate lithium intercalation mechanism is observed, including both solid solution and two-phase regions. While the Fe/Mn cation disorder causes the oxidation to proceed mostly via a solid solution mechanism, the Mn plateau remains associated with a two-phase process. <em>Ab initio</em> simulations indicate that Li-ion diffusion occurs along one-dimensional channels parallel to the crystallographic b-axis following a curved trajectory and find favourable Li/Fe and Li/Mn anti-site defect formation. Analysing the band gaps of the lithiated and delithiated phases revealed that Mn substitution of Fe can improve the electronic conductivity, suggesting asymmetric electronic behaviour.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"385 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138967","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}
Marta Bordonhos, Rosana V Pinto, Tânia Frade, Bingbing Chen, Farid Nouar, Georges Mouchaham, José R. B. Gomes, Christian Serre, Moisés Luzia Pinto
The microporous MIL-120(Al) MOF has been tested for CO 2 /CH 4 separation. The material has been synthesised in powder form at the kg-scale and shaped into spherical beads without significant loss in adsorption capacity (on average, ca. 7 % for CO 2 ). MIL-120(Al) is more selective towards CO 2 (IAST mean selectivity of 7.4-31.4 between 0.1-10 bar), showing a good adsorption capacity and a moderate enthalpy of adsorption (-34 to -53 kJ•mol -1 in the low loading regime). Molecular simulation studies have revealed a probable rotation of the μ 2 -OH groups with increasing CO 2 pressure altering the CO 2 adsorption capacity at high pressures. Breakthrough experiments have confirmed the CO 2 /CH 4 selectivity of MIL-120(Al) and have shown that the material can retain its original adsorption separation performance after regeneration following consecutive cycles (10 cycles) and prolonged exposure to high amounts of water vapour, demonstrating the potential of this MOF for biogas upgrading.Results and DiscussionAdsorption performance under dry conditions MIL-120(Al) has been synthesised at the kilogram scale using an environmentally friendly, scalable and high-yield synthesis method, following a previous protocol developed by some of us. 8 The characterisation details, provided in Section S1 in the Supporting Information (SI), confirm the structural integrity, porosity and thermal stability of the material. Single-component CO 2 and CH 4 adsorption isotherms measured at 25 °C for the powder form of MIL-120(Al) are represented in Figure 2A. Additional details are described in the Experimental section and in Section S2.A in the SI. The experimental data and corresponding isotherm model fittings are reported in Tables S2 andS3 in the SI. As expected, MIL-120(Al) shows a higher adsorption capacity for CO 2 than for CH 4 in the entire pressure range studied, suggesting the potential of this MOF for
{"title":"Towards Sustainable Biogas Upgrading: MIL-120(Al) as a Cost-Effective Water Stable MOF for CO2 /CH4 Separation","authors":"Marta Bordonhos, Rosana V Pinto, Tânia Frade, Bingbing Chen, Farid Nouar, Georges Mouchaham, José R. B. Gomes, Christian Serre, Moisés Luzia Pinto","doi":"10.1039/d5ta07225e","DOIUrl":"https://doi.org/10.1039/d5ta07225e","url":null,"abstract":"The microporous MIL-120(Al) MOF has been tested for CO 2 /CH 4 separation. The material has been synthesised in powder form at the kg-scale and shaped into spherical beads without significant loss in adsorption capacity (on average, ca. 7 % for CO 2 ). MIL-120(Al) is more selective towards CO 2 (IAST mean selectivity of 7.4-31.4 between 0.1-10 bar), showing a good adsorption capacity and a moderate enthalpy of adsorption (-34 to -53 kJ•mol -1 in the low loading regime). Molecular simulation studies have revealed a probable rotation of the μ 2 -OH groups with increasing CO 2 pressure altering the CO 2 adsorption capacity at high pressures. Breakthrough experiments have confirmed the CO 2 /CH 4 selectivity of MIL-120(Al) and have shown that the material can retain its original adsorption separation performance after regeneration following consecutive cycles (10 cycles) and prolonged exposure to high amounts of water vapour, demonstrating the potential of this MOF for biogas upgrading.Results and DiscussionAdsorption performance under dry conditions MIL-120(Al) has been synthesised at the kilogram scale using an environmentally friendly, scalable and high-yield synthesis method, following a previous protocol developed by some of us. 8 The characterisation details, provided in Section S1 in the Supporting Information (SI), confirm the structural integrity, porosity and thermal stability of the material. Single-component CO 2 and CH 4 adsorption isotherms measured at 25 °C for the powder form of MIL-120(Al) are represented in Figure 2A. Additional details are described in the Experimental section and in Section S2.A in the SI. The experimental data and corresponding isotherm model fittings are reported in Tables S2 andS3 in the SI. As expected, MIL-120(Al) shows a higher adsorption capacity for CO 2 than for CH 4 in the entire pressure range studied, suggesting the potential of this MOF for","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"24 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138969","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}
Di Sun, Xinru Lin, Zonghe Yu, Xingbin Li, Peng Yan, Yang Wang, Yuzhong Gao
The development of materials with dual degradation/antibacterial abilities is a promising strategy for environmental governance. In this study, a sharp cone warhammer-like all solid-state Z-scheme MIL-88A/Ag/MIL-88B (MAM) were prepared through nano-confined encapsulation and in situ semi-transformation strategies. This method synthesizes mesoporous MIL-88B, and then encapsulates silver nanoparticles (Ag NPs) in the pores of MIL-88B through nano-confined encapsulation. Through controllable in situ disassembly and reconstruction, the conical prismatic MIL88A was grown on the surface of Ag/MIL-88B to form MAM without additional Fe source. The material not only significantly inhibits the recombination of electron-hole pairs through strong interfacial couple, but also greatly enhances the SPR and electron channel interaction of Ag NPs, which significantly improves the light absorption and charge transport efficiency. The nanoconfinement and transformation processes simultaneously increase the pore volume and specific surface area of the material, thereby improving its adsorption ability. Its unique conical mace shape not only facilitates the exposure of more active site, but also facilitates the penetration of bacterial membranes. The MAM-30 showed excellent removal ability of meloxicam (MLX) under visible light by adsorption-photocatalysis (96.08%, 60 min). T.E.S.T. and wheat growth experiment indicated that the toxicity of MLX solution was significantly reduced after photocatalysis treatment. Meantime, the MAM-30 can completely inactivate E. coli, S. aureus, and MRSA within 60 min. The mechanisms of adsorption, degradation and antibacterial properties were analyzed. This paper provides new ideas for the development of photocatalytic degradation of pollutants and antibacterial materials based on metal-organic framework materials.
{"title":"Developing a sharp cone warhammer-like MIL-88A/Ag/MIL-88B Z-scheme heterojunction by controlled in situ semi-conversion strategy: Adsorption-photodegradation of meloxicam and antibacterial activity","authors":"Di Sun, Xinru Lin, Zonghe Yu, Xingbin Li, Peng Yan, Yang Wang, Yuzhong Gao","doi":"10.1039/d5ta09483f","DOIUrl":"https://doi.org/10.1039/d5ta09483f","url":null,"abstract":"The development of materials with dual degradation/antibacterial abilities is a promising strategy for environmental governance. In this study, a sharp cone warhammer-like all solid-state Z-scheme MIL-88A/Ag/MIL-88B (MAM) were prepared through nano-confined encapsulation and in situ semi-transformation strategies. This method synthesizes mesoporous MIL-88B, and then encapsulates silver nanoparticles (Ag NPs) in the pores of MIL-88B through nano-confined encapsulation. Through controllable in situ disassembly and reconstruction, the conical prismatic MIL88A was grown on the surface of Ag/MIL-88B to form MAM without additional Fe source. The material not only significantly inhibits the recombination of electron-hole pairs through strong interfacial couple, but also greatly enhances the SPR and electron channel interaction of Ag NPs, which significantly improves the light absorption and charge transport efficiency. The nanoconfinement and transformation processes simultaneously increase the pore volume and specific surface area of the material, thereby improving its adsorption ability. Its unique conical mace shape not only facilitates the exposure of more active site, but also facilitates the penetration of bacterial membranes. The MAM-30 showed excellent removal ability of meloxicam (MLX) under visible light by adsorption-photocatalysis (96.08%, 60 min). T.E.S.T. and wheat growth experiment indicated that the toxicity of MLX solution was significantly reduced after photocatalysis treatment. Meantime, the MAM-30 can completely inactivate E. coli, S. aureus, and MRSA within 60 min. The mechanisms of adsorption, degradation and antibacterial properties were analyzed. This paper provides new ideas for the development of photocatalytic degradation of pollutants and antibacterial materials based on metal-organic framework materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"57 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138968","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}
Siyuan Cheng, Ye Jiang, Guomeng Zhang, Yanan Liu, Xiao Dou, Xin Sun
A set of Mn–Ce composite catalysts with three-dimensionally ordered macroporous (3DOM) structures were synthesized via the PMMA colloidal crystal templating approach. Among them, 3DOM-Mn1Ce2 exhibited superior toluene oxidation performance, achieving 90% conversion at 244 °C, along with exceptional stability, reusability, and water resistance. XRD and SEM results confirmed the formation of a solid solution with a well-defined 3DOM structure. 3DOM-Mn1Ce2 possessed the largest BET surface area (61.02 m2 g−1) and an optimal pore structure. The intense synergistic effect between manganese and cerium accelerated the redox cycling between Mn3+/Mn4+ and Ce3+/Ce4+ pairs, and significantly enhanced the mobility of lattice oxygen and the low-temperature reducibility of the catalyst. The relative contributions of physicochemical properties to the catalytic activity for toluene oxidation were quantified by multiple linear regression (MLR) combined with principal component analysis (PCA), revealing that the Mn4+/Mn ratio exerted the most significant influence. The comparison of toluene-TPD and toluene-TPSR results on 3DOM and bulk Mn1Ce2 catalysts revealed that the 3DOM structure significantly enhances toluene adsorption and activation. In situ DRIFTS results revealed that the catalytic oxidation of toluene over 3DOM-Mn1Ce2 followed the Mars–van Krevelen (MvK) mechanism. The catalytic reaction pathway was proposed, identifying the cleavage of aromatic CC bonds in the benzoate intermediate as the rate-determining step.
{"title":"Three-dimensional ordered macroporous Mn–Ce composite oxide catalysts with excellent low-temperature toluene oxidation performance: synergistic effect and reaction mechanism","authors":"Siyuan Cheng, Ye Jiang, Guomeng Zhang, Yanan Liu, Xiao Dou, Xin Sun","doi":"10.1039/d5ta09295g","DOIUrl":"https://doi.org/10.1039/d5ta09295g","url":null,"abstract":"A set of Mn–Ce composite catalysts with three-dimensionally ordered macroporous (3DOM) structures were synthesized <em>via</em> the PMMA colloidal crystal templating approach. Among them, 3DOM-Mn1Ce2 exhibited superior toluene oxidation performance, achieving 90% conversion at 244 °C, along with exceptional stability, reusability, and water resistance. XRD and SEM results confirmed the formation of a solid solution with a well-defined 3DOM structure. 3DOM-Mn1Ce2 possessed the largest BET surface area (61.02 m<small><sup>2</sup></small> g<small><sup>−1</sup></small>) and an optimal pore structure. The intense synergistic effect between manganese and cerium accelerated the redox cycling between Mn<small><sup>3+</sup></small>/Mn<small><sup>4+</sup></small> and Ce<small><sup>3+</sup></small>/Ce<small><sup>4+</sup></small> pairs, and significantly enhanced the mobility of lattice oxygen and the low-temperature reducibility of the catalyst. The relative contributions of physicochemical properties to the catalytic activity for toluene oxidation were quantified by multiple linear regression (MLR) combined with principal component analysis (PCA), revealing that the Mn<small><sup>4+</sup></small>/Mn ratio exerted the most significant influence. The comparison of toluene-TPD and toluene-TPSR results on 3DOM and bulk Mn1Ce2 catalysts revealed that the 3DOM structure significantly enhances toluene adsorption and activation. <em>In situ</em> DRIFTS results revealed that the catalytic oxidation of toluene over 3DOM-Mn1Ce2 followed the Mars–van Krevelen (MvK) mechanism. The catalytic reaction pathway was proposed, identifying the cleavage of aromatic C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>C bonds in the benzoate intermediate as the rate-determining step.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"35 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139006","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}
Zareen Zuhra, Saba Sharafat, Muhammad Ahmad, Shafqat Ali, Zhang Zhaowei
Correction for ‘Metal–organic framework applications for microplastic remediation: exploring pathways and future potential’ by Zareen Zuhra et al., J. Mater. Chem. A, 2025, 13, 9619–9642, https://doi.org/10.1039/D4TA07876D.
Changzun Jiang, Yanting Chen, Wentao Yuan, Qianqian Li, Zhen Li
Dye/polymer carbon nitride (PCN) composite systems demonstrate considerable promise for photocatalytic hydrogen evolution (PHE), owing to their extensive spectral absorption range and enhanced charge separation efficiency. However, severe charge recombination, often arising from the inherent molecular structure of organic dyes and their consequent aggregation tendencies, remains a critical issue, thereby presenting a major challenge in modulating electronic processes through the extension of dye carrier lifetimes. Herein, this study employs integrated experimental and theoretical approaches to elucidate the impact of the bridge mode (conjugated versus nonconjugated) between electron donor (D) and acceptor (A) moieties on the aggregation behavior, recombination processes, and photocatalytic performance of dyes. Key findings reveal that the nonconjugated bridge of alkyl chains can efficiently hinder non-radiative transitions and charge recombination by twisted molecular conformations with suppressed intermolecular π-π interactions, thereby facilitating charge carrier transport. Consequently, organic dyes with nonconjugated bridges exhibit superior exciton dissociation and charge transport, which results in a significantly enhanced HER of 859.47 μmol h -1, representing a more than two-fold increase over that of the conjugation-linked analogue dye (401.31 μmol h -1 ). This work establishes bridge engineering as a powerful molecular-level strategy to control aggregation and charge recombination in organic photosensitizers, opening new avenues for designing highly efficient photocatalytic materials.
染料/聚合物氮化碳（PCN）复合体系由于其广泛的光谱吸收范围和增强的电荷分离效率，在光催化析氢（PHE）方面表现出相当大的前景。然而，由于有机染料固有的分子结构及其随之产生的聚集倾向，严重的电荷重组仍然是一个关键问题，因此，通过延长染料载流子寿命来调节电子过程是一个重大挑战。本研究采用实验和理论相结合的方法来阐明电子供体(D)和受体(A)之间的桥模式（共轭与非共轭）对染料的聚集行为、重组过程和光催化性能的影响。主要研究结果表明，烷基链的非共轭桥可以有效地抑制分子间π-π相互作用，从而抑制扭曲分子构象的非辐射跃迁和电荷重组，从而促进载流子的传输。因此，具有非共轭桥的有机染料具有较好的激子解离和电荷输运能力，其she值显著提高至859.47 μmol h -1，比共轭连接的类似染料（401.31 μmol h -1）提高了两倍以上。本研究建立了桥梁工程作为控制有机光敏剂聚集和电荷重组的强大分子水平策略，为设计高效光催化材料开辟了新的途径。
{"title":"Modulating Molecular Aggregates via Nonconjugated Bridges for Enhanced Photocatalytic Hydrogen Evolution","authors":"Changzun Jiang, Yanting Chen, Wentao Yuan, Qianqian Li, Zhen Li","doi":"10.1039/d5ta09516f","DOIUrl":"https://doi.org/10.1039/d5ta09516f","url":null,"abstract":"Dye/polymer carbon nitride (PCN) composite systems demonstrate considerable promise for photocatalytic hydrogen evolution (PHE), owing to their extensive spectral absorption range and enhanced charge separation efficiency. However, severe charge recombination, often arising from the inherent molecular structure of organic dyes and their consequent aggregation tendencies, remains a critical issue, thereby presenting a major challenge in modulating electronic processes through the extension of dye carrier lifetimes. Herein, this study employs integrated experimental and theoretical approaches to elucidate the impact of the bridge mode (conjugated versus nonconjugated) between electron donor (D) and acceptor (A) moieties on the aggregation behavior, recombination processes, and photocatalytic performance of dyes. Key findings reveal that the nonconjugated bridge of alkyl chains can efficiently hinder non-radiative transitions and charge recombination by twisted molecular conformations with suppressed intermolecular π-π interactions, thereby facilitating charge carrier transport. Consequently, organic dyes with nonconjugated bridges exhibit superior exciton dissociation and charge transport, which results in a significantly enhanced HER of 859.47 μmol h -1, representing a more than two-fold increase over that of the conjugation-linked analogue dye (401.31 μmol h -1 ). This work establishes bridge engineering as a powerful molecular-level strategy to control aggregation and charge recombination in organic photosensitizers, opening new avenues for designing highly efficient photocatalytic materials.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"295 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139008","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}
Alessandro Tabussi, Stamatis K. Serviou, Miroslav Medved, Vítězslav Hrubý, Juraj Filo, Petr Lazar, Marek Cigáň, Demetrios D. Chronopoulos, Michal Otyepka, Christoforos G Kokotos
Carbon-based materials have been widely applied as metal-free and effective photochemical promoters or catalysts for organic transformations, significantly advancing synthetic chemistry and enhancing the sustainability of the reactions. In this study, fluorographene (FG) was successfully employed as an efficient two-dimensional and non-metal photochemical promoter for the selective aerobic oxidation of sulfides to the corresponding sulfoxides in methanol under blue light at 456 nm and air as the oxidant. The application of the aforementioned protocol in a broad range of organic sulfides provided the corresponding sulfoxides in moderate to excellent yields. The catalytic mechanism was elucidated by the performance of several control experiments and theoretical calculations, confirming the predominant roles of singlet oxygen and superoxide anions for the successful oxidation of sulfides.
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Herein, we report a nickel-molybdenum carbide-based composite (NIMOC) catalyst, by physically mixing Ni/NC and MoC/NC serving as the preferential CO evolution (PCE) unit and preferential H2 evolution (PHE) one, respectively, to enable efficient electrochemical CO2 reduction reaction (eCO2RR) to syngas with accurately adjustable CO/H2 ratio that satisfies the requirements of downstream applications of syngas, besides to avoid the unfavorable interaction between the dual sites of Ni for CO evolution reaction (CER) and MoC for H2 evolution reaction (HER) of the supported bifunctional Ni-MoC/NC catalyst. This work not only generates an efficient eCO2RR catalyst for syngas production, but also unveils a new and promising PCE-PHE composite catalyst concept for eCO2RR to syngas with required CO/H2 ratio for the downstream transformations, in which the PCE unit mainly facilitates eCO2RR to CO but allows the HER reaction to happen whereas the PHE unit mainly catalyzes HER but allows the eCO2RR to CO to take place.
{"title":"Nickel-molybdenum carbide-based composite catalyst enables CO2 electroreduction to syngas with accurately adjustable CO/H2 ratio","authors":"Zhongkui Zhao, Chaofan Zhang, Boyuan Miao","doi":"10.1039/d5ta09912a","DOIUrl":"https://doi.org/10.1039/d5ta09912a","url":null,"abstract":"Herein, we report a nickel-molybdenum carbide-based composite (NIMOC) catalyst, by physically mixing Ni/NC and MoC/NC serving as the preferential CO evolution (PCE) unit and preferential H2 evolution (PHE) one, respectively, to enable efficient electrochemical CO2 reduction reaction (eCO2RR) to syngas with accurately adjustable CO/H2 ratio that satisfies the requirements of downstream applications of syngas, besides to avoid the unfavorable interaction between the dual sites of Ni for CO evolution reaction (CER) and MoC for H2 evolution reaction (HER) of the supported bifunctional Ni-MoC/NC catalyst. This work not only generates an efficient eCO2RR catalyst for syngas production, but also unveils a new and promising PCE-PHE composite catalyst concept for eCO2RR to syngas with required CO/H2 ratio for the downstream transformations, in which the PCE unit mainly facilitates eCO2RR to CO but allows the HER reaction to happen whereas the PHE unit mainly catalyzes HER but allows the eCO2RR to CO to take place.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"107 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129505","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}
![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
C bonds in the benzoate intermediate as the rate-determining step.
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