Irreversible dissolution of redox-active transition metals during the oxygen evolution reaction remains a major challenge in developing durable water electrolysis catalysts, particularly for Fe-containing spinel oxides. Despite strategies to mitigate Fe dissolution, its atomistic pathway and mechanism remain unclear. Here, we combine static and dynamic ab initio modeling with electrochemical tests to investigate Fe dissolution in NiFe2O4 and CoFe2O4 spinels. Instead of viewing Fe instability as an intrinsic property, we show that it arises from bond strength competition within the M–O–Fe (M = Ni or Co) linkages. A stronger M–O bond (as in Co–O) weakens the adjacent Fe–O bond under electrochemical bias, making Fe dissolution more favorable in CoFe2O4 than that in NiFe2O4. Such asymmetric bond competition leads to enhanced Fe dissolution while simultaneously facilitating surface reconstruction and catalyst deterioration. This work establishes bond competition as a decisive descriptor for metal dissolution, offering practical guidelines for designing stable OER catalysts.
在析氧反应中，氧化还原活性过渡金属的不可逆溶解仍然是开发耐用水电解催化剂的主要挑战，特别是含铁尖晶石氧化物。尽管有减缓铁溶解的策略，但其原子途径和机制仍不清楚。本文将静态和动态从头算模型与电化学测试相结合，研究了Fe在NiFe2O4和CoFe2O4尖晶石中的溶解。我们没有将铁的不稳定性视为一种内在性质，而是表明它是由M - o - Fe （M = Ni或Co）键内的键强度竞争引起的。在电化学偏压作用下，较强的M-O键（如Co-O）削弱了邻近的Fe - o键，使得Fe在CoFe2O4中的溶解比在NiFe2O4中的溶解更有利。这种不对称键竞争导致Fe溶解增强，同时促进表面重构和催化剂劣化。这项工作建立了键竞争作为金属溶解的决定性描述符，为设计稳定的OER催化剂提供了实用指南。
{"title":"Bond Competition in Iron Dissolution from Spinel Oxides during Water Oxidation","authors":"Shuhao Wang,Sicheng Wu,Kamran Dastafkan,Huihui Li,Qian Sun,Chengli Rong,Yan Nie,Qiang Zhang,Chuan Zhao","doi":"10.1021/acs.jpclett.5c03328","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03328","url":null,"abstract":"Irreversible dissolution of redox-active transition metals during the oxygen evolution reaction remains a major challenge in developing durable water electrolysis catalysts, particularly for Fe-containing spinel oxides. Despite strategies to mitigate Fe dissolution, its atomistic pathway and mechanism remain unclear. Here, we combine static and dynamic ab initio modeling with electrochemical tests to investigate Fe dissolution in NiFe2O4 and CoFe2O4 spinels. Instead of viewing Fe instability as an intrinsic property, we show that it arises from bond strength competition within the M–O–Fe (M = Ni or Co) linkages. A stronger M–O bond (as in Co–O) weakens the adjacent Fe–O bond under electrochemical bias, making Fe dissolution more favorable in CoFe2O4 than that in NiFe2O4. Such asymmetric bond competition leads to enhanced Fe dissolution while simultaneously facilitating surface reconstruction and catalyst deterioration. This work establishes bond competition as a decisive descriptor for metal dissolution, offering practical guidelines for designing stable OER catalysts.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"292 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-02DOI: 10.1021/acs.jpclett.5c03949
Verena Müller,Anna-Laurine Gaus,Daniel Hüger,Julian Picker,Christof Neumann,Max von Delius,Andrey Turchanin
We report on the self-assembly of linear three-ring aromatic thiols on Au(111)/mica substrates. Our study examines terphenylthiol (TPT) derivatives with distinct terminal groups −F (FTPT), −CF3 (CF3TPT) and −NO2 (NTPT) as well as a pyridinebiphenyl (PyBPT) compound. Using complementary surface science techniques─X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and scanning tunneling microscopy (STM)─we elucidate the structural properties of the resulting self-assembled monolayers (SAMs). The TPT, FTPT, CF3TPT and PyBPT molecules form densely packed SAMs with hexagonal unit cells exhibiting an area of 21.55 Å2 per molecule. For the NTPT SAM, two different molecular arrangements were observed to coexist: a hexagonal structure and a squared structure, with areas per molecule of 21.55 and 42.25 Å2, respectively.
{"title":"Self-Assembly of Linear Three-Ring Aromatic Thiols on Au(111)","authors":"Verena Müller,Anna-Laurine Gaus,Daniel Hüger,Julian Picker,Christof Neumann,Max von Delius,Andrey Turchanin","doi":"10.1021/acs.jpclett.5c03949","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03949","url":null,"abstract":"We report on the self-assembly of linear three-ring aromatic thiols on Au(111)/mica substrates. Our study examines terphenylthiol (TPT) derivatives with distinct terminal groups −F (FTPT), −CF3 (CF3TPT) and −NO2 (NTPT) as well as a pyridinebiphenyl (PyBPT) compound. Using complementary surface science techniques─X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), and scanning tunneling microscopy (STM)─we elucidate the structural properties of the resulting self-assembled monolayers (SAMs). The TPT, FTPT, CF3TPT and PyBPT molecules form densely packed SAMs with hexagonal unit cells exhibiting an area of 21.55 Å2 per molecule. For the NTPT SAM, two different molecular arrangements were observed to coexist: a hexagonal structure and a squared structure, with areas per molecule of 21.55 and 42.25 Å2, respectively.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"93 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two-dimensional (2D) Dion–Jacobson (DJ)-phase tin-based perovskites show great promise for field-effect transistors (FETs) due to their excellent charge transport properties and structural stability. However, the limited variety of diammonium cations has hindered their further development in electronic devices. In this work, we synthesized a 2D DJ-phase tin perovskite, 3AMPYSnI4, using asymmetric diammonium cation 3-(aminomethyl)pyridinium (3AMPY2+). Single-crystal analysis confirms a typical DJ-phase structure with zigzag-stacked inorganic layers. The 3AMPYSnI4 thin film is polycrystalline without a preferred orientation, exhibiting a high absorption coefficient (∼105 cm–1) and p-type nature. The 3AMPYSnI4 FETs show typical p-type transport behavior with a maximum hole mobility of 3.12 × 10–3 cm2 V–1 s–1 and demonstrate good operational stability. Moreover, under 460 nm illumination, the device achieves a responsivity of 1.20 × 102 A/W and a specific detectivity of 1.46 × 1012 Jones, highlighting its potential for visible-light detection. This study provides a new direction for developing 2D DJ-phase perovskites and their applications in high-performance optoelectronic devices.
{"title":"Two-Dimensional Dion–Jacobson-Phase Tin Perovskite Using Heteroaromatic Diammonium Cations for Phototransistors","authors":"Xinyue Wang,Tingting Dai,Bin Liu,Ting Liang,Zhidong Lou,Dan Li,Yufeng Hu,Yanbing Hou,Aiwei Tang,Feng Teng","doi":"10.1021/acs.jpclett.5c03760","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03760","url":null,"abstract":"Two-dimensional (2D) Dion–Jacobson (DJ)-phase tin-based perovskites show great promise for field-effect transistors (FETs) due to their excellent charge transport properties and structural stability. However, the limited variety of diammonium cations has hindered their further development in electronic devices. In this work, we synthesized a 2D DJ-phase tin perovskite, 3AMPYSnI4, using asymmetric diammonium cation 3-(aminomethyl)pyridinium (3AMPY2+). Single-crystal analysis confirms a typical DJ-phase structure with zigzag-stacked inorganic layers. The 3AMPYSnI4 thin film is polycrystalline without a preferred orientation, exhibiting a high absorption coefficient (∼105 cm–1) and p-type nature. The 3AMPYSnI4 FETs show typical p-type transport behavior with a maximum hole mobility of 3.12 × 10–3 cm2 V–1 s–1 and demonstrate good operational stability. Moreover, under 460 nm illumination, the device achieves a responsivity of 1.20 × 102 A/W and a specific detectivity of 1.46 × 1012 Jones, highlighting its potential for visible-light detection. This study provides a new direction for developing 2D DJ-phase perovskites and their applications in high-performance optoelectronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"216 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-01DOI: 10.1021/acs.jpclett.5c03600
Honggang Zhu,Yongtao Gao,Pinyi Zeng,Bin You,Lihua Qian,Chengliang Lu
Enhancing the oxygen evolution capacity of materials constitutes a pivotal strategy for augmenting electrochemical catalytic efficacy. Here we report enhanced oxygen evolution reaction (OER) activity in Sr2Ir1–xFexO4. The incorporation of Fe modifies the electronic structure of Ir and stabilizes its high oxidation state, facilitating the stabilization of reaction intermediates and accelerating the kinetics of the OER. Specifically, Sr2Ir0.91Fe0.09O4 requires only 264 mV to reach 10 mA cm–2 in 1 M KOH, exhibits a Tafel slope of as low as 52.9 mV dec–1, and delivers a 1.9-fold increase in electrochemically active surface area (ECSA). The catalytic activity of Sr2Ir1–xFexO4 samples is enhanced through electronic structure alteration of substituting elements, increasing the active site reactivity and oxygen evolution capability. This study provides insights into the design of an OER catalyst through 3d and 5d metal synergies, advancing electrocatalyst development.
提高材料的析氧能力是提高电化学催化效能的关键策略。在这里，我们报道了Sr2Ir1-xFexO4的析氧反应（OER）活性增强。Fe的加入改变了Ir的电子结构，稳定了其高氧化态，促进了反应中间体的稳定，加速了OER的动力学。具体来说，Sr2Ir0.91Fe0.09O4在1 M KOH下仅需264 mV即可达到10 mA cm-2， Tafel斜率低至52.9 mV dec1，电化学活性表面积（ECSA）增加1.9倍。Sr2Ir1-xFexO4样品的催化活性通过取代元素的电子结构改变而增强，增加了活性位点的反应活性和析氧能力。该研究通过3d和5d金属协同作用为OER催化剂的设计提供了见解，推动了电催化剂的发展。
{"title":"Enhancing the Oxygen Evolution Reaction Activity via Non-Noble-Metal Substitution in Spin–Orbit Coupled Sr2IrO4","authors":"Honggang Zhu,Yongtao Gao,Pinyi Zeng,Bin You,Lihua Qian,Chengliang Lu","doi":"10.1021/acs.jpclett.5c03600","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03600","url":null,"abstract":"Enhancing the oxygen evolution capacity of materials constitutes a pivotal strategy for augmenting electrochemical catalytic efficacy. Here we report enhanced oxygen evolution reaction (OER) activity in Sr2Ir1–xFexO4. The incorporation of Fe modifies the electronic structure of Ir and stabilizes its high oxidation state, facilitating the stabilization of reaction intermediates and accelerating the kinetics of the OER. Specifically, Sr2Ir0.91Fe0.09O4 requires only 264 mV to reach 10 mA cm–2 in 1 M KOH, exhibits a Tafel slope of as low as 52.9 mV dec–1, and delivers a 1.9-fold increase in electrochemically active surface area (ECSA). The catalytic activity of Sr2Ir1–xFexO4 samples is enhanced through electronic structure alteration of substituting elements, increasing the active site reactivity and oxygen evolution capability. This study provides insights into the design of an OER catalyst through 3d and 5d metal synergies, advancing electrocatalyst development.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"2011 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Safe and efficient hydrogen (H2) storage remains a key challenge for a carbon-neutral energy future. Clathrate hydrates, ice-like lattices of hydrogen-bonded water, provide a sustainable platform for solid-state H2 storage under moderate conditions; however, the molecular interactions governing their stability remain poorly understood. Using powder X-ray diffraction and Raman spectroscopy, we demonstrate the first H2-isoxazole (ISXZ) hydrate and identify a C4–H···O host–guest linkage that stabilizes the structure II lattice. Comparative studies on pure ISXZ and N2-ISXZ hydrates reveal that even when small cages are vacant or occupied by bulkier N2, ISXZ maintains lattice stability through this interaction. These findings establish ISXZ as a prototype heteroaromatic promoter and highlight C–H···O bonding as a general motif for designing next-generation gas-storage materials.
{"title":"Isoxazole-Stabilized Clathrate Hydrate for Hydrogen Storage","authors":"Gaurav Vishwakarma,Emmerson Hondo,Kan Jeenmuang,Rajnish Kumar,Praveen Linga","doi":"10.1021/acs.jpclett.5c03690","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03690","url":null,"abstract":"Safe and efficient hydrogen (H2) storage remains a key challenge for a carbon-neutral energy future. Clathrate hydrates, ice-like lattices of hydrogen-bonded water, provide a sustainable platform for solid-state H2 storage under moderate conditions; however, the molecular interactions governing their stability remain poorly understood. Using powder X-ray diffraction and Raman spectroscopy, we demonstrate the first H2-isoxazole (ISXZ) hydrate and identify a C4–H···O host–guest linkage that stabilizes the structure II lattice. Comparative studies on pure ISXZ and N2-ISXZ hydrates reveal that even when small cages are vacant or occupied by bulkier N2, ISXZ maintains lattice stability through this interaction. These findings establish ISXZ as a prototype heteroaromatic promoter and highlight C–H···O bonding as a general motif for designing next-generation gas-storage materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"82 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Despite outstanding catalytic potential, stabilizing single-atom-thick metallenes presents a fundamental challenge in materials design. Through first-principles structure search calculations, we have identified a novel two-dimensional (2D) Janus nanomaterial Pt(111)@CP, in which the single atomic Pt (111) metallene layer serves as one exposed surface, effectively stabilized by coupling with the robust nonmetallic CP framework composed of sp3-hybridized C atoms and sp3-hybridized P atoms possessing lone pair electrons. The unique Pt(111)@CP nanostructure can exhibit excellent dynamic, thermodynamic, mechanical and thermal stability, as well as metallic conductivity. Additionally, it can demonstrate considerably high HER catalytic performance, with both sides playing important roles. Remarkably, it can maintain high HER catalytic activity over a wide range of θH* coverages. Its active site density can reach 1.022 × 1016 sites/cm2, exceeding many reported materials and even state-of-the-art Pt. Further, by substituting Pt atoms with other Group VIII transition metals, we derived a series of novel 2D Janus TM(111)@CP monolayers (TM = Ru, Rh, Pd, Os and Ir) from the Pt(111)@CP structure. All five newly designed TM(111)@CP monolayers featuring the TM (111) metallene surfaces demonstrate high stability and metallic conductivity. They also maintain high HER catalytic activity over a wide range of θH* coverages, with active site densities reaching 1.473 × 1015 to 9.888 × 1015 sites/cm2, comparable to or exceeding the precious metal Pt. The relevant catalytic mechanisms are analyzed. This study presents an innovative strategy for stabilizing metallenes and developing high-performance metallene-related electrocatalysts for HER and even broader energy conversion applications.
{"title":"Stabilizing Atomically Thin Pt (111) Metallene and Its Derivatives by Coupling with a Unique CP Nonmetallic Framework for Efficient HER Catalysis","authors":"Ziyue Cui, Qian Tang, Mingyue Lv, Guangtao Yu, Wei Chen","doi":"10.1021/acs.jpclett.5c03029","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03029","url":null,"abstract":"Despite outstanding catalytic potential, stabilizing single-atom-thick metallenes presents a fundamental challenge in materials design. Through first-principles structure search calculations, we have identified a novel two-dimensional (2D) Janus nanomaterial Pt(111)@CP, in which the single atomic Pt (111) metallene layer serves as one exposed surface, effectively stabilized by coupling with the robust nonmetallic CP framework composed of sp<sup>3</sup>-hybridized C atoms and sp<sup>3</sup>-hybridized P atoms possessing lone pair electrons. The unique Pt(111)@CP nanostructure can exhibit excellent dynamic, thermodynamic, mechanical and thermal stability, as well as metallic conductivity. Additionally, it can demonstrate considerably high HER catalytic performance, with both sides playing important roles. Remarkably, it can maintain high HER catalytic activity over a wide range of θ<sub>H*</sub> coverages. Its active site density can reach 1.022 × 10<sup>16</sup> sites/cm<sup>2</sup>, exceeding many reported materials and even state-of-the-art Pt. Further, by substituting Pt atoms with other Group VIII transition metals, we derived a series of novel 2D Janus TM(111)@CP monolayers (TM = Ru, Rh, Pd, Os and Ir) from the Pt(111)@CP structure. All five newly designed TM(111)@CP monolayers featuring the TM (111) metallene surfaces demonstrate high stability and metallic conductivity. They also maintain high HER catalytic activity over a wide range of θ<sub>H*</sub> coverages, with active site densities reaching 1.473 × 10<sup>15</sup> to 9.888 × 10<sup>15</sup> sites/cm<sup>2</sup>, comparable to or exceeding the precious metal Pt. The relevant catalytic mechanisms are analyzed. This study presents an innovative strategy for stabilizing metallenes and developing high-performance metallene-related electrocatalysts for HER and even broader energy conversion applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"93 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1021/acs.jpclett.5c03593
Hui Wang,Yanmei Dong,Jun Xie,Yubo Yuan,Caichen Yang,Shu He,Yuanxu Liu,Xiangang Lin,Yangyang Li
Electronic interface interaction (EII) plays an important role in regulating the structure-function relationship of metal/oxide heterogeneous catalytic systems. In this work, we prepared Al2O3/Ag inverse oxide/metal catalysts with a facile synthetic method without using any organic ligand. The composites were supported by well-defined silver nanocubes (Ag NCs) and covered by an oxide layer with variable coverage as confirmed by transmission electron microscopy (TEM) and high-sensitivity low-energy ion scattering spectroscopy (HS-LEIS) characterizations. The catalytic performance toward the reduction of 4-nitrophenol (4-NP) in excess NaBH4 obviously enhanced with increasing coverage of alumina overlayer; the composite principally provided more surface adsorption sites for reactants, confirmed by the increasing saturated adsorption capacity toward 4-NP. In comparison with pristine Ag NCs and bulk Al2O3, optimized Al2O3/c-Ag showed superior catalytic performance with about complete conversion of 4-NP within 2 min, keeping high stability for six cycles; the reaction possessed lower apparent activation energy (35.0 kJ/mol), and the corresponding pseudo-first-order kinetic rate constant (2.11 min-1) was about 3.27 times greater than that of Ag NCs (0.65 min-1). In addition, X-ray photoelectron spectroscopy (XPS) characterization indicated that overall Ag 3d peaks shifted to lower binding energy with increasing percentage of oxide layer, indicating an inclination of metal-oxide interface electron transfer, and Ag NCs acted as a charge contributor, thus directly influencing the catalytic performance in such an electron inducing reaction. This report provides a profound understanding of the electronic interaction between metal and nonreducible oxides, helping to construct a more efficient and stable silver-based catalyst for catalytic reduction of aromatic nitro compounds.
{"title":"Electronic Interface Interaction on Al2O3/Ag Inverse Catalysts for Enhanced Catalytic Reduction of 4-NP.","authors":"Hui Wang,Yanmei Dong,Jun Xie,Yubo Yuan,Caichen Yang,Shu He,Yuanxu Liu,Xiangang Lin,Yangyang Li","doi":"10.1021/acs.jpclett.5c03593","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03593","url":null,"abstract":"Electronic interface interaction (EII) plays an important role in regulating the structure-function relationship of metal/oxide heterogeneous catalytic systems. In this work, we prepared Al2O3/Ag inverse oxide/metal catalysts with a facile synthetic method without using any organic ligand. The composites were supported by well-defined silver nanocubes (Ag NCs) and covered by an oxide layer with variable coverage as confirmed by transmission electron microscopy (TEM) and high-sensitivity low-energy ion scattering spectroscopy (HS-LEIS) characterizations. The catalytic performance toward the reduction of 4-nitrophenol (4-NP) in excess NaBH4 obviously enhanced with increasing coverage of alumina overlayer; the composite principally provided more surface adsorption sites for reactants, confirmed by the increasing saturated adsorption capacity toward 4-NP. In comparison with pristine Ag NCs and bulk Al2O3, optimized Al2O3/c-Ag showed superior catalytic performance with about complete conversion of 4-NP within 2 min, keeping high stability for six cycles; the reaction possessed lower apparent activation energy (35.0 kJ/mol), and the corresponding pseudo-first-order kinetic rate constant (2.11 min-1) was about 3.27 times greater than that of Ag NCs (0.65 min-1). In addition, X-ray photoelectron spectroscopy (XPS) characterization indicated that overall Ag 3d peaks shifted to lower binding energy with increasing percentage of oxide layer, indicating an inclination of metal-oxide interface electron transfer, and Ag NCs acted as a charge contributor, thus directly influencing the catalytic performance in such an electron inducing reaction. This report provides a profound understanding of the electronic interaction between metal and nonreducible oxides, helping to construct a more efficient and stable silver-based catalyst for catalytic reduction of aromatic nitro compounds.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"4 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing high-efficiency single-atom catalysts (SACs) is essential for the carbon dioxide reduction reaction (CO2RR) to produce fuels and chemicals, yet achieving optimal performance remains challenging. In this work, we applied a grain boundary (GB) strategy to rationally design a series of MoS2 supported SACs for electrocatalytic CO2RR. Concretely, different 3d transition metal (TM) atoms were respectively anchored at three types of MoS2 GBs (e.g., 5|7, 8|8, and 4|8 GBs) to form various TM@GB SACs. Our density-functional theory (DFT) calculations revealed that, in comparison with the MoS2 perfect monolayer, strong interactions between TM atoms and MoS2 GBs shift down the d-band center of these atoms, hence improving the CO2RR activity of TM@GB SACs. Among TM@GBs, V@5|7, Cr@8|8, and V@4|8 GBs were demonstrated to possess excellent catalytic activity, enabling spontaneous CO2 reduction to CO at applied electrode potentials of -0.30, -0.10, and -0.26 V (vs SHE), respectively. Further, a pivotal descriptor (ψ) based on the inherent structural properties of GB and TM was proposed to correlate the structure with the CO2RR activity. Our findings highlight the potential of GB engineering as a strategic tool for modulating the properties of SACs, broadening the applications in catalyst design and optimization.
开发高效的单原子催化剂（SACs）对于二氧化碳还原反应（CO2RR）生产燃料和化学品至关重要，但实现最佳性能仍然具有挑战性。在这项工作中，我们应用晶界（GB）策略来合理设计一系列MoS2负载的sac用于电催化CO2RR。具体地说，不同的三维过渡金属（TM）原子分别锚定在三种类型的MoS2 gb（例如，5|7、8|8和4|8 gb）上，形成不同的TM@GB SACs。我们的密度泛函理论（DFT）计算表明，与MoS2完美单层相比，TM原子与MoS2 gb之间的强相互作用使这些原子的d带中心向下移动，从而提高了TM@GB SACs的CO2RR活性。在TM@GBs、V@5 bbb70、Cr@8|8和V@4|8中，GBs被证明具有优异的催化活性，可以在分别为-0.30、-0.10和-0.26 V （vs SHE）的电极电位下自发地将CO2还原为CO。此外，基于GB和TM的固有结构特性，提出了一个关键描述符（ψ）来将结构与CO2RR活性关联起来。我们的研究结果突出了GB工程作为调节sac性质的战略工具的潜力，扩大了催化剂设计和优化的应用。
{"title":"MoS2 Grain Boundary-Supported Single-Atom Catalysts for Efficient Electrocatalytic CO2 Conversion to CO.","authors":"Yuxing Lin,Meijie Wang,Yaowei Xiang,Lei Li,Xing Chen,Yameng Li,Rao Huang,Yuhua Wen","doi":"10.1021/acs.jpclett.5c03749","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03749","url":null,"abstract":"Developing high-efficiency single-atom catalysts (SACs) is essential for the carbon dioxide reduction reaction (CO2RR) to produce fuels and chemicals, yet achieving optimal performance remains challenging. In this work, we applied a grain boundary (GB) strategy to rationally design a series of MoS2 supported SACs for electrocatalytic CO2RR. Concretely, different 3d transition metal (TM) atoms were respectively anchored at three types of MoS2 GBs (e.g., 5|7, 8|8, and 4|8 GBs) to form various TM@GB SACs. Our density-functional theory (DFT) calculations revealed that, in comparison with the MoS2 perfect monolayer, strong interactions between TM atoms and MoS2 GBs shift down the d-band center of these atoms, hence improving the CO2RR activity of TM@GB SACs. Among TM@GBs, V@5|7, Cr@8|8, and V@4|8 GBs were demonstrated to possess excellent catalytic activity, enabling spontaneous CO2 reduction to CO at applied electrode potentials of -0.30, -0.10, and -0.26 V (vs SHE), respectively. Further, a pivotal descriptor (ψ) based on the inherent structural properties of GB and TM was proposed to correlate the structure with the CO2RR activity. Our findings highlight the potential of GB engineering as a strategic tool for modulating the properties of SACs, broadening the applications in catalyst design and optimization.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"40 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1021/acs.jpclett.5c03717
Ke Zhou
Mechanosensitive ion nanochannels regulate transport by undergoing conformational changes within the nanopores. However, achieving precise control over these conformational states remains a major challenge for both artificial soft and solid pores. Here, we propose an alternative mechanism that modulates the charge carrier density inside nanopores, inspired by transistors in solid-state electronics. This strategy leverages a novel phenomenon of confinement-regulated ion clustering in two-dimensional extremely confined nanochannels, revealed by extensive μs-scale enhanced-sampling molecular simulations based on an ab initio-refined force field and nucleation theory. The resulting force-ion transistor enables the mechanically gated control of ion transport and provides a conceptual foundation for designing ionic mechanical logic gates. Our findings offer new insights into piezochannel mechanosensing and electromechanical coupling in biosystems beyond conformational signaling, opening pathways to integrate artificial ion channels with neuromorphic devices for processing mechanical stimuli.
{"title":"Ion Clustering Regulated by Extreme Nanoconfinement Enables Mechanosensitive Nanochannels.","authors":"Ke Zhou","doi":"10.1021/acs.jpclett.5c03717","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03717","url":null,"abstract":"<p><p>Mechanosensitive ion nanochannels regulate transport by undergoing conformational changes within the nanopores. However, achieving precise control over these conformational states remains a major challenge for both artificial soft and solid pores. Here, we propose an alternative mechanism that modulates the charge carrier density inside nanopores, inspired by transistors in solid-state electronics. This strategy leverages a novel phenomenon of confinement-regulated ion clustering in two-dimensional extremely confined nanochannels, revealed by extensive μs-scale enhanced-sampling molecular simulations based on an <i>ab initio</i>-refined force field and nucleation theory. The resulting <i>force-ion transistor</i> enables the mechanically gated control of ion transport and provides a conceptual foundation for designing ionic mechanical logic gates. Our findings offer new insights into piezochannel mechanosensing and electromechanical coupling in biosystems beyond conformational signaling, opening pathways to integrate artificial ion channels with neuromorphic devices for processing mechanical stimuli.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146083660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hot carrier (HC) cooling represents a dominant nonradiative loss pathway that ultimately constrains the efficiency of perovskite solar cells (PSCs). Despite the ubiquity of intrinsic vacancy defects in halide perovskites, their mechanistic influence on HC relaxation dynamics has remained elusive and is often overlooked, largely because the ultrafast time scales, intricate defect-phonon interactions, and subtle band-edge perturbations make these effects difficult to isolate and quantify. Here, first-principles calculations coupled with nonadiabatic molecular dynamics (NAMD) are employed to systematically assess how intrinsic vacancy defects affect HC cooling behavior in FAPbI3. We demonstrate that while vacancy defects significantly modulate the bandgap of FAPbI3, the carrier relaxation rate does not scale directly with the gap magnitude. Notably, iodine and formamidinium vacancies selectively hinder the cooling of hot electrons and hot holes, respectively. This defect-mediated suppression stems from two synergistic mechanisms: weakened electron-phonon (e-ph) coupling and a transition of carrier relaxation pathways from fast, direct relaxation to slower, stepwise processes. These effects synergistically prolong the HC lifetimes and mitigate energy dissipation during the cooling process. Our findings establish a defect-type-specific framework for tuning HC dynamics and highlight defect engineering as a powerful strategy to enhance hot carrier utilization in next-generation high-efficiency photovoltaic devices.
{"title":"Tailoring Hot Carrier Cooling Dynamics via Targeted Vacancy Design in FAPbI3 for High-Efficiency Photovoltaics.","authors":"Xingyun Luo,Zichen Yan,Hao Ma,Xueqin Sun,Yanlu Li,Xian Zhao","doi":"10.1021/acs.jpclett.5c04030","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04030","url":null,"abstract":"Hot carrier (HC) cooling represents a dominant nonradiative loss pathway that ultimately constrains the efficiency of perovskite solar cells (PSCs). Despite the ubiquity of intrinsic vacancy defects in halide perovskites, their mechanistic influence on HC relaxation dynamics has remained elusive and is often overlooked, largely because the ultrafast time scales, intricate defect-phonon interactions, and subtle band-edge perturbations make these effects difficult to isolate and quantify. Here, first-principles calculations coupled with nonadiabatic molecular dynamics (NAMD) are employed to systematically assess how intrinsic vacancy defects affect HC cooling behavior in FAPbI3. We demonstrate that while vacancy defects significantly modulate the bandgap of FAPbI3, the carrier relaxation rate does not scale directly with the gap magnitude. Notably, iodine and formamidinium vacancies selectively hinder the cooling of hot electrons and hot holes, respectively. This defect-mediated suppression stems from two synergistic mechanisms: weakened electron-phonon (e-ph) coupling and a transition of carrier relaxation pathways from fast, direct relaxation to slower, stepwise processes. These effects synergistically prolong the HC lifetimes and mitigate energy dissipation during the cooling process. Our findings establish a defect-type-specific framework for tuning HC dynamics and highlight defect engineering as a powerful strategy to enhance hot carrier utilization in next-generation high-efficiency photovoltaic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"180 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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