Pub Date : 2025-09-24DOI: 10.1016/j.actphy.2025.100194
Shantao Zhang , TianAo Hou , Yandong Wang , Zhimin Fang , Yu Wu , Haolin Wang , Tao Chen , Shuang Chen , Wenhua Zhang , Shengzhong Liu (Frank) , Shangfeng Yang
In the rapidly evolving field of photovoltaic technology, self-assembled monolayers (SAMs) have become essential hole-selective layers (HSLs) for inverted perovskite solar cells (PSCs). SAMs not only determine interfacial hole extraction but also significantly influence the film quality of the atop perovskite layers, consequently affecting the efficiency and stability of perovskite solar cells. Among various SAMs, carbazole-based SAMs, exemplified by 4PACZ, have emerged as prominent due to their electron-rich characteristics, making them some of the most prevalent HSLs in modern inverted PSCs. Nevertheless, 4PACZ exhibits significant limitations: one major issue is its limited molecular dipole, which leads to insufficient energy level alignment between the treated substrate and the perovskite, causing substantial interfacial energy loss. Another critical challenge is the flat structure of the carbazole unit, which often promotes molecular stacking, resulting in incomplete substrate coverage and non-uniform film formation, thereby compromising both device performance and stability. In this study, we designed a novel SAM based on a polycyclic aromatic hydrocarbon derivative, (4-(8H-dinaphtho[2,3-c:2′,3′-g]carbazol-8-yl)butyl)phosphonic acid (4PADNC), with the aim of optimizing hole transport in inverted PSCs. This SAM incorporates the structurally extended dinaphtho[2,3-c:2′,3′-g]carbazole (DNC) as the functional terminal group, replacing the single carbazole unit in the traditional material 4PACZ. The key structural difference is that the DNC group provides a significantly expanded π-conjugated skeleton and enhanced electron-rich characteristics. These features not only greatly enhance hole extraction and transport at the interface but also induce a significant increase in the molecular dipole moment, which is crucial for effectively adjusting the work function of ITO, ensuring proper alignment with the perovskite layer. Additionally, there is an intramolecular dihedral angle of approximately 34.62° in the DNC unit at the core of 4PADNC. This non-planar configuration contrasts sharply with the planar carbazole structure. The larger dihedral angle effectively suppresses excessive π-π stacking between molecules, which not only aids in forming a denser and more ordered molecular layer on the ITO surface but also provides a more favorable and defect-free substrate for the growth of the upper perovskite. With these upgrades, the inverted PSCs based on 4PADNC achieved a PCE as high as 24.32 %, compared to 22.89 % for the control devices based on 4PACZ. Furthermore, the 4PADNC-based devices also exhibited superior thermal stability and operational stability.
{"title":"π-Conjugation-extended dinaphthocarbazole phosphonic acid as a hole-selective layer for inverted perovskite solar cells","authors":"Shantao Zhang , TianAo Hou , Yandong Wang , Zhimin Fang , Yu Wu , Haolin Wang , Tao Chen , Shuang Chen , Wenhua Zhang , Shengzhong Liu (Frank) , Shangfeng Yang","doi":"10.1016/j.actphy.2025.100194","DOIUrl":"10.1016/j.actphy.2025.100194","url":null,"abstract":"<div><div>In the rapidly evolving field of photovoltaic technology, self-assembled monolayers (SAMs) have become essential hole-selective layers (HSLs) for inverted perovskite solar cells (PSCs). SAMs not only determine interfacial hole extraction but also significantly influence the film quality of the atop perovskite layers, consequently affecting the efficiency and stability of perovskite solar cells. Among various SAMs, carbazole-based SAMs, exemplified by 4PACZ, have emerged as prominent due to their electron-rich characteristics, making them some of the most prevalent HSLs in modern inverted PSCs. Nevertheless, 4PACZ exhibits significant limitations: one major issue is its limited molecular dipole, which leads to insufficient energy level alignment between the treated substrate and the perovskite, causing substantial interfacial energy loss. Another critical challenge is the flat structure of the carbazole unit, which often promotes molecular stacking, resulting in incomplete substrate coverage and non-uniform film formation, thereby compromising both device performance and stability. In this study, we designed a novel SAM based on a polycyclic aromatic hydrocarbon derivative, (4-(8H-dinaphtho[2,3-c:2′,3′-g]carbazol-8-yl)butyl)phosphonic acid (4PADNC), with the aim of optimizing hole transport in inverted PSCs. This SAM incorporates the structurally extended dinaphtho[2,3-c:2′,3′-g]carbazole (DNC) as the functional terminal group, replacing the single carbazole unit in the traditional material 4PACZ. The key structural difference is that the DNC group provides a significantly expanded π-conjugated skeleton and enhanced electron-rich characteristics. These features not only greatly enhance hole extraction and transport at the interface but also induce a significant increase in the molecular dipole moment, which is crucial for effectively adjusting the work function of ITO, ensuring proper alignment with the perovskite layer. Additionally, there is an intramolecular dihedral angle of approximately 34.62° in the DNC unit at the core of 4PADNC. This non-planar configuration contrasts sharply with the planar carbazole structure. The larger dihedral angle effectively suppresses excessive π-π stacking between molecules, which not only aids in forming a denser and more ordered molecular layer on the ITO surface but also provides a more favorable and defect-free substrate for the growth of the upper perovskite. With these upgrades, the inverted PSCs based on 4PADNC achieved a PCE as high as 24.32 %, compared to 22.89 % for the control devices based on 4PACZ. Furthermore, the 4PADNC-based devices also exhibited superior thermal stability and operational stability.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100194"},"PeriodicalIF":13.5,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923298","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 : 2025-09-23DOI: 10.1016/j.actphy.2025.100192
Xinming Nie , Xinhe Wu
{"title":"Schottky/S-scheme composite heterojunctions for efficient CO2 photoreduction","authors":"Xinming Nie , Xinhe Wu","doi":"10.1016/j.actphy.2025.100192","DOIUrl":"10.1016/j.actphy.2025.100192","url":null,"abstract":"","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100192"},"PeriodicalIF":13.5,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923323","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 : 2025-09-20DOI: 10.1016/j.actphy.2025.100190
Deyun Ma , Fenglan Liang , Qingquan Xue , Yanping Liu , Chunqiang Zhuang , Shijie Li
The construction of S-scheme heterojunction photocatalysts has emerged as a promising strategy to address the urgent need for efficient antibiotic wastewater remediation. However, persistent challenges in achieving interfacial intimacy and precise charge transfer regulation between semiconductors have hindered their practical implementation. In this work, we engineered a hierarchical Cd0.5Zn0.5S/BiOBr S-scheme heterojunction via a controlled solvothermal synthesis, where BiOBr microspheres serve as the core, and Cd0.5Zn0.5S nanoparticles form a conformal shell. This architecture ensures maximal interfacial contact and directional charge dynamics, critical for optimizing photocatalytic efficiency. The optimized heterojunction exhibits superior catalytic performance, achieving tetracycline (TC) degradation rate constants 3.3- and 1.6-fold greater than pristine BiOBr and Cd0.5Zn0.5S, respectively. This enhancement stems from the synergistic interplay of efficient charge separation and preserved redox capacities inherent to the S-scheme mechanism. Furthermore, the TC degradation process and mechanism were elucidated. This study provides a new perspective on developing defective S-scheme heterojunctions for antibiotic wastewater purification with high performance.
{"title":"Interfacial engineering of Cd0.5Zn0.5S/BiOBr S-scheme heterojunction with oxygen vacancies for effective photocatalytic antibiotic removal","authors":"Deyun Ma , Fenglan Liang , Qingquan Xue , Yanping Liu , Chunqiang Zhuang , Shijie Li","doi":"10.1016/j.actphy.2025.100190","DOIUrl":"10.1016/j.actphy.2025.100190","url":null,"abstract":"<div><div>The construction of S-scheme heterojunction photocatalysts has emerged as a promising strategy to address the urgent need for efficient antibiotic wastewater remediation. However, persistent challenges in achieving interfacial intimacy and precise charge transfer regulation between semiconductors have hindered their practical implementation. In this work, we engineered a hierarchical Cd<sub>0.5</sub>Zn<sub>0.5</sub>S/BiOBr S-scheme heterojunction via a controlled solvothermal synthesis, where BiOBr microspheres serve as the core, and Cd<sub>0.5</sub>Zn<sub>0.5</sub>S nanoparticles form a conformal shell. This architecture ensures maximal interfacial contact and directional charge dynamics, critical for optimizing photocatalytic efficiency. The optimized heterojunction exhibits superior catalytic performance, achieving tetracycline (TC) degradation rate constants 3.3- and 1.6-fold greater than pristine BiOBr and Cd<sub>0.5</sub>Zn<sub>0.5</sub>S, respectively. This enhancement stems from the synergistic interplay of efficient charge separation and preserved redox capacities inherent to the S-scheme mechanism. Furthermore, the TC degradation process and mechanism were elucidated. This study provides a new perspective on developing defective S-scheme heterojunctions for antibiotic wastewater purification with high performance.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100190"},"PeriodicalIF":13.5,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145118509","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 : 2025-09-17DOI: 10.1016/j.actphy.2025.100189
Mengxiu Li, Jiahui Mao, Jiangfeng Ni, Liang Li
Lithium ferrate Li5FeO4 is a promising cathode prelithiation additive for lithium-ion batteries, boasting a high theoretical capacity of 867 mAh g−1, which compensates for lithium loss due to solid electrolyte interphase (SEI) formation during the initial cycle. However, its practical application faces significant challenges due to inherent chemical instability. The material is extremely sensitive to air, readily undergoing deleterious side reactions with atmospheric carbon dioxide and moisture to form electrochemically inert Li2CO3 surface layers. This degradation in the atmosphere presents several major issues. It not only substantially reduces active lithium content but also induces severe slurry gelation during electrode manufacturing. In addition, it promotes continuous gas generation and electrolyte decomposition during battery operation, and leads to a significant increase in electrochemical impedance. Previous stabilization attempts via carbon coating or metal doping have shown limited success, often introducing new problems such as capacity reduction or inadequate protection, highlighting the urgent need for a more comprehensive and effective modification method. To address these challenges, this study proposes an efficient Lewis acid-induced regeneration strategy through thermal modification with PF5. This approach effectively removes surface inert impurities and facilitates the in-situ construction of a composite layer of Li3PO4 and LiF on the Li5FeO4 particles. The regenerated Li5FeO4 exhibits excellent dispersion, air stability, and electrolyte interfacial compatibility, effectively suppressing slurry gelation and interfacial side reactions. In comparison with the bare counterpart, the regenerated Li5FeO4 shows a significantly reduced viscosity upon slurry processing and gas generation during high-temperature storage. When 1.5 % (wt) regenerated Li5FeO4 is introduced to the LiFePO4 cathode in the full cells, the cathode maintains a high capacity of 135.0 mAh g−1 and a retention rate of 95.3 % after 200 cycles. In contrast, the control LiFePO4 cathode without Li5FeO4 only retains 113.7 mAh g−1 with a capacity retention of 92.2 %. This approach integrates impurity removal, interfacial stabilization, and performance enhancement of Li5FeO4 into one strategy, which will find extensive applications in long-cycle lithium-ion batteries.
高铁酸锂Li5FeO4是一种很有前途的锂离子电池正极预锂化添加剂，具有高达867 mAh g−1的理论容量，可以弥补初始循环过程中固体电解质间相（SEI）形成造成的锂损失。然而，由于其固有的化学不稳定性，其实际应用面临着重大挑战。这种材料对空气极其敏感，容易与大气中的二氧化碳和水分发生有害的副反应，形成电化学惰性的Li2CO3表面层。大气中的这种退化提出了几个主要问题。它不仅大大降低了活性锂含量，而且在电极制造过程中引起了严重的浆液凝胶化。此外，它促进电池在工作过程中不断产生气体和电解液分解，导致电化学阻抗显著增加。以前通过碳涂层或金属掺杂的稳定尝试取得的成功有限，经常会引入新的问题，如容量降低或保护不足，这突出了对更全面有效的改性方法的迫切需要。为了解决这些挑战，本研究提出了一种通过PF5热改性的Lewis酸诱导再生策略。该方法有效地去除了表面惰性杂质，有利于在Li5FeO4颗粒上原位构建Li3PO4和LiF复合层。再生的Li5FeO4具有良好的分散性、空气稳定性和电解质界面相容性，可有效抑制浆液凝胶和界面副反应。与裸露的Li5FeO4相比，再生后的Li5FeO4在浆料加工和高温储存过程中产生气体时，粘度明显降低。在充满电池的LiFePO4阴极中加入1.5% （wt）的再生Li5FeO4，在200次循环后，阴极保持135.0 mAh g−1的高容量和95.3%的保留率。相比之下，不含Li5FeO4的LiFePO4阴极仅保留113.7 mAh g−1，容量保留率为92.2%。该方法集杂质去除、界面稳定和Li5FeO4性能增强于一体，将在长循环锂离子电池中得到广泛应用。
{"title":"Three birds with one stone: modification of Li5FeO4 with thermal induction of Lewis acid","authors":"Mengxiu Li, Jiahui Mao, Jiangfeng Ni, Liang Li","doi":"10.1016/j.actphy.2025.100189","DOIUrl":"10.1016/j.actphy.2025.100189","url":null,"abstract":"<div><div>Lithium ferrate Li<sub>5</sub>FeO<sub>4</sub> is a promising cathode prelithiation additive for lithium-ion batteries, boasting a high theoretical capacity of 867 mAh g<sup>−1</sup>, which compensates for lithium loss due to solid electrolyte interphase (SEI) formation during the initial cycle. However, its practical application faces significant challenges due to inherent chemical instability. The material is extremely sensitive to air, readily undergoing deleterious side reactions with atmospheric carbon dioxide and moisture to form electrochemically inert Li<sub>2</sub>CO<sub>3</sub> surface layers. This degradation in the atmosphere presents several major issues. It not only substantially reduces active lithium content but also induces severe slurry gelation during electrode manufacturing. In addition, it promotes continuous gas generation and electrolyte decomposition during battery operation, and leads to a significant increase in electrochemical impedance. Previous stabilization attempts via carbon coating or metal doping have shown limited success, often introducing new problems such as capacity reduction or inadequate protection, highlighting the urgent need for a more comprehensive and effective modification method. To address these challenges, this study proposes an efficient Lewis acid-induced regeneration strategy through thermal modification with PF<sub>5</sub>. This approach effectively removes surface inert impurities and facilitates the in-situ construction of a composite layer of Li<sub>3</sub>PO<sub>4</sub> and LiF on the Li<sub>5</sub>FeO<sub>4</sub> particles. The regenerated Li<sub>5</sub>FeO<sub>4</sub> exhibits excellent dispersion, air stability, and electrolyte interfacial compatibility, effectively suppressing slurry gelation and interfacial side reactions. In comparison with the bare counterpart, the regenerated Li<sub>5</sub>FeO<sub>4</sub> shows a significantly reduced viscosity upon slurry processing and gas generation during high-temperature storage. When 1.5 % (wt) regenerated Li<sub>5</sub>FeO<sub>4</sub> is introduced to the LiFePO<sub>4</sub> cathode in the full cells, the cathode maintains a high capacity of 135.0 mAh g<sup>−1</sup> and a retention rate of 95.3 % after 200 cycles. In contrast, the control LiFePO<sub>4</sub> cathode without Li<sub>5</sub>FeO<sub>4</sub> only retains 113.7 mAh g<sup>−1</sup> with a capacity retention of 92.2 %. This approach integrates impurity removal, interfacial stabilization, and performance enhancement of Li<sub>5</sub>FeO<sub>4</sub> into one strategy, which will find extensive applications in long-cycle lithium-ion batteries.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 4","pages":"Article 100189"},"PeriodicalIF":13.5,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146006636","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 : 2025-09-16DOI: 10.1016/j.actphy.2025.100188
Shuai Bi , Xixi Wang , Wei Zhai , Zhenyu Shi , Zijian Li , Li Zhai , An Zhang , Yuhui Tian , Ting Cheng , Yao Yao , Zhiying Wu , Jiawei Liu , Hua Zhang
Phase, which refers to the specific atomic arrangement, is one of the key parameters to determine the physicochemical properties and functions of nanomaterials. Recently, phase engineering of nanomaterials (PEN) has emerged as a promising research direction in materials science, since precise control over atomic arrangements enables the synthesis of nanomaterials with unconventional phases that are different from their thermodynamically stable counterparts, resulting in unique physicochemical properties. Therefore, PEN provides a new strategy for developing novel functional nanomaterials to enhance their performance in various applications. This review focuses on PEN strategies for preparing novel noble metals and transition metal dichalcogenides (TMDs) with unconventional phases. It provides a comprehensive summary of crucial synthetic methods, such as direct synthesis and phase transformation, demonstrates their phase-dependent properties and catalytic performance, and highlights the significant impact of phase on the functions and applications of nanomaterials. Finally, we discuss the challenges and future directions for PEN, including in-depth studies on synthetic mechanisms, effective strategies to improve the stability of unconventional-phase nanomaterials, and innovative AI-aided structural design. These efforts aim to provide theoretical and technical guidance on both fundamental research and practical applications in the field of PEN.
{"title":"Phase engineering of nanomaterials: from fundamentals to application frontiers","authors":"Shuai Bi , Xixi Wang , Wei Zhai , Zhenyu Shi , Zijian Li , Li Zhai , An Zhang , Yuhui Tian , Ting Cheng , Yao Yao , Zhiying Wu , Jiawei Liu , Hua Zhang","doi":"10.1016/j.actphy.2025.100188","DOIUrl":"10.1016/j.actphy.2025.100188","url":null,"abstract":"<div><div>Phase, which refers to the specific atomic arrangement, is one of the key parameters to determine the physicochemical properties and functions of nanomaterials. Recently, phase engineering of nanomaterials (PEN) has emerged as a promising research direction in materials science, since precise control over atomic arrangements enables the synthesis of nanomaterials with unconventional phases that are different from their thermodynamically stable counterparts, resulting in unique physicochemical properties. Therefore, PEN provides a new strategy for developing novel functional nanomaterials to enhance their performance in various applications. This review focuses on PEN strategies for preparing novel noble metals and transition metal dichalcogenides (TMDs) with unconventional phases. It provides a comprehensive summary of crucial synthetic methods, such as direct synthesis and phase transformation, demonstrates their phase-dependent properties and catalytic performance, and highlights the significant impact of phase on the functions and applications of nanomaterials. Finally, we discuss the challenges and future directions for PEN, including in-depth studies on synthetic mechanisms, effective strategies to improve the stability of unconventional-phase nanomaterials, and innovative AI-aided structural design. These efforts aim to provide theoretical and technical guidance on both fundamental research and practical applications in the field of PEN.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100188"},"PeriodicalIF":13.5,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923328","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}
Photocatalysis of H2O2 production using O2 and water is a cost-effective and environmental process, but developing high-performance photocatalysts is still a challenge. Herein, a WO3@polymer S-scheme photocatalyst was synthesized by in situ growing the Schiff-base polymer, tris-(4-aminophenyl)amine (TAPA)- terephthaldicarboxaldehyde (PDA) (labeled as TP) on the surface of WO3 nanofibers (WO3@TP) at room temperature. The obtained WO3@TP S-scheme heterojunction exhibited rapid carrier separation ability and short photogenerated carriers transfer distance. The optimal WO3@TP composite (WT-10) realized the H2O2 evolution rate of 3242 μmol g−1 h−1, which was 137.3 and 4.6-fold higher than bare WO3 and TP, respectively. The combination of advanced characterizations regarding in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS), theoretical calculation, and femtosecond transient absorption spectroscopy (fs-TAS) validates the charge transfer mechanism within the WO3@TP S-scheme heterojunction. The occurrence of a dual-channel pathway (O2 reduction reaction (ORR) and water oxidation reaction (WOR)) within the reaction system has been confirmed via electron paramagnetic resonance (EPR) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), thereby contributing to the highly efficient H2O2 evolution. This study not only gives an in-depth understanding of the ultrafast charge migration behavior in S-scheme heterojunction but also offers the rational design of inorganic@organic photocatalysts applied to solar-driven H2O2 production.
{"title":"WO3@TP inorganic@organic S-scheme photocatalyst for boosting H2O2 production","authors":"Wenjun Zhu , Chenbin Ai , Kaiqiang Xu , Yatai Zhou , Xidong Zhang , Yong Zhang","doi":"10.1016/j.actphy.2025.100184","DOIUrl":"10.1016/j.actphy.2025.100184","url":null,"abstract":"<div><div>Photocatalysis of H<sub>2</sub>O<sub>2</sub> production using O<sub>2</sub> and water is a cost-effective and environmental process, but developing high-performance photocatalysts is still a challenge. Herein, a WO<sub>3</sub>@polymer S-scheme photocatalyst was synthesized by in situ growing the Schiff-base polymer, tris-(4-aminophenyl)amine (TAPA)- terephthaldicarboxaldehyde (PDA) (labeled as TP) on the surface of WO<sub>3</sub> nanofibers (WO<sub>3</sub>@TP) at room temperature. The obtained WO<sub>3</sub>@TP S-scheme heterojunction exhibited rapid carrier separation ability and short photogenerated carriers transfer distance. The optimal WO<sub>3</sub>@TP composite (WT-10) realized the H<sub>2</sub>O<sub>2</sub> evolution rate of 3242 μmol g<sup>−1</sup> h<sup>−1</sup>, which was 137.3 and 4.6-fold higher than bare WO<sub>3</sub> and TP, respectively. The combination of advanced characterizations regarding in situ irradiated X-ray photoelectron spectroscopy (ISI-XPS), theoretical calculation, and femtosecond transient absorption spectroscopy (<em>fs</em>-TAS) validates the charge transfer mechanism within the WO<sub>3</sub>@TP S-scheme heterojunction. The occurrence of a dual-channel pathway (O<sub>2</sub> reduction reaction (ORR) and water oxidation reaction (WOR)) within the reaction system has been confirmed via electron paramagnetic resonance (EPR) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), thereby contributing to the highly efficient H<sub>2</sub>O<sub>2</sub> evolution. This study not only gives an in-depth understanding of the ultrafast charge migration behavior in S-scheme heterojunction but also offers the rational design of inorganic@organic photocatalysts applied to solar-driven H<sub>2</sub>O<sub>2</sub> production.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100184"},"PeriodicalIF":13.5,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923299","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 : 2025-09-10DOI: 10.1016/j.actphy.2025.100185
Jingjing Liu, Aoqi Wei, Hao Zhang, Shuwang Duo
Recent advances in tin disulfide (SnS2)-based heterojunctions have demonstrated their great potential for photocatalysis and sensing applications, owing to their optimal bandgap (2.0–2.3 eV), remarkable stability, environmental compatibility, and outstanding surface reactivity. Despite these advantages, a comprehensive review systematically addressing this emerging field remains lacking. This review first outlines the state-of-the-art synthesis strategies for SnS2 heterostructures. It then critically evaluates their photocatalytic performance in key applications, including hydrogen evolution, environmental remediation, and hydrogen peroxide production. The gas-sensing capabilities are subsequently analyzed, with special emphasis on nitrogen dioxide and ammonia detection. Mechanistic studies reveal that the enhanced performance originates from tailored heterojunction designs: S-scheme configurations significantly boost charge separation in photocatalysis; n-n/p-n junctions optimize active site distribution and gas adsorption in sensing applications. The interfacial synergy between SnS2 and coupled semiconductors is identified as the key factor governing performance improvements. Finally, some conclusions and perspectives as well as future challenges are presented.
{"title":"SnS2-based heterostructures: advances in photocatalytic and gas-sensing applications","authors":"Jingjing Liu, Aoqi Wei, Hao Zhang, Shuwang Duo","doi":"10.1016/j.actphy.2025.100185","DOIUrl":"10.1016/j.actphy.2025.100185","url":null,"abstract":"<div><div>Recent advances in tin disulfide (SnS<sub>2</sub>)-based heterojunctions have demonstrated their great potential for photocatalysis and sensing applications, owing to their optimal bandgap (2.0–2.3 eV), remarkable stability, environmental compatibility, and outstanding surface reactivity. Despite these advantages, a comprehensive review systematically addressing this emerging field remains lacking. This review first outlines the state-of-the-art synthesis strategies for SnS<sub>2</sub> heterostructures. It then critically evaluates their photocatalytic performance in key applications, including hydrogen evolution, environmental remediation, and hydrogen peroxide production. The gas-sensing capabilities are subsequently analyzed, with special emphasis on nitrogen dioxide and ammonia detection. Mechanistic studies reveal that the enhanced performance originates from tailored heterojunction designs: S-scheme configurations significantly boost charge separation in photocatalysis; n-n/p-n junctions optimize active site distribution and gas adsorption in sensing applications. The interfacial synergy between SnS<sub>2</sub> and coupled semiconductors is identified as the key factor governing performance improvements. Finally, some conclusions and perspectives as well as future challenges are presented.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100185"},"PeriodicalIF":13.5,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145060381","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 : 2025-09-09DOI: 10.1016/j.actphy.2025.100180
Débora Ferreira dos Santos Morais , José Luis Tirado , Carlos Pérez-Vicente , Fabiana Villela da Motta , Pedro Lavela , Mauricio Bomio , Sergio Lavela
Na3V2(PO4)3 (NVP) is a promising cathode material for sodium-ion batteries owing to its NASICON-type framework, which enables efficient reversible sodium insertion. However, its practical performance is limited by slow charge transfer at high cycling rates and cycling instability. Here, we report a facile impregnation method to deposit Nb2O5 on NVP particles, aiming to enhance high-rate capability and long-term cycling stability. Structural and spectroscopic analyses (XRD, electron microscopy, Raman, XPS, and X-ray fluorescence spectroscopy) confirm the crystallinity of NVP and the uniform presence of Nb2O5 on particle surfaces without compromising sodium reversibility. Electrochemical measurements reveal that Nb2O5-coated samples show the highest diffusion coefficients, ensuring superior high-rate performance and cycling stability. The 3 % Nb2O5 coating delivers the highest diffusion coefficients, superior cycling stability, and sustained capacity retention at a 1C rate. Cyclic voltammetry and impedance spectroscopy indicate enhanced surface capacitance, facilitating rapid sodium storage. XPS shows the conversion of Nb2O5 into NbF5, resulting from HF scavenging, which improved interfacial stability. Extended cycling tests validate the long-term durability of the coated electrode. These results demonstrate that Nb2O5 surface modification is an effective strategy to overcome the intrinsic limitations of NVP, offering a viable route to high-performance sodium-ion batteries.
{"title":"Unlocking the performance of sodium-ion batteries by coating Na3V2(PO4)3 with Nb2O5","authors":"Débora Ferreira dos Santos Morais , José Luis Tirado , Carlos Pérez-Vicente , Fabiana Villela da Motta , Pedro Lavela , Mauricio Bomio , Sergio Lavela","doi":"10.1016/j.actphy.2025.100180","DOIUrl":"10.1016/j.actphy.2025.100180","url":null,"abstract":"<div><div>Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> (NVP) is a promising cathode material for sodium-ion batteries owing to its NASICON-type framework, which enables efficient reversible sodium insertion. However, its practical performance is limited by slow charge transfer at high cycling rates and cycling instability. Here, we report a facile impregnation method to deposit Nb<sub>2</sub>O<sub>5</sub> on NVP particles, aiming to enhance high-rate capability and long-term cycling stability. Structural and spectroscopic analyses (XRD, electron microscopy, Raman, XPS, and X-ray fluorescence spectroscopy) confirm the crystallinity of NVP and the uniform presence of Nb<sub>2</sub>O<sub>5</sub> on particle surfaces without compromising sodium reversibility. Electrochemical measurements reveal that Nb<sub>2</sub>O<sub>5</sub>-coated samples show the highest diffusion coefficients, ensuring superior high-rate performance and cycling stability. The 3 % Nb<sub>2</sub>O<sub>5</sub> coating delivers the highest diffusion coefficients, superior cycling stability, and sustained capacity retention at a 1C rate. Cyclic voltammetry and impedance spectroscopy indicate enhanced surface capacitance, facilitating rapid sodium storage. XPS shows the conversion of Nb<sub>2</sub>O<sub>5</sub> into NbF<sub>5</sub>, resulting from HF scavenging, which improved interfacial stability. Extended cycling tests validate the long-term durability of the coated electrode. These results demonstrate that Nb<sub>2</sub>O<sub>5</sub> surface modification is an effective strategy to overcome the intrinsic limitations of NVP, offering a viable route to high-performance sodium-ion batteries.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 2","pages":"Article 100180"},"PeriodicalIF":13.5,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463976","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 : 2025-09-05DOI: 10.1016/j.actphy.2025.100181
Vanita Vanita , Roland Schoch , Pascal Puphal , Hasan Yilmaz , Matthias Bauer , Oliver Clemens
In this study, we explore the potential of the RP-type bilayer manganite LaSr2Mn2O6.96 as an intercalation-based cathode material for all-solid-state fluoride ion batteries (FIBs). Structural changes of LaSr2Mn2O6.96 during fluoride intercalation and de-intercalation were analyzed viaex-situ X-ray diffraction, revealing that F− insertion induces the formation of three distinct tetragonal phases. To understand the complex behavior of these phases, we examined the changes in the Mn oxidation state and coordination environment using X-ray absorption spectroscopy and magnetic measurements. Under stack pressure (20 kN), electrochemical cycling of LaSr2Mn2O6.96 in the potential range of 1 V to −1 V exhibited a continuous increase in specific capacity from capacity of ∼30 mAh g−1 to ∼ 68 mAh g−1 over 200 cycles, with ∼99% coulombic efficiency and no signs of capacity fading. This makes the bilayer manganite LaSr2Mn2O6.96 a promising candidate for a cycling stable cathode for all-solid-state FIBs, especially under the application of stack pressure.
在这项研究中，我们探索了rp型双层锰矿LaSr2Mn2O6.96作为全固态氟离子电池（FIBs）插层阴极材料的潜力。通过x射线衍射分析了LaSr2Mn2O6.96在氟嵌入和脱嵌入过程中的结构变化，发现F−的插入诱导了三种不同的四方相的形成。为了了解这些相的复杂行为，我们使用x射线吸收光谱和磁测量检查了Mn氧化态和配位环境的变化。在堆叠压力（20 kN）下，LaSr2Mn2O6.96在1 V至−1 V的电势范围内电化学循环200次，比容量从~ 30 mAh g−1持续增加到~ 68 mAh g−1，库仑效率为~ 99%，且无容量衰减迹象。这使得双层锰酸盐LaSr2Mn2O6.96成为全固态光纤循环稳定阴极的有希望的候选者，特别是在堆叠压力的应用下。
{"title":"Structural and electrochemical behaviour of bilayer manganite LaSr2Mn2O6.96 cathode for all-solid-state fluoride ion batteries","authors":"Vanita Vanita , Roland Schoch , Pascal Puphal , Hasan Yilmaz , Matthias Bauer , Oliver Clemens","doi":"10.1016/j.actphy.2025.100181","DOIUrl":"10.1016/j.actphy.2025.100181","url":null,"abstract":"<div><div>In this study, we explore the potential of the RP-type bilayer manganite LaSr<sub>2</sub>Mn<sub>2</sub>O<sub>6.96</sub> as an intercalation-based cathode material for all-solid-state fluoride ion batteries (FIBs). Structural changes of LaSr<sub>2</sub>Mn<sub>2</sub>O<sub>6.96</sub> during fluoride intercalation and de-intercalation were analyzed <em>via</em> <em>ex-situ</em> X-ray diffraction, revealing that F<sup>−</sup> insertion induces the formation of three distinct tetragonal phases. To understand the complex behavior of these phases, we examined the changes in the Mn oxidation state and coordination environment using X-ray absorption spectroscopy and magnetic measurements. Under stack pressure (20 kN), electrochemical cycling of LaSr<sub>2</sub>Mn<sub>2</sub>O<sub>6.96</sub> in the potential range of 1 V to −1 V exhibited a continuous increase in specific capacity from capacity of ∼30 mAh g<sup>−1</sup> to ∼ 68 mAh g<sup>−1</sup> over 200 cycles, with ∼99% coulombic efficiency and no signs of capacity fading. This makes the bilayer manganite LaSr<sub>2</sub>Mn<sub>2</sub>O<sub>6.96</sub> a promising candidate for a cycling stable cathode for all-solid-state FIBs, especially under the application of stack pressure.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100181"},"PeriodicalIF":13.5,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923329","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 : 2025-09-04DOI: 10.1016/j.actphy.2025.100182
Zhenhuan Wang , Weifei Wei , Ruijie Ma , Dou Luo , Zhanxiang Chen , Jun Zhang , Liyang Yu , Gang Li , Zhenghui Luo
The design of high-performance small-molecule acceptors (SMAs) for organic solar cells (OSCs) remains a central challenge, particularly under the growing demand for environmentally friendly processing conditions. While halogenation has been widely employed to optimize electronic structures and molecular packing, its reliance on toxic halogenated solvents and the limited tunability of intermolecular interactions highlight the need for alternative strategies. In this context, core functionalization with cyano (CN) groups provides a unique opportunity, as the CN unit combines strong electron-withdrawing ability, high polarity, and linear geometry, potentially offering synergistic regulation of both optoelectronic properties and supramolecular assembly. However, systematic studies on core cyanation remain scarce, and its precise role in balancing charge transfer, molecular ordering, and energy loss in OSCs has not been thoroughly clarified.
Here, we report a cyano-functionalized benzo[a]phenazine (BP)-core SMA, denoted as NA8, to explore how core cyanation influences device performance. The introduction of the CN group reduces the intramolecular charge transfer, resulting in a blue-shifted absorption and a slightly enlarged optical bandgap compared with the non-cyanated analogue NA1. Despite this apparent drawback, NA8 demonstrates superior molecular packing, as evidenced by GIWAXS measurements showing a crystalline coherence length more than twice that of NA1 (101.3 Å vs. 44.6 Å). This improvement originates from the significantly enhanced dipole moment of NA8 (4.26 D vs. 2.21 D for NA1), which facilitates stronger electrostatic and noncovalent interactions (e.g., S···N and H···N contacts), thereby stabilizing more ordered packing motifs.
At the blend-film level, AFM reveals that PM6:NA8 exhibits a rougher yet more clearly phase-separated morphology compared with PM6:NA1, providing continuous transport pathways. Photo-CELIV measurements confirm higher carrier mobility (2.36 × 10−4 cm2 V−1 s−1 vs. 1.29 × 10−4 cm2 V−1 s−1), while transient absorption spectroscopy shows faster exciton dissociation and reduced bimolecular recombination. Together, these synergistic effects explain why the PM6:NA8 device achieves an outstanding power conversion efficiency of 19.04 % using non-halogenated o-xylene, compared with 15.14 % for PM6:NA1. The improvement primarily arises from the significantly enhanced short-circuit current density (27.35 mA cm−2) and fill factor (78.3 %), while the open-circuit voltage is only moderately reduced (0.889 V vs. 0.914 V) due to increased reorganization energy associated with C–C bond vibrations in the CN-substituted BP core. Our study identifies core cyanation as a powerful molecular engineering strategy to concurrently tune energy levels, strengthen molecular packing, and optimize nanos
设计用于有机太阳能电池（OSCs）的高性能小分子受体（sma）仍然是一个核心挑战，特别是在对环保加工条件日益增长的需求下。虽然卤化已被广泛用于优化电子结构和分子包装，但它对有毒卤化溶剂的依赖以及分子间相互作用的有限可调性突出了替代策略的必要性。在这种情况下，氰基（CN）基团的核心功能化提供了一个独特的机会，因为CN单元结合了强的吸电子能力、高极性和线性几何形状，可能提供光电性能和超分子组装的协同调节。然而，对核心氰化的系统研究仍然很少，其在平衡osc中的电荷转移、分子有序和能量损失中的确切作用尚未完全阐明。在这里，我们报告了氰化苯并[a]非那嗪(BP)-核心SMA，标记为NA8，以探索核心氰化如何影响设备性能。CN基团的引入减少了分子内电荷转移，导致蓝移吸收，与非氰化类似物NA1相比，光学带隙略有扩大。尽管有这个明显的缺点，NA8表现出优越的分子包装，正如GIWAXS测量所证明的那样，其晶体相干长度是NA1的两倍多（101.3 Å vs. 44.6 Å）。这种改进源于NA8的偶极矩显著增强（NA1为4.26 D， NA1为2.21 D），这促进了更强的静电和非共价相互作用（例如S··N和H··N接触），从而稳定了更有序的包装基序。在混合膜水平上，AFM显示PM6:NA8与PM6:NA1相比表现出更粗糙但更清晰的相分离形态，提供了连续的运输途径。光- celiv测量证实了更高的载流子迁移率（2.36 × 10−4 cm2 V−1 s−1 vs. 1.29 × 10−4 cm2 V−1 s−1），而瞬态吸收光谱显示了更快的激子解离和减少的双分子重组。总的来说，这些协同效应解释了为什么PM6:NA8器件使用非卤化邻二甲苯实现了19.04%的出色功率转换效率，而PM6:NA1器件的功率转换效率为15.14%。这种改进主要是由于显著提高了短路电流密度（27.35 mA cm−2）和填充因子（78.3%），而开路电压仅适度降低（0.889 V vs 0.914 V），这是由于cn取代的BP核心中C-C键振动相关的重组能增加。我们的研究确定了核心氰化是一种强大的分子工程策略，可以同时调节能级，加强分子包装，优化纳米级形态，为下一代有机光伏电池的设计提供有价值的指导。
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