Pub Date : 2025-08-21DOI: 10.1016/j.actphy.2025.100158
Mian Wei , Chang Cheng , Bowen He , Bei Cheng , Kezhen Qi , Chuanbiao Bie
S-scheme heterojunctions have garnered significant attention for efficient photocatalytic H2 evolution due to their superior charge separation and maximized redox potential. In this study, we developed a novel pyrene-benzothiadiazole conjugated polymer (YBTPy) through Yamamoto coupling, followed by the in situ deposition of CdS nanoparticles via a solvothermal method to construct a CdS/YBTPy S-scheme heterojunction photocatalyst. The optimized composite, designated as CP5, demonstrated a hydrogen production rate of 5.01 mmol h−1 g−1, representing a 4.2-fold enhancement compared to pristine CdS (1.20 mmol h−1 g−1). The characteristic S-scheme charge transfer pathway at the heterojunction interface was elucidated using in situ irradiated X-ray photoelectron spectroscopy in conjunction with Kelvin probe force microscopy. Additionally, femtosecond transient absorption spectroscopy was employed to investigate the dynamics of photogenerated charge carriers. This work provides a new theoretical foundation for the design of organic–inorganic hybrid S-scheme photocatalytic systems.
s -方案异质结由于其优越的电荷分离和最大的氧化还原电位而引起了人们对高效光催化氢演化的极大关注。在这项研究中，我们通过山本偶联开发了一种新型的芘-苯并噻唑共轭聚合物（YBTPy），然后通过溶剂热法原位沉积CdS纳米粒子，构建了CdS/YBTPy S-scheme异质结光催化剂。优化后的复合材料CP5的产氢率为5.01 mmol h−1 g−1，比原始CdS （1.20 mmol h−1 g−1）提高了4.2倍。利用原位辐照x射线光电子能谱结合开尔文探针力显微镜分析了异质结界面S-scheme电荷转移的特征路径。此外，利用飞秒瞬态吸收光谱研究了光生载流子的动力学。该工作为有机-无机杂化S-scheme光催化体系的设计提供了新的理论基础。
{"title":"Inorganic-organic CdS/YBTPy S-scheme photocatalyst for efficient hydrogen production and its mechanism","authors":"Mian Wei , Chang Cheng , Bowen He , Bei Cheng , Kezhen Qi , Chuanbiao Bie","doi":"10.1016/j.actphy.2025.100158","DOIUrl":"10.1016/j.actphy.2025.100158","url":null,"abstract":"<div><div>S-scheme heterojunctions have garnered significant attention for efficient photocatalytic H<sub>2</sub> evolution due to their superior charge separation and maximized redox potential. In this study, we developed a novel pyrene-benzothiadiazole conjugated polymer (YBTPy) through Yamamoto coupling, followed by the <em>in situ</em> deposition of CdS nanoparticles <em>via</em> a solvothermal method to construct a CdS/YBTPy S-scheme heterojunction photocatalyst. The optimized composite, designated as CP5, demonstrated a hydrogen production rate of 5.01 mmol h<sup>−1</sup> g<sup>−1</sup>, representing a 4.2-fold enhancement compared to pristine CdS (1.20 mmol h<sup>−1</sup> g<sup>−1</sup>). The characteristic S-scheme charge transfer pathway at the heterojunction interface was elucidated using <em>in situ</em> irradiated X-ray photoelectron spectroscopy in conjunction with Kelvin probe force microscopy. Additionally, femtosecond transient absorption spectroscopy was employed to investigate the dynamics of photogenerated charge carriers. This work provides a new theoretical foundation for the design of organic–inorganic hybrid S-scheme photocatalytic systems.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100158"},"PeriodicalIF":13.5,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144917953","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 : 2025-08-20DOI: 10.1016/j.actphy.2025.100170
Yinghao Zhang , Huaxin Liu , Hanrui Ding , Zhi Zheng , Wentao Deng , Guoqiang Zou , Laiqiang Xu , Hongshuai Hou , Xiaobo Ji
In response to the growing demand for renewable energy, rechargeable batteries, such as lithium-ion batteries, are finding increasingly widespread applications in energy storage and daily life. Currently, the pursuit of batteries with high specific energy and enhanced safety is constrained by limitations in the electrolyte bulk and interfacial reactions. Consequently, modulating the electrolyte and its interphases is key to overcoming current bottlenecks and developing next-generation batteries. As an emerging nanomaterial, the rich surface functional groups and dopable sites of carbon dots (CDs) enable them to simultaneously regulate bulk ion dynamics and interface stability through surface chemistry design, showcasing immense potential in addressing the critical challenges in electrolytes. This review systematically summarizes the cutting-edge applications of CDs in electrolytes for lithium-ion, sodium-ion, and zinc-ion batteries. It introduces the structural characteristics, classification, and synthesis methods of CDs, and outlines their multifaceted roles as additives in liquid electrolytes, fillers in solid-state electrolytes, and interfacial regulators for solid composite electrolytes. A special focus is placed on elucidating the mechanisms of CDs in regulating ion deposition, constructing functionalized interfacial layers, and optimizing the electrolyte microenvironment. Finally, this review discusses the challenges and future outlook for CDs in electrolyte engineering, aiming to provide new perspectives and theoretical support for the design of battery systems with high specific energy and high safety.
{"title":"The application of carbon dots in electrolytes of advanced batteries","authors":"Yinghao Zhang , Huaxin Liu , Hanrui Ding , Zhi Zheng , Wentao Deng , Guoqiang Zou , Laiqiang Xu , Hongshuai Hou , Xiaobo Ji","doi":"10.1016/j.actphy.2025.100170","DOIUrl":"10.1016/j.actphy.2025.100170","url":null,"abstract":"<div><div>In response to the growing demand for renewable energy, rechargeable batteries, such as lithium-ion batteries, are finding increasingly widespread applications in energy storage and daily life. Currently, the pursuit of batteries with high specific energy and enhanced safety is constrained by limitations in the electrolyte bulk and interfacial reactions. Consequently, modulating the electrolyte and its interphases is key to overcoming current bottlenecks and developing next-generation batteries. As an emerging nanomaterial, the rich surface functional groups and dopable sites of carbon dots (CDs) enable them to simultaneously regulate bulk ion dynamics and interface stability through surface chemistry design, showcasing immense potential in addressing the critical challenges in electrolytes. This review systematically summarizes the cutting-edge applications of CDs in electrolytes for lithium-ion, sodium-ion, and zinc-ion batteries. It introduces the structural characteristics, classification, and synthesis methods of CDs, and outlines their multifaceted roles as additives in liquid electrolytes, fillers in solid-state electrolytes, and interfacial regulators for solid composite electrolytes. A special focus is placed on elucidating the mechanisms of CDs in regulating ion deposition, constructing functionalized interfacial layers, and optimizing the electrolyte microenvironment. Finally, this review discusses the challenges and future outlook for CDs in electrolyte engineering, aiming to provide new perspectives and theoretical support for the design of battery systems with high specific energy and high safety.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100170"},"PeriodicalIF":13.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923322","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 : 2025-08-20DOI: 10.1016/j.actphy.2025.100169
Zihan Cheng , Kai Jiang , Jun Jiang , Henggang Wang , Hengwei Lin
Integrating stimuli-responsive luminescence with dynamic emission properties offers a powerful strategy to enhance information encryption through multi-level authentication systems. By rationally tuning the singlet-triplet energy gap (ΔEST) of a material, simultaneous activation of phosphorescence (Phos) and delayed fluorescence (DF) can be achieved, enabling programmable dynamic afterglow behavior. In this work, we report the first carbon dot (CD)-based thermoresponsive dynamic afterglow material, synthesized via in situ covalent immobilization of CDs within a cyanuric acid matrix. The resulting system demonstrates a thermally driven green-to-blue afterglow transition across a wide temperature range (273.15–423.15 K), exhibiting dual-mode thermochromic afterglow (TCA) and time-resolved afterglow (TRA) characteristics. Notably, a blue-to-green afterglow transition occurs above the threshold temperature of 348.15 K, where TRA dominates due to temperature-dependent exciton redistribution. This synergistic TCA-TRA interplay endows the material with unprecedented dynamic afterglow modulation capabilities. Structural and photophysical analyses confirm that covalent fixation reduces the ΔEST of CDs from 0.46 to 0.28 eV, as designed. This ΔEST engineering enables thermal control over the Phos/DF equilibrium, directly governing the observed dynamic emission. Finally, the potential applications of the prepared material in thermal monitoring and high-security information protection are also demonstrated.
{"title":"Achieving thermal-stimulus-responsive dynamic afterglow from carbon dots by singlet-triplet energy gap engineering through covalent fixation","authors":"Zihan Cheng , Kai Jiang , Jun Jiang , Henggang Wang , Hengwei Lin","doi":"10.1016/j.actphy.2025.100169","DOIUrl":"10.1016/j.actphy.2025.100169","url":null,"abstract":"<div><div>Integrating stimuli-responsive luminescence with dynamic emission properties offers a powerful strategy to enhance information encryption through multi-level authentication systems. By rationally tuning the singlet-triplet energy gap (Δ<em>E</em><sub>ST</sub>) of a material, simultaneous activation of phosphorescence (Phos) and delayed fluorescence (DF) can be achieved, enabling programmable dynamic afterglow behavior. In this work, we report the first carbon dot (CD)-based thermoresponsive dynamic afterglow material, synthesized <em>via in situ</em> covalent immobilization of CDs within a cyanuric acid matrix. The resulting system demonstrates a thermally driven green-to-blue afterglow transition across a wide temperature range (273.15–423.15 K), exhibiting dual-mode thermochromic afterglow (TCA) and time-resolved afterglow (TRA) characteristics. Notably, a blue-to-green afterglow transition occurs above the threshold temperature of 348.15 K, where TRA dominates due to temperature-dependent exciton redistribution. This synergistic TCA-TRA interplay endows the material with unprecedented dynamic afterglow modulation capabilities. Structural and photophysical analyses confirm that covalent fixation reduces the Δ<em>E</em><sub>ST</sub> of CDs from 0.46 to 0.28 eV, as designed. This Δ<em>E</em><sub>ST</sub> engineering enables thermal control over the Phos/DF equilibrium, directly governing the observed dynamic emission. Finally, the potential applications of the prepared material in thermal monitoring and high-security information protection are also demonstrated.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 2","pages":"Article 100169"},"PeriodicalIF":13.5,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464342","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 : 2025-08-19DOI: 10.1016/j.actphy.2025.100166
Ze Luo , Yukun Zhu , Yadan luo , Guangmin Ren , Yonghong Wang , Hua Tang
Addressing the global energy and environmental crisis necessitates the development of sustainable photocatalytic technologies capable of efficiently converting biomass into high-value chemicals and clean fuels. In this study, we develop a novel one-dimensional/two-dimensional (1D/2D) In2O3/ZnIn2S4 S-scheme heterojunction photocatalyst through in situ growth process. This rationally designed architecture combines rod-like In2O3 with sheet-like ZnIn2S4 nanosheets, facilitating directional charge transport and providing a high density of active sites. Consequently, the optimized In2O3/ZnIn2S4 heterojunction achieved a 5-hydroxymethylfurfural (HMF) conversion rate of 81.6 % with a high selectivity of 78.2 % toward 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). Furthermore, it exhibited a hydrogen (H2) evolution rate of 257.69 μmol g−1 h−1 under 420 nm LED irradiation. These results demonstrate the efficacy of S-scheme heterojunctions in enabling spatial charge separation and boosting photocatalytic activity, offering a promising strategy for solar-driven biomass valorization and sustainable H2 production.
{"title":"Photocatalytic selective oxidation of 5-hydroxymethylfurfural coupled with H2 evolution over In2O3/ZnIn2S4 S-scheme heterojunction","authors":"Ze Luo , Yukun Zhu , Yadan luo , Guangmin Ren , Yonghong Wang , Hua Tang","doi":"10.1016/j.actphy.2025.100166","DOIUrl":"10.1016/j.actphy.2025.100166","url":null,"abstract":"<div><div>Addressing the global energy and environmental crisis necessitates the development of sustainable photocatalytic technologies capable of efficiently converting biomass into high-value chemicals and clean fuels. In this study, we develop a novel one-dimensional/two-dimensional (1D/2D) In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> S-scheme heterojunction photocatalyst through <em>in situ</em> growth process. This rationally designed architecture combines rod-like In<sub>2</sub>O<sub>3</sub> with sheet-like ZnIn<sub>2</sub>S<sub>4</sub> nanosheets, facilitating directional charge transport and providing a high density of active sites. Consequently, the optimized In<sub>2</sub>O<sub>3</sub>/ZnIn<sub>2</sub>S<sub>4</sub> heterojunction achieved a 5-hydroxymethylfurfural (HMF) conversion rate of 81.6 % with a high selectivity of 78.2 % toward 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). Furthermore, it exhibited a hydrogen (H<sub>2</sub>) evolution rate of 257.69 μmol g<sup>−1</sup> h<sup>−1</sup> under 420 nm LED irradiation. These results demonstrate the efficacy of S-scheme heterojunctions in enabling spatial charge separation and boosting photocatalytic activity, offering a promising strategy for solar-driven biomass valorization and sustainable H<sub>2</sub> production.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100166"},"PeriodicalIF":13.5,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923325","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 : 2025-08-19DOI: 10.1016/j.actphy.2025.100164
Guoqiang Peng , Xiuyan Li , Min Li , Zhibo Su , Falu Hu , Guowei Zhou
Over the past decades, excessive CO2 emissions have led to various environmental issues. Solar-driven photocatalytic conversion of CO2 into valuable chemicals offers a promising solution for energy and environmental problems. Recently, a class of porous coordination polymers that self-assemble from organic linkers and metal ions or clusters, metal-organic frameworks (MOFs), have been widely explored for photoinduced CO2 conversion because of their great CO2 capture ability and adjustable structures. However, the development of MOFs with high efficiency for CO2 conversion remains a significant challenge. In this review, we elaborate on four key engineering strategies for constructing efficient MOFs toward photocatalytic CO2 reduction: ligand engineering, secondary building unit (SBU) engineering, defect engineering, and morphology engineering. These strategies focus on optimizing key structural properties of MOFs that critically influence their catalytic performance in CO2 photoreduction, notably light absorption, CO2 adsorption capacity, and charge separation and transport. The established design principles and modulation strategies demonstrate broad applicability and can be extended to guide the rational design of diverse MOF-based functional systems. Furthermore, we critically evaluate the advantages and disadvantages of each strategy, highlighting their specific contributions and inherent limitations. Finally, we outline the development prospects and identify promising future research directions for MOF-based photocatalytic CO2 reduction.
{"title":"Engineering efficient metal-organic frameworks for photocatalytic CO2 reduction","authors":"Guoqiang Peng , Xiuyan Li , Min Li , Zhibo Su , Falu Hu , Guowei Zhou","doi":"10.1016/j.actphy.2025.100164","DOIUrl":"10.1016/j.actphy.2025.100164","url":null,"abstract":"<div><div>Over the past decades, excessive CO<sub>2</sub> emissions have led to various environmental issues. Solar-driven photocatalytic conversion of CO<sub>2</sub> into valuable chemicals offers a promising solution for energy and environmental problems. Recently, a class of porous coordination polymers that self-assemble from organic linkers and metal ions or clusters, metal-organic frameworks (MOFs), have been widely explored for photoinduced CO<sub>2</sub> conversion because of their great CO<sub>2</sub> capture ability and adjustable structures. However, the development of MOFs with high efficiency for CO<sub>2</sub> conversion remains a significant challenge. In this review, we elaborate on four key engineering strategies for constructing efficient MOFs toward photocatalytic CO<sub>2</sub> reduction: ligand engineering, secondary building unit (SBU) engineering, defect engineering, and morphology engineering. These strategies focus on optimizing key structural properties of MOFs that critically influence their catalytic performance in CO<sub>2</sub> photoreduction, notably light absorption, CO<sub>2</sub> adsorption capacity, and charge separation and transport. The established design principles and modulation strategies demonstrate broad applicability and can be extended to guide the rational design of diverse MOF-based functional systems. Furthermore, we critically evaluate the advantages and disadvantages of each strategy, highlighting their specific contributions and inherent limitations. Finally, we outline the development prospects and identify promising future research directions for MOF-based photocatalytic CO<sub>2</sub> reduction.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 2","pages":"Article 100164"},"PeriodicalIF":13.5,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145360974","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 : 2025-08-19DOI: 10.1016/j.actphy.2025.100165
Chunhui Gao , Lurong Li , Guanwei Peng , Jinni Shen , Wenxin Dai , Zizhong Zhang
Integrating photocatalytic cofactor regeneration with enzymatic cascades enables sustainable CO2 valorization but faces challenges like limited hydrogen sources and homogeneous mediator and photogenerated holes-induced enzyme deactivation. This study demonstrates that the low oxidation potential of L-ascorbic acid (L-AA) can enhance proton supply and promote the formation of [Cp∗Rh(bpy)H]+ intermediates. Only 0.26 mg (≈0.12 mmol L−1) [Cp∗Rh(bpy)Cl]Cl can achieve efficient/selective reduced nicotinamide adenine dinucleotide (NADH) regeneration, which is more than twice as effective as the typical sacrificial agent triethanolamine (TEOA). A novel strategy was developed via electrostatic self-assembly of [Cp∗Rh(bpy)H2O]2+ onto CdIn2S4 microsphere photocatalysts. This innovative integration physically separated free mediators and photogenerated holes from enzymes, effectively suppressing enzyme deactivation through spatial compartmentalization. The optimal integrated photocatalytic system achieved 90 % NADH regeneration efficiency within 40 min of 420 nm light irradiation, outperforming previously reported systems. When coupled with formate dehydrogenase (FDH), the integrated system achieved formic acid generation rates of 443.5 μmol g−1 h−1 (one light−dark cycle) and 202.7 μmol g−1 h−1 (continuous light), representing 1.2- and 3.2-fold improvements over free mediator systems, respectively. This study provides an efficient and sustainable new strategy for light driven coenzyme regeneration and enzyme catalyzed CO2 synthesis of high value-added chemicals.
{"title":"Efficient photocatalytic NADH regeneration and enzymatic CO2 reduction over [Cp∗Rh(bpy)H2O]2+ self-assembled CdIn2S4 flower-like microspheres","authors":"Chunhui Gao , Lurong Li , Guanwei Peng , Jinni Shen , Wenxin Dai , Zizhong Zhang","doi":"10.1016/j.actphy.2025.100165","DOIUrl":"10.1016/j.actphy.2025.100165","url":null,"abstract":"<div><div>Integrating photocatalytic cofactor regeneration with enzymatic cascades enables sustainable CO<sub>2</sub> valorization but faces challenges like limited hydrogen sources and homogeneous mediator and photogenerated holes-induced enzyme deactivation. This study demonstrates that the low oxidation potential of L-ascorbic acid (L-AA) can enhance proton supply and promote the formation of [Cp∗Rh(bpy)H]<sup>+</sup> intermediates. Only 0.26 mg (≈0.12 mmol L<sup>−1</sup>) [Cp∗Rh(bpy)Cl]Cl can achieve efficient/selective reduced nicotinamide adenine dinucleotide (NADH) regeneration, which is more than twice as effective as the typical sacrificial agent triethanolamine (TEOA). A novel strategy was developed <em>via</em> electrostatic self-assembly of [Cp∗Rh(bpy)H<sub>2</sub>O]<sup>2+</sup> onto CdIn<sub>2</sub>S<sub>4</sub> microsphere photocatalysts. This innovative integration physically separated free mediators and photogenerated holes from enzymes, effectively suppressing enzyme deactivation through spatial compartmentalization. The optimal integrated photocatalytic system achieved 90 % NADH regeneration efficiency within 40 min of 420 nm light irradiation, outperforming previously reported systems. When coupled with formate dehydrogenase (FDH), the integrated system achieved formic acid generation rates of 443.5 μmol g<sup>−1</sup> h<sup>−1</sup> (one light−dark cycle) and 202.7 μmol g<sup>−1</sup> h<sup>−1</sup> (continuous light), representing 1.2- and 3.2-fold improvements over free mediator systems, respectively. This study provides an efficient and sustainable new strategy for light driven coenzyme regeneration and enzyme catalyzed CO<sub>2</sub> synthesis of high value-added chemicals.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 3","pages":"Article 100165"},"PeriodicalIF":13.5,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923327","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 : 2025-08-19DOI: 10.1016/j.actphy.2025.100168
Jiayao Wang , Guixu Pan , Ning Wang , Shihan Wang , Yaolin Zhu , Yunfeng Li
Donor-π-Acceptor (D-π-A) conjugated polymers represent an emerging class of materials featuring alternating electron donor (D), π-bridge (π), and electron acceptor (A) units, which exhibit significant potential in enhancing visible-light absorption and optimizing charge separation and redistribution. To overcome the limitations of graphitic carbon nitride (g-C3N4) while capitalizing on the structural merits of D-π-A systems, a series of 4-aromatic amine derivatives modified g-C3N4 photocatalysts was designed and synthesized through precise molecular level regulation with tailored local electron delocalization. This strategy allows for a systematic investigation of the relationship between electron delocalization extent and photocatalytic H2O2 production. Furthermore, the electron-withdrawing induction effect for regulating electron delocalization results in a substantial enhancement of photoinduced electron transfer to surface reactive sites. The as-synthesized optimum photocatalyst exhibits a remarkable H2O2 production performance, which is 30.44 times higher than that of the pristine g-C3N4. The mechanism study reveals that the photocatalytic H2O2 production in D-π-A-type g-C3N4 proceeds primarily via a two-electron oxygen reduction reaction (ORR).
{"title":"Preparation of donor-π-acceptor type graphitic carbon nitride photocatalytic systems via molecular level regulation for high-efficient H2O2 production","authors":"Jiayao Wang , Guixu Pan , Ning Wang , Shihan Wang , Yaolin Zhu , Yunfeng Li","doi":"10.1016/j.actphy.2025.100168","DOIUrl":"10.1016/j.actphy.2025.100168","url":null,"abstract":"<div><div>Donor-<em>π</em>-Acceptor (D-<em>π</em>-A) conjugated polymers represent an emerging class of materials featuring alternating electron donor (D), <em>π</em>-bridge (<em>π</em>), and electron acceptor (A) units, which exhibit significant potential in enhancing visible-light absorption and optimizing charge separation and redistribution. To overcome the limitations of graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) while capitalizing on the structural merits of D-<em>π</em>-A systems, a series of 4-aromatic amine derivatives modified g-C<sub>3</sub>N<sub>4</sub> photocatalysts was designed and synthesized through precise molecular level regulation with tailored local electron delocalization. This strategy allows for a systematic investigation of the relationship between electron delocalization extent and photocatalytic H<sub>2</sub>O<sub>2</sub> production. Furthermore, the electron-withdrawing induction effect for regulating electron delocalization results in a substantial enhancement of photoinduced electron transfer to surface reactive sites. The as-synthesized optimum photocatalyst exhibits a remarkable H<sub>2</sub>O<sub>2</sub> production performance, which is 30.44 times higher than that of the pristine g-C<sub>3</sub>N<sub>4</sub>. The mechanism study reveals that the photocatalytic H<sub>2</sub>O<sub>2</sub> production in D-<em>π</em>-A-type g-C<sub>3</sub>N<sub>4</sub> proceeds primarily via a two-electron oxygen reduction reaction (ORR).</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100168"},"PeriodicalIF":13.5,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913613","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 : 2025-08-15DOI: 10.1016/j.actphy.2025.100160
Xin Zhou , Yiting Huo , Songyu Yang , Bowen He , Xiaojing Wang , Zhen Wu , Jianjun Zhang
Covalent organic frameworks (COFs), recognized for their precisely tunable microstructures and high surface area, are promising photocatalysts for hydrogen peroxide (H2O2) production. However, the critical influence of pH on the stability of COF during the photocatalytic H2O2 production remains poorly understood. In this work, the photocatalytic H2O2 production performance of an imine-linked COF is significantly enhanced through a simple protonation strategy. Crucially, the protonated COF exhibits excellent stability under weakly acidic conditions (pH ≥ 3), but undergoes irreversible hydrolyzed under strongly acidic conditions (pH < 3). The protonation occurs specifically at the nitrogen atoms of imine units and serves a dual function: it suppresses ultrafast charge recombination (as revealed by femtosecond transient absorption spectroscopy) and directly provides a proton source for H2O2 generation. Moreover, fluoride ions (F−) are introduced into the photocatalytic system to further improve the photocatalytic H2O2 production rate. The strong electronegativity of F− facilitates electron transfer from COF to F−, thus realizing the spatial separation of photogenerated carriers. Mechanistic studies confirm that H2O2 production follows a two-electron oxygen reduction reaction pathway. These findings elucidate the pH-dependent stability and activity of protonated COFs, provide fundamental insights into charge carrier dynamics, and establishe design principles to develop highly efficient and stable COF-based photocatalysts for solar-driven H2O2 generation.
{"title":"Understanding the effect of pH on protonated COF during photocatalytic H2O2 production by femtosecond transient absorption spectroscopy","authors":"Xin Zhou , Yiting Huo , Songyu Yang , Bowen He , Xiaojing Wang , Zhen Wu , Jianjun Zhang","doi":"10.1016/j.actphy.2025.100160","DOIUrl":"10.1016/j.actphy.2025.100160","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs), recognized for their precisely tunable microstructures and high surface area, are promising photocatalysts for hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) production. However, the critical influence of pH on the stability of COF during the photocatalytic H<sub>2</sub>O<sub>2</sub> production remains poorly understood. In this work, the photocatalytic H<sub>2</sub>O<sub>2</sub> production performance of an imine-linked COF is significantly enhanced through a simple protonation strategy. Crucially, the protonated COF exhibits excellent stability under weakly acidic conditions (pH ≥ 3), but undergoes irreversible hydrolyzed under strongly acidic conditions (pH < 3). The protonation occurs specifically at the nitrogen atoms of imine units and serves a dual function: it suppresses ultrafast charge recombination (as revealed by femtosecond transient absorption spectroscopy) and directly provides a proton source for H<sub>2</sub>O<sub>2</sub> generation. Moreover, fluoride ions (F<sup>−</sup>) are introduced into the photocatalytic system to further improve the photocatalytic H<sub>2</sub>O<sub>2</sub> production rate. The strong electronegativity of F<sup>−</sup> facilitates electron transfer from COF to F<sup>−</sup>, thus realizing the spatial separation of photogenerated carriers. Mechanistic studies confirm that H<sub>2</sub>O<sub>2</sub> production follows a two-electron oxygen reduction reaction pathway. These findings elucidate the pH-dependent stability and activity of protonated COFs, provide fundamental insights into charge carrier dynamics, and establishe design principles to develop highly efficient and stable COF-based photocatalysts for solar-driven H<sub>2</sub>O<sub>2</sub> generation.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100160"},"PeriodicalIF":13.5,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144907852","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 : 2025-08-14DOI: 10.1016/j.actphy.2025.100152
Xinwan Zhao , Yue Cao , Minjun Lei , Zhiliang Jin , Noritatsu Tsubaki
Two-dimensional covalent organic frameworks (COFs) are considered among the most potential crystalline porous materials for solar-driven hydrogen production. However, it is usually necessary to introduce noble metal cocatalysts to boost the hydrogen evolution capacity of COFs. In this work, a unique S-scheme heterojunction structured TtTfp-COF/NiS composite material was effectively developed by growing metal sulfide on the typical two-dimensional covalent organic framework TtTfp-COF through a simple solvothermal synthesis method. In this structure, linear structure of rod-like NiS is more stable and convenient for further surface modification. It also provides key active sites and promotes efficient electron transfer, significantly enhancing the hydrogen evolution efficiency. The covalent organic framework enhances charge carrier transport efficiency by controlling the spatial organization of precursors and ligands. It is indicated by the experimental findings that a hydrogen evolution rate of 5978 μmol g−1 h−1 can be achieved for the NT-20 sample, which about 11.5 times higher than that of the initial TtTfp-COF (520 μmol g−1 h−1). In addition, the material exhibits a notable quantum efficiency of 1.96 % when exposed to 420 nm illumination. Both experimental results and theoretical analyses have been confirmed to improve the hydrogen evolution rate via photocatalysis and the charge transfer mechanism within the S-scheme heterojunction has been thoroughly elucidated. The design and development of non-precious metal COF-based photocatalysts are provided with new insights in this article, and new ideas for the construction of S-scheme heterojunctions are offered by the synergistic combination of inorganic and organic materials in photocatalysis.
{"title":"Constructing S-scheme heterojunctions by integrating covalent organic frameworks with transition metal sulfides for efficient noble-metal-free photocatalytic hydrogen evolution","authors":"Xinwan Zhao , Yue Cao , Minjun Lei , Zhiliang Jin , Noritatsu Tsubaki","doi":"10.1016/j.actphy.2025.100152","DOIUrl":"10.1016/j.actphy.2025.100152","url":null,"abstract":"<div><div>Two-dimensional covalent organic frameworks (COFs) are considered among the most potential crystalline porous materials for solar-driven hydrogen production. However, it is usually necessary to introduce noble metal cocatalysts to boost the hydrogen evolution capacity of COFs. In this work, a unique S-scheme heterojunction structured TtTfp-COF/NiS composite material was effectively developed by growing metal sulfide on the typical two-dimensional covalent organic framework TtTfp-COF through a simple solvothermal synthesis method. In this structure, linear structure of rod-like NiS is more stable and convenient for further surface modification. It also provides key active sites and promotes efficient electron transfer, significantly enhancing the hydrogen evolution efficiency. The covalent organic framework enhances charge carrier transport efficiency by controlling the spatial organization of precursors and ligands. It is indicated by the experimental findings that a hydrogen evolution rate of 5978 μmol g<sup>−1</sup> h<sup>−1</sup> can be achieved for the NT-20 sample, which about 11.5 times higher than that of the initial TtTfp-COF (520 μmol g<sup>−1</sup> h<sup>−1</sup>). In addition, the material exhibits a notable quantum efficiency of 1.96 % when exposed to 420 nm illumination. Both experimental results and theoretical analyses have been confirmed to improve the hydrogen evolution rate <em>via</em> photocatalysis and the charge transfer mechanism within the S-scheme heterojunction has been thoroughly elucidated. The design and development of non-precious metal COF-based photocatalysts are provided with new insights in this article, and new ideas for the construction of S-scheme heterojunctions are offered by the synergistic combination of inorganic and organic materials in photocatalysis.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100152"},"PeriodicalIF":13.5,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144894773","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 : 2025-08-14DOI: 10.1016/j.actphy.2025.100159
Ruyan Liu , Zhenrui Ni , Olim Ruzimuradov , Khayit Turayev , Tao Liu , Luo Yu , Panyong Kuang
While H2 features high energy density, environmental friendliness, and renewability, its efficient production is limited by the sluggish kinetics of the oxygen evolution reaction (OER). Here, we report a Pt@PtNi3 core@shell alloy electrocatalyst that, through Ni incorporation, modulates the occupancy of Pt 5d antibonding orbitals and simultaneously enhances both hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) activities. The optimized Pt@PtNi3-500 delivers an ultralow overpotential of 21 mV at 10 mA cm−2 for HER under acidic conditions and a low onset potential of 1.27 V for UOR under alkaline conditions, surpassing monometallic Pt and Ni counterparts. When employed in an asymmetric acid-alkaline electrolyzer (HER/UOR), Pt@PtNi3-500 achieves a 68.3 % reduction in electrical energy consumption for H2 production compared to traditional alkaline water splitting (HER/OER). Mechanistic investigations reveal that appropriate Ni incorporation in Pt@PtNi3 increases the occupancy of Pt 5d–H 1s antibonding orbitals, which not only reinforces H+ adsorption but also weakens the overly strong H∗ binding. Simultaneously, it reduces the energy barrier for ∗NH2 dehydrogenation, thereby synergistically accelerating both H2 generation and urea decomposition. This work provides new insights into the design of alloy electrocatalysts for high-efficiency H2 production.
虽然H2具有高能量密度、环境友好和可再生的特点，但其高效生产受到析氧反应（OER）动力学缓慢的限制。在这里，我们报道了一种Pt@PtNi3 core@shell合金电催化剂，通过Ni的加入，调节Pt 5d反键轨道的占用，同时提高析氢反应（HER）和尿素氧化反应（UOR）的活性。优化后的Pt@PtNi3-500在酸性条件下为HER提供了21 mV、10 mA cm−2的超低过电位，在碱性条件下为UOR提供了1.27 V的低起始电位，超过了单金属Pt和Ni。当在不对称酸碱性电解槽（HER/UOR）中使用时，Pt@PtNi3-500与传统的碱性水分解（HER/OER）相比，H2生产的电能消耗降低了68.3%。机制研究表明，Pt@PtNi3中适当的Ni掺入增加了Pt 5d-H 1s反键轨道的占用，这不仅加强了H+的吸附，而且减弱了过强的H *结合。同时，它降低了NH2脱氢的能垒，从而协同加速H2生成和尿素分解。本研究为高效制氢合金电催化剂的设计提供了新的思路。
{"title":"Ni-induced modulation of Pt 5d–H 1s antibonding orbitals for enhanced hydrogen evolution and urea oxidation","authors":"Ruyan Liu , Zhenrui Ni , Olim Ruzimuradov , Khayit Turayev , Tao Liu , Luo Yu , Panyong Kuang","doi":"10.1016/j.actphy.2025.100159","DOIUrl":"10.1016/j.actphy.2025.100159","url":null,"abstract":"<div><div>While H<sub>2</sub> features high energy density, environmental friendliness, and renewability, its efficient production is limited by the sluggish kinetics of the oxygen evolution reaction (OER). Here, we report a Pt@PtNi<sub>3</sub> core@shell alloy electrocatalyst that, through Ni incorporation, modulates the occupancy of Pt 5<em>d</em> antibonding orbitals and simultaneously enhances both hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) activities. The optimized Pt@PtNi<sub>3</sub>-500 delivers an ultralow overpotential of 21 mV at 10 mA cm<sup>−2</sup> for HER under acidic conditions and a low onset potential of 1.27 V for UOR under alkaline conditions, surpassing monometallic Pt and Ni counterparts. When employed in an asymmetric acid-alkaline electrolyzer (HER/UOR), Pt@PtNi<sub>3</sub>-500 achieves a 68.3 % reduction in electrical energy consumption for H<sub>2</sub> production compared to traditional alkaline water splitting (HER/OER). Mechanistic investigations reveal that appropriate Ni incorporation in Pt@PtNi<sub>3</sub> increases the occupancy of Pt 5<em>d</em>–H 1<em>s</em> antibonding orbitals, which not only reinforces H<sup>+</sup> adsorption but also weakens the overly strong H∗ binding. Simultaneously, it reduces the energy barrier for ∗NH<sub>2</sub> dehydrogenation, thereby synergistically accelerating both H<sub>2</sub> generation and urea decomposition. This work provides new insights into the design of alloy electrocatalysts for high-efficiency H<sub>2</sub> production.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100159"},"PeriodicalIF":13.5,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144892887","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号