Pub Date : 2025-08-13DOI: 10.1016/j.actphy.2025.100157
Jiangyuan Qiu , Tao Yu , Junxin Chen , Wenxuan Li , Xiaoxuan Zhang , Jinsheng Li , Rui Guo , Zaiyin Huang , Xuanwen Liu
Although the design of heterojunction piezoelectric catalysts has significantly enhanced catalytic activity, the regulatory mechanisms of heterojunction interfaces on surface potential wells during piezoelectric processes and their impact on carrier migration still lack systematic investigation. This work constructs an enhance interface interaction heterointerface between amorphous FeOOH and Bi12O17Cl2 (BOC) in Bi12O17Cl2@FeOOH through a self-assembly strategy. This strong interfacial interaction significantly enhances interface polarity can substantially suppress the stress-responsive capability of surface charges on BOC (maximum reduction reached as high as 63 %–98 % of original value). This significantly reduces the depth of surface potential wells during piezoelectric processes, thereby effectively weakening piezoelectric charge confinement while promoting charge transfer. Concurrently, Bi–O–Fe chemical bonds formed at the interface and establish charge transport channels. These synergistic mechanisms elevate the H2O2 production rate to 3.04 mmol g−1 h−1 for participate in the piezoelectric self-Fenton reaction and the removal rate of total organic carbon increased 3 fold (18.6 % vs 55.8 %).
{"title":"Modulate surface potential well depth of Bi12O17Cl2 by FeOOH in Bi12O17Cl2@FeOOH heterojunction to boost piezoelectric charge transfer and piezo-self-Fenton catalysis","authors":"Jiangyuan Qiu , Tao Yu , Junxin Chen , Wenxuan Li , Xiaoxuan Zhang , Jinsheng Li , Rui Guo , Zaiyin Huang , Xuanwen Liu","doi":"10.1016/j.actphy.2025.100157","DOIUrl":"10.1016/j.actphy.2025.100157","url":null,"abstract":"<div><div>Although the design of heterojunction piezoelectric catalysts has significantly enhanced catalytic activity, the regulatory mechanisms of heterojunction interfaces on surface potential wells during piezoelectric processes and their impact on carrier migration still lack systematic investigation. This work constructs an enhance interface interaction heterointerface between amorphous FeOOH and Bi<sub>12</sub>O<sub>17</sub>Cl<sub>2</sub> (BOC) in Bi<sub>12</sub>O<sub>17</sub>Cl<sub>2</sub>@FeOOH through a self-assembly strategy. This strong interfacial interaction significantly enhances interface polarity can substantially suppress the stress-responsive capability of surface charges on BOC (maximum reduction reached as high as 63 %–98 % of original value). This significantly reduces the depth of surface potential wells during piezoelectric processes, thereby effectively weakening piezoelectric charge confinement while promoting charge transfer. Concurrently, Bi–O–Fe chemical bonds formed at the interface and establish charge transport channels. These synergistic mechanisms elevate the H<sub>2</sub>O<sub>2</sub> production rate to 3.04 mmol g<sup>−1</sup> h<sup>−1</sup> for participate in the piezoelectric self-Fenton reaction and the removal rate of total organic carbon increased 3 fold (18.6 % <em>vs</em> 55.8 %).</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100157"},"PeriodicalIF":13.5,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145264484","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 : 2025-08-11DOI: 10.1016/j.actphy.2025.100156
Chunyuan Kang , Xiaoyu Li , Fan Yang, Bai Yang
Carbonized polymer dots (CPDs) have emerged as promising room temperature phosphorescent (RTP) materials owing to their tunable luminescence and facile synthesis. However, current strategies relying on hydrogen/covalent bond for luminescence enhancement suffer from limited phosphorescence intensity, and color diversity (primarily green). This work proposes constructing ionic-bond crosslinked network as a novel design strategy to address these limitations. Owing to the high strength, non-directionality and non-saturation of ionic bond, crosslinked networks are constructed to immobilize chromophores and suppress non-radiative transitions. By incorporating lithium ions into poly(acrylic acid)-based CPDs, the photoluminescence quantum yield is dramatically enhanced from 1.1 % to 48.4 %, with a 40-fold increase in phosphorescence intensity. Further introduction of zinc ions enables tunable RTP emission from green to yellow via transition metal doping. This strategy achieves effective regulation of RTP intensity and wavelength in CPDs, providing a versatile platform for designing advanced organic phosphorescent materials with tailored RTP properties.
{"title":"Ionic-bond crosslinked carbonized polymer dots for tunable and enhanced room temperature phosphorescence","authors":"Chunyuan Kang , Xiaoyu Li , Fan Yang, Bai Yang","doi":"10.1016/j.actphy.2025.100156","DOIUrl":"10.1016/j.actphy.2025.100156","url":null,"abstract":"<div><div>Carbonized polymer dots (CPDs) have emerged as promising room temperature phosphorescent (RTP) materials owing to their tunable luminescence and facile synthesis. However, current strategies relying on hydrogen/covalent bond for luminescence enhancement suffer from limited phosphorescence intensity, and color diversity (primarily green). This work proposes constructing ionic-bond crosslinked network as a novel design strategy to address these limitations. Owing to the high strength, non-directionality and non-saturation of ionic bond, crosslinked networks are constructed to immobilize chromophores and suppress non-radiative transitions. By incorporating lithium ions into poly(acrylic acid)-based CPDs, the photoluminescence quantum yield is dramatically enhanced from 1.1 % to 48.4 %, with a 40-fold increase in phosphorescence intensity. Further introduction of zinc ions enables tunable RTP emission from green to yellow via transition metal doping. This strategy achieves effective regulation of RTP intensity and wavelength in CPDs, providing a versatile platform for designing advanced organic phosphorescent materials with tailored RTP properties.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100156"},"PeriodicalIF":13.5,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145264485","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 : 2025-08-09DOI: 10.1016/j.actphy.2025.100155
Chengxin Chen , Hongfei Shi , Xiaoyan Cai , Liang Mao , Zhe Chen
Designing and establishing dual-functional S-scheme heterojunction photocatalysts with efficient separation of photoproduced carriers and intense oxidation/reduction capabilities holds immense practical value for their photocatalytic application in energy conversion and environmental purification. Herein, a novel series of x% CoWO4/CdIn2S4 (x% reflects the weight ratio of CWO to CIS; x = 10, 20, 30, 40 and 50) composites have been systematically designed and synthesized via electrospinning technique and hydrothermal methods. Their photocatalytic properties were assessed through HCHO removal and H2 generation under visible light. As anticipated, the optimized 30 % CWO/CIS heterojunction presented an outstanding H2 generation performance of 865.14 μmol g−1 h−1 with AQE = 3.6 % at λ = 420 nm, and achieved a 69 % removal percentage for HCHO within 1 h. Meanwhile, the pathway of HCHO degradation was presented based on insitu diffuse reflectance infrared Fourier transform spectroscopy (insitu DRIFTS) technique. The great catalytic performance was primarily ascribed to the enhancement in the visible–light absorption, number of active sites, and the construction of S-scheme heterojunction. Furthermore, the S-scheme charge transfer mechanism for the CWO/CIS catalyst system has been confirmed by insitu X–ray photoelectron spectroscopy (insitu XPS), electron spin resonance data, radical capturing experiments, and density functional theory (DFT) calculations. This research contributes valuable understanding for the systematic design and development of bifunctional S-scheme heterojunctions for gaseous pollutants removal and H2 production.
{"title":"Enhanced bifunctional photocatalytic performances for H2 evolution and HCHO elimination with an S-scheme CoWO4/CdIn2S4 heterojunction","authors":"Chengxin Chen , Hongfei Shi , Xiaoyan Cai , Liang Mao , Zhe Chen","doi":"10.1016/j.actphy.2025.100155","DOIUrl":"10.1016/j.actphy.2025.100155","url":null,"abstract":"<div><div>Designing and establishing dual-functional S-scheme heterojunction photocatalysts with efficient separation of photoproduced carriers and intense oxidation/reduction capabilities holds immense practical value for their photocatalytic application in energy conversion and environmental purification. Herein, a novel series of <em>x</em>% CoWO<sub>4</sub>/CdIn<sub>2</sub>S<sub>4</sub> (<em>x</em>% reflects the weight ratio of CWO to CIS; <em>x</em> = 10, 20, 30, 40 and 50) composites have been systematically designed and synthesized <em>via</em> electrospinning technique and hydrothermal methods. Their photocatalytic properties were assessed through HCHO removal and H<sub>2</sub> generation under visible light. As anticipated, the optimized 30 % CWO/CIS heterojunction presented an outstanding H<sub>2</sub> generation performance of 865.14 μmol g<sup>−1</sup> h<sup>−1</sup> with AQE = 3.6 % at <em>λ</em> = 420 nm, and achieved a 69 % removal percentage for HCHO within 1 h. Meanwhile, the pathway of HCHO degradation was presented based on <em>in</em> <em>situ</em> diffuse reflectance infrared Fourier transform spectroscopy (<em>in</em> <em>situ</em> DRIFTS) technique. The great catalytic performance was primarily ascribed to the enhancement in the visible–light absorption, number of active sites, and the construction of S-scheme heterojunction. Furthermore, the S-scheme charge transfer mechanism for the CWO/CIS catalyst system has been confirmed by <em>in</em> <em>situ</em> X–ray photoelectron spectroscopy (<em>in</em> <em>situ</em> XPS), electron spin resonance data, radical capturing experiments, and density functional theory (DFT) calculations. This research contributes valuable understanding for the systematic design and development of bifunctional S-scheme heterojunctions for gaseous pollutants removal and H<sub>2</sub> production.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 12","pages":"Article 100155"},"PeriodicalIF":13.5,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144842251","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 : 2025-08-08DOI: 10.1016/j.actphy.2025.100154
Chengyan Ge , Jiawei Hu , Xingyu Liu , Yuxi Song , Chao Liu , Zhigang Zou
Hydrogen (H2) production technology utilizing solar energy is an essential strategy for questing carbon-neutral, but designing the optimal heterostructured photocatalysts is one of the great challenges. To date, the self-integration of highly-dispersed black NiO clusters with ZIS microspheres was successfully achieved during the solvothermal process. These constructed NiO/ZIS S-scheme heterostructured composites could provide more active for photocatalytic H2 evolution (PHE) under visible light. The optimal 2-NiO/ZIS showed the best PHE rate of 2474.0 μmol g−1 h−1, highest apparent quantum yield (AQY) value of 36.67 % and excellent structural stability. Furthermore, NiO/ZIS composites also exhibited the high PHE rates in natural seawater. The charge separation behaviors of the catalyst were systematically evaluated using advanced spectroscopic characterization techniques, specifically in-situ XPS, time-resolved photoluminescence (TRPL) tested in water and transient absorption spectroscopy (TAS). The experimental analysis and theoretical calculation results elucidated the S-scheme charge transfer mechanism for NiO/ZIS. The promoted PHE activity was ascribed to the combined effect between black NiO clusters and ZIS, which enhanced light harvesting ability, accelerated charge carrier transportation and separation, remained high redox ability, and improved surface reaction kinetics. This study offers the insights into constructing S-scheme heterostructured composites with photothermal effect.
{"title":"Self-integrated black NiO clusters with ZnIn2S4 microspheres for photothermal-assisted hydrogen evolution by S-scheme electron transfer mechanism","authors":"Chengyan Ge , Jiawei Hu , Xingyu Liu , Yuxi Song , Chao Liu , Zhigang Zou","doi":"10.1016/j.actphy.2025.100154","DOIUrl":"10.1016/j.actphy.2025.100154","url":null,"abstract":"<div><div>Hydrogen (H<sub>2</sub>) production technology utilizing solar energy is an essential strategy for questing carbon-neutral, but designing the optimal heterostructured photocatalysts is one of the great challenges. To date, the self-integration of highly-dispersed black NiO clusters with ZIS microspheres was successfully achieved during the solvothermal process. These constructed NiO/ZIS S-scheme heterostructured composites could provide more active for photocatalytic H<sub>2</sub> evolution (PHE) under visible light. The optimal 2-NiO/ZIS showed the best PHE rate of 2474.0 μmol g<sup>−1</sup> h<sup>−1</sup>, highest apparent quantum yield (AQY) value of 36.67 % and excellent structural stability. Furthermore, NiO/ZIS composites also exhibited the high PHE rates in natural seawater. The charge separation behaviors of the catalyst were systematically evaluated using advanced spectroscopic characterization techniques, specifically <em>in-situ</em> XPS, time-resolved photoluminescence (TRPL) tested in water and transient absorption spectroscopy (TAS). The experimental analysis and theoretical calculation results elucidated the S-scheme charge transfer mechanism for NiO/ZIS. The promoted PHE activity was ascribed to the combined effect between black NiO clusters and ZIS, which enhanced light harvesting ability, accelerated charge carrier transportation and separation, remained high redox ability, and improved surface reaction kinetics. This study offers the insights into constructing S-scheme heterostructured composites with photothermal effect.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100154"},"PeriodicalIF":13.5,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195945","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 : 2025-08-08DOI: 10.1016/j.actphy.2025.100149
Chengxiao Zhao , Zhaolin Li , Dongfang Wu , Xiaofei Yang
Covalent triazine frameworks (CTFs) represent an attractive family of metal-free visible light-responsive covalent organic frameworks (COFs), possessing promising characteristics such as large specific surface area, rich nitrogen content, permanent porosity, and high thermal and chemical stability for photocatalytic hydrogen production via water splitting. Nevertheless, the majority of CTFs are confronted with difficulty in chemical synthesis and generally suffer from low electric conductivity and severe photogenerated charge carrier recombination during photocatalytic hydrogen evolution reaction (HER). The hydrogen-evolving performance highly depends on the structure of π-conjugated CTFs and the synthetic methods, and controlled synthesis of well-defined nanostructures is still highly challenging. In this work, we report the organic acid-catalyzed synthesis of porous CTF nanoarchitectures templated by mesoporous silica molecular sieve SBA-15 with a highly ordered hexagonal structure. The SBA-15 templated CTF-S2 nanorods exhibited a substantial increase in photocatalytic HER efficiency, with an impressive 14-fold enhancement compared to the micro-sized bulk CTF-1 (4.1 μmol h−1). This remarkable improvement in the photocatalytic HER over SBA-templated CTF-S2 nanostructure is attributed to the extended visible light absorption, accelerated charge carrier transfer and the optimized band structure.
{"title":"SBA-15 templated covalent triazine frameworks for boosted photocatalytic hydrogen production","authors":"Chengxiao Zhao , Zhaolin Li , Dongfang Wu , Xiaofei Yang","doi":"10.1016/j.actphy.2025.100149","DOIUrl":"10.1016/j.actphy.2025.100149","url":null,"abstract":"<div><div>Covalent triazine frameworks (CTFs) represent an attractive family of metal-free visible light-responsive covalent organic frameworks (COFs), possessing promising characteristics such as large specific surface area, rich nitrogen content, permanent porosity, and high thermal and chemical stability for photocatalytic hydrogen production via water splitting. Nevertheless, the majority of CTFs are confronted with difficulty in chemical synthesis and generally suffer from low electric conductivity and severe photogenerated charge carrier recombination during photocatalytic hydrogen evolution reaction (HER). The hydrogen-evolving performance highly depends on the structure of <em>π</em>-conjugated CTFs and the synthetic methods, and controlled synthesis of well-defined nanostructures is still highly challenging. In this work, we report the organic acid-catalyzed synthesis of porous CTF nanoarchitectures templated by mesoporous silica molecular sieve SBA-15 with a highly ordered hexagonal structure. The SBA-15 templated CTF-S2 nanorods exhibited a substantial increase in photocatalytic HER efficiency, with an impressive 14-fold enhancement compared to the micro-sized bulk CTF-1 (4.1 μmol h<sup>−1</sup>). This remarkable improvement in the photocatalytic HER over SBA-templated CTF-S2 nanostructure is attributed to the extended visible light absorption, accelerated charge carrier transfer and the optimized band structure.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100149"},"PeriodicalIF":13.5,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195917","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}
Tandem S-scheme heterojunctions have emerged as a highly promising innovation in photocatalysis, offering an effective solution for environmental remediation. Unlike traditional Z-scheme or type-II photocatalysts, the S-scheme architecture selectively retains high-energy photocarriers that actively participate in redox reactions. This unique mechanism enhances charge separation, strengthens internal electric fields, and enhance light absorption. However, the single junction of S-scheme suffers from low quantum efficiency. Therefore, engineering a multicomponent system with S-scheme effectively improve the photocatalytic properties. Tandem S-scheme systems consist of multiple semiconductors/materials with staggered energy band positions to create a stepwise or directional charge transferal mechanism. This stepwise potential gradient is responsible for more enhanced charge separation, light absorption, redox ability, stability, and overall photocatalytic activity. This article provides an in-depth overview of the principles governing tandem S-scheme heterojunctions, discussing the design of tandem S-scheme heterojunctions through semiconductor pairing, co-catalyst addition, and mediator inclusion for maximum charge mobility and minimum recombination. The various synthesis pathways are explored along with the kinetics and thermodynamics of tandem S-scheme heterojunction. A range of advanced characterization tools, including density functional theory (DFT) simulations, in-situ X-ray photoelectron spectroscopy (XPS), transient absorption spectroscopy (TAS), photoluminescence (PL), and electrochemical impedance spectroscopy (EIS) studies are discussed, which together offer valuable insight into electronic behaviours and interfacial dynamics. Applications of these heterojunctions are discussed across major domains such as carbon dioxide reduction, H2 evolution, and degradation of organic pollutants. While the potential is clear, challenges such as complex synthesis procedures, material stability, and scalability still need to be addressed. To overcome the limitations, the article suggests future research paths. Overall, tandem S-scheme heterojunctions stand out as an excellent approach for building efficient and sustainable photocatalytic technologies.
{"title":"Designing tandem S-scheme photo-catalytic systems: Mechanistic insights, characterization techniques, and applications","authors":"Rohit Kumar , Anita Sudhaik , Aftab Asalam Pawaz Khan , Van-Huy Nguyen , Archana Singh , Pardeep Singh , Sourbh Thakur , Pankaj Raizada","doi":"10.1016/j.actphy.2025.100150","DOIUrl":"10.1016/j.actphy.2025.100150","url":null,"abstract":"<div><div>Tandem S-scheme heterojunctions have emerged as a highly promising innovation in photocatalysis, offering an effective solution for environmental remediation. Unlike traditional Z-scheme or type-II photocatalysts, the S-scheme architecture selectively retains high-energy photocarriers that actively participate in redox reactions. This unique mechanism enhances charge separation, strengthens internal electric fields, and enhance light absorption. However, the single junction of S-scheme suffers from low quantum efficiency. Therefore, engineering a multicomponent system with S-scheme effectively improve the photocatalytic properties. Tandem S-scheme systems consist of multiple semiconductors/materials with staggered energy band positions to create a stepwise or directional charge transferal mechanism. This stepwise potential gradient is responsible for more enhanced charge separation, light absorption, redox ability, stability, and overall photocatalytic activity. This article provides an in-depth overview of the principles governing tandem S-scheme heterojunctions, discussing the design of tandem S-scheme heterojunctions through semiconductor pairing, co-catalyst addition, and mediator inclusion for maximum charge mobility and minimum recombination. The various synthesis pathways are explored along with the kinetics and thermodynamics of tandem S-scheme heterojunction. A range of advanced characterization tools, including density functional theory (DFT) simulations, <em>in-situ</em> X-ray photoelectron spectroscopy (XPS), transient absorption spectroscopy (TAS), photoluminescence (PL), and electrochemical impedance spectroscopy (EIS) studies are discussed, which together offer valuable insight into electronic behaviours and interfacial dynamics. Applications of these heterojunctions are discussed across major domains such as carbon dioxide reduction, H<sub>2</sub> evolution, and degradation of organic pollutants. While the potential is clear, challenges such as complex synthesis procedures, material stability, and scalability still need to be addressed. To overcome the limitations, the article suggests future research paths. Overall, tandem S-scheme heterojunctions stand out as an excellent approach for building efficient and sustainable photocatalytic technologies.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 11","pages":"Article 100150"},"PeriodicalIF":13.5,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826479","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 : 2025-08-07DOI: 10.1016/j.actphy.2025.100153
Xinyu Xu , Jiale Lu , Bo Su , Jiayi Chen , Xiong Chen , Sibo Wang
The selective oxidation of methane to value-added chemicals under mild conditions presents a sustainable yet challenging route, hindered by sluggish CH4 activation and overoxidation. Herein, we report a delicate strategy combining Ti doping and Au loading to construct a high-performance Au/Ti-CeO2 photocatalyst for ethane production from oxidative methane coupling. The optimized catalyst achieves a C2H6 production rate of 2971.4 μmol g−1 h−1 with 85.1 % C2+ selectivity, stably operating over 20 reaction cycles. In situ X-ray photoelectron spectroscopy, electron paramagnetic resonance, and diffuse reflectance infrared Fourier transform spectroscopy analyses reveal that Ti doping introduces impurity energy levels into CeO2, promoting directional electron migration to surface Au nanoparticles (NPs) via a built-in electric field. The Au NPs act as electron accumulation sites to activate O2, facilitate ∗CH3 radical coupling into C2H6, and stabilize reactive intermediates, thus enhancing charge separation and suppressing intermediate overoxidation. This study highlights the significance of synergistic modulation via elemental doping and cocatalyst engineering in tuning charge dynamics and surface reactivity for efficient photocatalytic methane conversion.
{"title":"Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO2","authors":"Xinyu Xu , Jiale Lu , Bo Su , Jiayi Chen , Xiong Chen , Sibo Wang","doi":"10.1016/j.actphy.2025.100153","DOIUrl":"10.1016/j.actphy.2025.100153","url":null,"abstract":"<div><div>The selective oxidation of methane to value-added chemicals under mild conditions presents a sustainable yet challenging route, hindered by sluggish CH<sub>4</sub> activation and overoxidation. Herein, we report a delicate strategy combining Ti doping and Au loading to construct a high-performance Au/Ti-CeO<sub>2</sub> photocatalyst for ethane production from oxidative methane coupling. The optimized catalyst achieves a C<sub>2</sub>H<sub>6</sub> production rate of 2971.4 μmol g<sup>−1</sup> h<sup>−1</sup> with 85.1 % C<sub>2+</sub> selectivity, stably operating over 20 reaction cycles. <em>In situ</em> X-ray photoelectron spectroscopy, electron paramagnetic resonance, and diffuse reflectance infrared Fourier transform spectroscopy analyses reveal that Ti doping introduces impurity energy levels into CeO<sub>2</sub>, promoting directional electron migration to surface Au nanoparticles (NPs) <em>via</em> a built-in electric field. The Au NPs act as electron accumulation sites to activate O<sub>2</sub>, facilitate ∗CH<sub>3</sub> radical coupling into C<sub>2</sub>H<sub>6</sub>, and stabilize reactive intermediates, thus enhancing charge separation and suppressing intermediate overoxidation. This study highlights the significance of synergistic modulation <em>via</em> elemental doping and cocatalyst engineering in tuning charge dynamics and surface reactivity for efficient photocatalytic methane conversion.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 11","pages":"Article 100153"},"PeriodicalIF":13.5,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144841274","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 : 2025-08-07DOI: 10.1016/j.actphy.2025.100151
Xian-Wei Lv , Xinyuan Ding , Jiaxing Gong , Xuhuan Yan , Dayong Huang , Jianxin Geng , Zhong-Yong Yuan
The conversion efficiency and stability of energy-related devices are significantly influenced by the photocatalysts and electrocatalysts. Orbital hybridization has emerged as a crucial strategy to enhance catalytic performance, with significant advancements made in recent years. This review focuses on the progress, challenges, and future prospects of orbital hybridization in photocatalysis and electrocatalysis. It begins with the fundamentals of orbital hybridization, covering basic principles and three typical classifications (reaction-level, structure-level, and cascaded orbital hybridization). It further introduces the vital roles of orbital hybridization in improving bonding efficiency, intrinsic activity, selectivity, and stability of the catalysts. Subsequently, recent advances in tuning orbital hybridization to enhance various photocatalytic and electrocatalytic reactions (e.g., HER, OER, ORR, and NRR) are highlighted. After that, modulation strategies (e.g., alloying, heteroatom doping, heterostructure construction, defect engineering, and coordination environment modulation) for orbital hybridization are summarized and discussed from both structural and reaction perspectives. Finally, this review presents the challenges faced in utilizing orbital hybridization to improve catalyst performance and outlines future prospects. By summarizing design strategies related to orbital hybridization, it offers new insights for the tailored construction and optimization of high-activity catalysts, advancing efficient and sustainable energy conversion and storage technologies.
{"title":"Research progress on rbital hybridization in photocatalysis and electrocatalysis","authors":"Xian-Wei Lv , Xinyuan Ding , Jiaxing Gong , Xuhuan Yan , Dayong Huang , Jianxin Geng , Zhong-Yong Yuan","doi":"10.1016/j.actphy.2025.100151","DOIUrl":"10.1016/j.actphy.2025.100151","url":null,"abstract":"<div><div>The conversion efficiency and stability of energy-related devices are significantly influenced by the photocatalysts and electrocatalysts. Orbital hybridization has emerged as a crucial strategy to enhance catalytic performance, with significant advancements made in recent years. This review focuses on the progress, challenges, and future prospects of orbital hybridization in photocatalysis and electrocatalysis. It begins with the fundamentals of orbital hybridization, covering basic principles and three typical classifications (reaction-level, structure-level, and cascaded orbital hybridization). It further introduces the vital roles of orbital hybridization in improving bonding efficiency, intrinsic activity, selectivity, and stability of the catalysts. Subsequently, recent advances in tuning orbital hybridization to enhance various photocatalytic and electrocatalytic reactions (e.g., HER, OER, ORR, and NRR) are highlighted. After that, modulation strategies (e.g., alloying, heteroatom doping, heterostructure construction, defect engineering, and coordination environment modulation) for orbital hybridization are summarized and discussed from both structural and reaction perspectives. Finally, this review presents the challenges faced in utilizing orbital hybridization to improve catalyst performance and outlines future prospects. By summarizing design strategies related to orbital hybridization, it offers new insights for the tailored construction and optimization of high-activity catalysts, advancing efficient and sustainable energy conversion and storage technologies.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 2","pages":"Article 100151"},"PeriodicalIF":13.5,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145340341","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 : 2025-08-05DOI: 10.1016/j.actphy.2025.100147
Qishen Wang , Changzhao Chen , Mengqing Li , Lingmin Wu , Kai Dai
This study presents an innovative photocatalytic system utilizing waste biomass resources for sustainable synthesis of hydrogen peroxide (H2O2) and high-value lignin derivatives. A lignin derived carbon quantum dots (LCQDs) loaded S-scheme heterojunction photocatalyst LCQDs/Bi2WO6 (LCD/BWO) was synthesized via hydrothermal method. The LCD/BWO composite demonstrates exceptional H2O2 production rate (3.776 mmol h−1 g−1) and maintains 89.72 % activity retention after 5 cycles under visible light irradiation, representing a 5.97-fold enhancement over catalyst BWO-A. The performance leap stems from synergistic effects between LCQDs and oxygen vacancies (OVs) defects: the unique up-conversion luminescence of LCQDs combined with S-scheme charge transfer mechanism enhances light absorption and carrier separation efficiency, while interfacial OVs act as electron traps to prolong carrier lifetime. In situ electron paramagnetic resonance (In situ EPR) analysis revealed substantial generation of •O2− and •OH radicals on catalyst surfaces. Band structure characterization confirms optimized H2O2 synthesis through consecutive single-electron reactions. Synergistic regulation of band positions significantly enhances oxygen reduction reaction (ORR) and water oxidation reaction (WOR) capabilities. As lignin primarily originates from agricultural/forestry waste, this work not only provides new design strategies for efficient photocatalytic systems but also advances high-value utilization of waste biomass resources.
{"title":"Lignin derived carbon quantum dots and oxygen vacancies coregulated S-scheme LCQDs/Bi2WO6 heterojunction for photocatalytic H2O2 production","authors":"Qishen Wang , Changzhao Chen , Mengqing Li , Lingmin Wu , Kai Dai","doi":"10.1016/j.actphy.2025.100147","DOIUrl":"10.1016/j.actphy.2025.100147","url":null,"abstract":"<div><div>This study presents an innovative photocatalytic system utilizing waste biomass resources for sustainable synthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and high-value lignin derivatives. A lignin derived carbon quantum dots (LCQDs) loaded S-scheme heterojunction photocatalyst LCQDs/Bi<sub>2</sub>WO<sub>6</sub> (LCD/BWO) was synthesized <em>via</em> hydrothermal method. The LCD/BWO composite demonstrates exceptional H<sub>2</sub>O<sub>2</sub> production rate (3.776 mmol h<sup>−1</sup> g<sup>−1</sup>) and maintains 89.72 % activity retention after 5 cycles under visible light irradiation, representing a 5.97-fold enhancement over catalyst BWO-A. The performance leap stems from synergistic effects between LCQDs and oxygen vacancies (OVs) defects: the unique up-conversion luminescence of LCQDs combined with S-scheme charge transfer mechanism enhances light absorption and carrier separation efficiency, while interfacial OVs act as electron traps to prolong carrier lifetime. <em>In situ</em> electron paramagnetic resonance (<em>In situ</em> EPR) analysis revealed substantial generation of •O<sub>2</sub><sup>−</sup> and •OH radicals on catalyst surfaces. Band structure characterization confirms optimized H<sub>2</sub>O<sub>2</sub> synthesis through consecutive single-electron reactions. Synergistic regulation of band positions significantly enhances oxygen reduction reaction (ORR) and water oxidation reaction (WOR) capabilities. As lignin primarily originates from agricultural/forestry waste, this work not only provides new design strategies for efficient photocatalytic systems but also advances high-value utilization of waste biomass resources.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 11","pages":"Article 100147"},"PeriodicalIF":13.5,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144809381","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 : 2025-08-05DOI: 10.1016/j.actphy.2025.100148
Yiting Huo , Xin Zhou , Feifan Zhao , Chenbin Ai , Zhen Wu , Zhidong Chang , Bicheng Zhu
The conversion of CO2 into value-added hydrocarbons via photocatalysis holds great promise for sustainable energy, yet achieving high activity and selectivity remains challenging. Herein, a novel TiO2/CdS heterostructured photocatalyst exhibits exceptional performance in CO2 photoreduction. The optimized catalyst delivers a 4.2-fold increase in CH4 production rate compared to pristine TiO2, with a remarkable 65.4 % selectivity toward CH4 (34.6 % CO). The enhanced activity arises from the unique morphology, facilitating CO2 adsorption and mass transfer, and the intimate S-scheme heterojunction between CdS and TiO2, which boosts charge separation while preserving strong redox potentials. Critically, femtosecond transient absorption spectroscopy (fs-TAS) combined with in situ DRIFTS provides direct evidence for the S-scheme pathway and identifies sulfur sites on CdS as key for stabilizing ∗CH3O, ∗CHO and ∗CO intermediates, steering selectivity toward CH4. In addition, theoretical calculations based on density functional theory (DFT) further complement the experimental findings. The calculations confirm the electronic structure characteristics of the S-scheme heterojunction, revealing the energy levels and charge transfer mechanisms at the atomic scale. This not only deepens our understanding of the photocatalytic process but also provides a theoretical basis for further optimizing the photocatalyst design. Overall, our work demonstrates the outstanding performance of the TiO2/CdS heterostructured photocatalyst in CO2 photoreduction.
{"title":"Boosting photocatalytic CO2 methanation through TiO2/CdS S-scheme heterojunction and fs-TAS mechanism study","authors":"Yiting Huo , Xin Zhou , Feifan Zhao , Chenbin Ai , Zhen Wu , Zhidong Chang , Bicheng Zhu","doi":"10.1016/j.actphy.2025.100148","DOIUrl":"10.1016/j.actphy.2025.100148","url":null,"abstract":"<div><div>The conversion of CO<sub>2</sub> into value-added hydrocarbons <em>via</em> photocatalysis holds great promise for sustainable energy, yet achieving high activity and selectivity remains challenging. Herein, a novel TiO<sub>2</sub>/CdS heterostructured photocatalyst exhibits exceptional performance in CO<sub>2</sub> photoreduction. The optimized catalyst delivers a 4.2-fold increase in CH<sub>4</sub> production rate compared to pristine TiO<sub>2</sub>, with a remarkable 65.4 % selectivity toward CH<sub>4</sub> (34.6 % CO). The enhanced activity arises from the unique morphology, facilitating CO<sub>2</sub> adsorption and mass transfer, and the intimate S-scheme heterojunction between CdS and TiO<sub>2</sub>, which boosts charge separation while preserving strong redox potentials. Critically, femtosecond transient absorption spectroscopy (fs-TAS) combined with in situ DRIFTS provides direct evidence for the S-scheme pathway and identifies sulfur sites on CdS as key for stabilizing ∗CH<sub>3</sub>O, ∗CHO and ∗CO intermediates, steering selectivity toward CH<sub>4</sub>. In addition, theoretical calculations based on density functional theory (DFT) further complement the experimental findings. The calculations confirm the electronic structure characteristics of the S-scheme heterojunction, revealing the energy levels and charge transfer mechanisms at the atomic scale. This not only deepens our understanding of the photocatalytic process but also provides a theoretical basis for further optimizing the photocatalyst design. Overall, our work demonstrates the outstanding performance of the TiO<sub>2</sub>/CdS heterostructured photocatalyst in CO<sub>2</sub> photoreduction.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 11","pages":"Article 100148"},"PeriodicalIF":13.5,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826433","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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