物理化学学报最新文献

{"title":"Engineering efficient metal-organic frameworks for photocatalytic CO2 reduction","authors":"Guoqiang Peng ,&nbsp;Xiuyan Li ,&nbsp;Min Li ,&nbsp;Zhibo Su ,&nbsp;Falu Hu ,&nbsp;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 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.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 2","pages":"Article 100164"},"PeriodicalIF":13.5,"publicationDate":"2026-02-01","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}

{"title":"Structurally engineered solvent-free LiFePO4 electrodes via hot-pressing with efficient ion transport pathways for lithium extraction from brine","authors":"Hui Zhang ,&nbsp;Zijian Zhao ,&nbsp;Yajing Wang ,&nbsp;Kai Ni ,&nbsp;Yanfei Wang ,&nbsp;Liang Zhu ,&nbsp;Jianyun Liu ,&nbsp;Xiaoyu Zhao","doi":"10.1016/j.actphy.2025.100130","DOIUrl":"10.1016/j.actphy.2025.100130","url":null,"abstract":"<div><div>The development of high-mass-loading electrodes with robust ion transport characteristics is crucial for efficient electrochemical lithium extraction from brine. Herein, we report a solvent-free hot-pressing strategy to fabricate structurally engineered LiFePO₄ electrodes with enhanced electrochemical performance and mechanical stability. By integrating etched titanium foil as a current collector and multi-walled carbon nanotubes as a conductive additive, a three-dimensionally interconnected porous structure was formed, enabling accelerated ion diffusion and improved structural integrity. Micro-CT and Avizo-based analysis revealed that the dry press-coated electrodes possess higher porosity, lower tortuosity and more connected ion channels compared to conventional slurry-coated electrodes. Electrochemical tests demonstrated a significantly higher lithium-ion diffusion coefficient and lower charge transfer resistance of the dry press-coated electrodes. Under optimized conditions, the dry press-coated electrodes, possessing a mass loading of 19.4 mg cm⁻², delivered a lithium extraction capacity of 4.13 mg cm⁻² with a purity of 93.91 % over 15 cycles in simulated Uyuni brine. This work establishes a scalable hot-pressing method and elucidates its fundamental physicochemical advantages for lithium-selective electrochemical separation.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 2","pages":"Article 100130"},"PeriodicalIF":13.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414888","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}

{"title":"Core cyanation of benzo[a]phenazine acceptor enables 19.04 % binary organic solar cells with green solvent compatibility","authors":"Zhenhuan Wang ,&nbsp;Weifei Wei ,&nbsp;Ruijie Ma ,&nbsp;Dou Luo ,&nbsp;Zhanxiang Chen ,&nbsp;Jun Zhang ,&nbsp;Liyang Yu ,&nbsp;Gang Li ,&nbsp;Zhenghui Luo","doi":"10.1016/j.actphy.2025.100182","DOIUrl":"10.1016/j.actphy.2025.100182","url":null,"abstract":"&lt;div&gt;&lt;div&gt;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.&lt;/div&gt;&lt;div&gt;Here, we report a cyano-functionalized benzo[&lt;em&gt;a&lt;/em&gt;]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.&lt;/div&gt;&lt;div&gt;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&lt;sup&gt;−4&lt;/sup&gt; cm&lt;sup&gt;2&lt;/sup&gt; V&lt;sup&gt;−1&lt;/sup&gt; s&lt;sup&gt;−1&lt;/sup&gt; vs. 1.29 × 10&lt;sup&gt;−4&lt;/sup&gt; cm&lt;sup&gt;2&lt;/sup&gt; V&lt;sup&gt;−1&lt;/sup&gt; s&lt;sup&gt;−1&lt;/sup&gt;), 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 &lt;em&gt;o&lt;/em&gt;-xylene, compared with 15.14 % for PM6:NA1. The improvement primarily arises from the significantly enhanced short-circuit current density (27.35 mA cm&lt;sup&gt;−2&lt;/sup&gt;) 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","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 2","pages":"Article 100182"},"PeriodicalIF":13.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463974","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}

{"title":"Research progress on rbital hybridization in photocatalysis and electrocatalysis","authors":"Xian-Wei Lv ,&nbsp;Xinyuan Ding ,&nbsp;Jiaxing Gong ,&nbsp;Xuhuan Yan ,&nbsp;Dayong Huang ,&nbsp;Jianxin Geng ,&nbsp;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":"2026-02-01","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}

{"title":"Achieving thermal-stimulus-responsive dynamic afterglow from carbon dots by singlet-triplet energy gap engineering through covalent fixation","authors":"Zihan Cheng ,&nbsp;Kai Jiang ,&nbsp;Jun Jiang ,&nbsp;Henggang Wang ,&nbsp;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>_ST) 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>_ST of CDs from 0.46 to 0.28 eV, as designed. This Δ<em>E</em>_ST 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":"2026-02-01","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}

{"title":"Electrochemical lithium extraction by the faradaic materials: advances, challenges and enhancement approaches","authors":"Lei Wang ,&nbsp;Panpan Zhang ,&nbsp;Zhiyuan Guo ,&nbsp;Jing Wang ,&nbsp;Jie Ma ,&nbsp;Zhi-yong Ji","doi":"10.1016/j.actphy.2025.100127","DOIUrl":"10.1016/j.actphy.2025.100127","url":null,"abstract":"<div><div>The rapid growth of the electric vehicle industry has led to a surge in demand for lithium products, driving the development of advanced lithium extraction technologies. Among these, electrochemical lithium extraction has emerged as a promising approach due to its superior lithium selectivity towards competing cations (like Na⁺ and Mg²⁺), high energy efficiency, and environmental sustainability. Many works about the faradaic materials, operation modes/parameters, and cell configurations have been published. Although some reviews about electrochemical lithium extraction technology have been published, there remains a lack of comprehensive reviews that systematically summarize advancements of faradaic materials employed in lithium extraction, analyze how their nature affects the lithium extraction performance, and elucidate the relationship between performance-enhancing strategies and their impact on critical extraction metrics. Here, we systematically introduce the principle of electrochemical lithium extraction technologies and all the performance indices reported in the literature, including the lithium intercalation capacity, lithium extraction rate, capacity retention, selectivity factor (or purity), energy consumption, and current efficiency. We present a comprehensive analysis of the reported faradaic materials used to extract lithium, involving LiFePO₄, LiMn₂O₄, layered nickel cobalt manganese oxides, Li₃V₂(PO₄)₃, and Li_1.6Mn_1.6O₄, establish the interconnection between their attributes and performance, and compare the advantages and disadvantages of each material. Furthermore, we categorize and evaluate different performance-enhancing strategies, including material-design approaches (e.g., 3D structure fabrication, crystal regulation, element doping, and surface coating) and operation-optimized methods in water-flow direction, circuit operation mode, and operation parameters; we further clarify how each method influences specific aspects of electrochemical lithium extraction performance and the underlying mechanisms responsible for these improvements. The industrialization progress of electrochemical lithium extraction technology based on each faradaic material is reviewed, and the cost of these materials is introduced. By establishing a connection between material design, operational optimization, and performance outcomes, this review aims to provide valuable insights for researchers and engineers working on the next generation of faradaic materials employed in electrochemical lithium extraction and to inspire innovative approaches in faradaic material development and process optimization, paving the way for more sustainable and cost-effective lithium recovery from brines.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100127"},"PeriodicalIF":13.5,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334188","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}

{"title":"Hydroxyl-functionalized molecular engineering mitigates 2D phase barriers for efficient wide-bandgap and all-perovskite tandem solar cells","authors":"Binbin Liu ,&nbsp;Yang Chen ,&nbsp;Tianci Jia ,&nbsp;Chen Chen,&nbsp;Zhanghao Wu,&nbsp;Yuhui Liu,&nbsp;Yuhang Zhai,&nbsp;Tianshu Ma,&nbsp;Changlei Wang","doi":"10.1016/j.actphy.2025.100128","DOIUrl":"10.1016/j.actphy.2025.100128","url":null,"abstract":"<div><div>All-perovskite tandem solar cells (TSCs) demonstrate exceptional potential to overcome the single-junction efficiency limit through enhanced photon harvesting across the solar spectrum and suppressed thermalization effects, achieving theoretical power conversion efficiencies surpassing 44%. Wide-bandgap perovskites solar cells (WBG PSCs) are crucial for tandem photovoltaics, and have witnessed exponential progress during the last decade. However, these devices suffer from severe open-circuit voltage (<em>V</em>_OC) deficits, primarily due to interfacial recombination and carrier transport losses. A major contributor to these losses is the uncontrolled formation of insulating two-dimensional (2D) perovskite phases during surface passivation. Here, we introduce 4-hydroxyphenylethyl ammonium iodide (p-OHPEAI) as a multifunctional molecular additive to address this critical trade-off. Unlike conventional phenethyl ammonium iodide (PEAI), which forms the insulating 2D phase and the invert electric field by vertical molecular orientation that impedes charge extraction, the hydroxyl group (-OH) in p-OHPEAI enables parallel molecular adsorption on perovskite surfaces via synergistic interactions between amino (-NH₃) and -OH groups. This configuration effectively eliminates the formation of insulating 2D perovskite phase, passivates undercoordinated halide and lead vacancies, reducing non-radiative recombination. Additionally, the polarity of p-OHPEAI generates a dipole moment at the perovskite/electron transport layer (ETL) interface, optimizing energy-level alignment and facilitating electron extraction. By incorporating p-OHPEAI into 1.77 eV WBG PSCs, we achieved a remarkable <em>V</em>_OC of 1.344 V, corresponding to a minimal voltage deficit of 0.426 V, which is among the lowest reported <em>V</em>_OC-deficit values for the inverted WBG PSCs with bandgaps ranging from 1.75 to 1.80 eV. The optimized device delivered a power conversion efficiency (PCE) of 19.24%, demonstrating superior performance compared to conventional PEAI-passivated cells. When integrated into all-perovskite TSCs, this strategy enabled a champion PCE of 28.50% (with a certified efficiency of 28.19%). Furthermore, the devices exhibited excellent operational stability, maintaining over 90% of their initial efficiency after 350 h of continuous illumination, highlighting the robustness of the hydroxyl-driven passivation approach. The introduction of hydroxyl groups in passivation molecules provides a versatile strategy to balance defect suppression and charge transport, bridging the gap between high voltage and efficient carrier extraction.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100128"},"PeriodicalIF":13.5,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334187","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}

{"title":"Self-integrated black NiO clusters with ZnIn2S4 microspheres for photothermal-assisted hydrogen evolution by S-scheme electron transfer mechanism","authors":"Chengyan Ge ,&nbsp;Jiawei Hu ,&nbsp;Xingyu Liu ,&nbsp;Yuxi Song ,&nbsp;Chao Liu ,&nbsp;Zhigang Zou","doi":"10.1016/j.actphy.2025.100154","DOIUrl":"10.1016/j.actphy.2025.100154","url":null,"abstract":"<div><div>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 <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":"2026-01-01","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}

{"title":"Unveiling the direct-to-indirect bandgap transition mechanism in the photocatalytic hydrogen evolution of ZnxCd1−xS solid solution","authors":"Huoshuai Huang ,&nbsp;Zhidong Wei ,&nbsp;Jiawei Yan ,&nbsp;Jiasheng Chi ,&nbsp;Qianxiang Su ,&nbsp;Mingxia Chen ,&nbsp;Zhi Jiang ,&nbsp;Yangzhou Sun ,&nbsp;Wenfeng Shangguan","doi":"10.1016/j.actphy.2025.100141","DOIUrl":"10.1016/j.actphy.2025.100141","url":null,"abstract":"<div><div>Solid solution strategy could improve the photocatalytic performance thermodynamically, yet the study focusing on the carrier dynamics of the solid solution catalysts was equally important. Herein, a series of Zn_<em>x</em>Cd_{1−<em>x</em>}S solid solutions were successfully synthesized based on band structure regulation, and the carrier dynamics were investigated by femtosecond transient absorption spectroscopy (TAS) and DFT, which unveiled a variation of the mixed direct-to-indirect bandgap transition mechanism in Zn_<em>x</em>Cd_{1−<em>x</em>}S solid solution. The indirect bandgap exhibited a lower photocarrier recombination rate and, more importantly, could also serve as a trapping center for photocarrier, thus promoting the efficiency of charge separation. Consequently, Zn_<em>x</em>Cd_{1−<em>x</em>}S solid solutions achieved an approximately eleven-fold enhancement in the hydrogen evolution rate (1426.66 μmol h⁻¹) relative to that of bare CdS (129.83 μmol h⁻¹) under visible light (&gt;420 nm). This work proposed that the enhanced photocatalytic performance could originate from both thermodynamic and kinetic aspects simultaneously, and that the alteration of the photocarrier transition mechanism is one of the main factors affecting the kinetics.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100141"},"PeriodicalIF":13.5,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195916","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}

{"title":"Covalent bond modulation of charge transfer for sensitive heavy metal ion analysis in a self-powered electrochemical sensing platform","authors":"Yun Chen ,&nbsp;Daijie Deng ,&nbsp;Li Xu ,&nbsp;Xingwang Zhu ,&nbsp;Henan Li ,&nbsp;Chengming Sun","doi":"10.1016/j.actphy.2025.100144","DOIUrl":"10.1016/j.actphy.2025.100144","url":null,"abstract":"<div><div>Rational design of photoelectric active materials for photoanodes in photocatalytic fuel cells is crucial for developing highly sensitive self-powered electrochemical sensors. Achieving directional migration and shortening transmission pathways of charge in photoanodes remains a fundamental challenge for enhancing the oxygen evolution reaction performance of photocatalytic fuel cells. Herein, tungsten species atomically dispersed on carbon-rich graphitic carbon nitride (W-CN-C) with the N–W–O covalent bond was designed as the photoanode for constructing a self-powered photocatalytic fuel cell sensing of heavy metal copper ions. W-CN-C was synthesized by self-assembly, exfoliation, and thermal-induced treatment processes. The N–W–O covalent bonds by anchoring tungsten atoms on carbon-rich carbon nitride served as an interfacial charge transport channel, facilitating the separation and migration of charge carriers. The carbon content increase by forming a carbon-rich structure can enhance π-electron delocalization in the W-CN-C, significantly broadening sunlight utilization range. The dispersed tungsten atoms provide effectively active sites, promoting the kinetics of the oxygen evolution reaction between the W-CN-C photoanode and electrolyte interface. The synergistic effects significantly enhance the visible light absorption ability and charge separation and transfer efficiency, improving the photoelectric conversion efficiency of W-CN-C photoanode, exhibiting superior oxygen evolution reaction performance, leading to the amplified open circuit potential in the photocatalytic fuel cell system based on excellent oxygen reduction reaction performance of the Pt@C electrocatalyst cathode. The specific identification probe for copper ions was effectively anchored on the W-CN-C photoanode to construct a self-powered photocatalytic fuel cell sensing platform for copper ions detection. The complex formed by copper ions with the probe hindered electron transport at the W-CN-C photoanode, altering the output detection signal of the photocatalytic fuel cell, thus demonstrating a broad detection range spanning five orders of magnitude (2.0× 10⁻² ∼ 9.2 × 10² nmolmol∙L⁻¹), a low limit of detection (7.0 pmol∙L⁻¹), high selectivity against common interferents, and applicability for detecting heavy metal copper ions in the aquatic environment. Furthermore, the platform allowed for self-powered and portable determination of copper ions using a multimeter as a signal output device, achieving a detection range of 0.25 ∼ 1.3 × 10² nmol∙L⁻¹ and a limit of 84 pmol∙L⁻¹. This work proposes an approach for developing a high-performance photoanode utilizing atomically dispersed metals to introduce covalent bonds as charge transfer channels, paving the way for highly sensitive self-powered electrochemical sensors for environmental monitoring.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100144"},"PeriodicalIF":13.5,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145359557","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}