Pub Date : 2025-07-18DOI: 10.1016/j.actphy.2025.100132
Haotong Ma , Mingyu Heng , Yang Xu , Wei Bi , Yingchun Miao , Shuning Xiao
Photocatalytic CO2 reduction under atmospheric concentrations remains highly challenging yet critical for practical carbon-neutral applications. In this study, a Cu-loaded, carbon-doped boron nitride (Cu/BCN) photocatalyst was synthesized by a microwave-assisted molten salt method. This approach enables simultaneous carbon incorporation into the BN lattice and selective deposition of Cu nanoparticles, forming an efficient heterostructure. The synergy between C doping and Cu loading modulates the band structure, enhances visible-light absorption, promotes charge separation, and improves CO2 adsorption. The optimized Cu/BCN photocatalyst achieved a CO production rate of 30.62 μmol g−1 h−1 with 95.8 % selectivity under ambient CO2 conditions. Combined experimental and DFT analyses confirm that the Cu/BCN interface facilitates charge transfer and lowers the energy barrier for ∗COOH formation. This work demonstrates a promising route toward efficient CO2 utilization directly from air, offering a scalable strategy for atmospheric carbon conversion.
{"title":"Synergistic Carbon Doping and Cu Loading on Boron Nitride via Microwave Synthesis for Enhanced Atmospheric CO2 Photoreduction","authors":"Haotong Ma , Mingyu Heng , Yang Xu , Wei Bi , Yingchun Miao , Shuning Xiao","doi":"10.1016/j.actphy.2025.100132","DOIUrl":"10.1016/j.actphy.2025.100132","url":null,"abstract":"<div><div>Photocatalytic CO<sub>2</sub> reduction under atmospheric concentrations remains highly challenging yet critical for practical carbon-neutral applications. In this study, a Cu-loaded, carbon-doped boron nitride (Cu/BCN) photocatalyst was synthesized by a microwave-assisted molten salt method. This approach enables simultaneous carbon incorporation into the BN lattice and selective deposition of Cu nanoparticles, forming an efficient heterostructure. The synergy between C doping and Cu loading modulates the band structure, enhances visible-light absorption, promotes charge separation, and improves CO<sub>2</sub> adsorption. The optimized Cu/BCN photocatalyst achieved a CO production rate of 30.62 μmol g<sup>−1</sup> h<sup>−1</sup> with 95.8 % selectivity under ambient CO<sub>2</sub> conditions. Combined experimental and DFT analyses confirm that the Cu/BCN interface facilitates charge transfer and lowers the energy barrier for ∗COOH formation. This work demonstrates a promising route toward efficient CO<sub>2</sub> utilization directly from air, offering a scalable strategy for atmospheric carbon conversion.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 11","pages":"Article 100132"},"PeriodicalIF":10.8,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694549","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 : 2025-07-14DOI: 10.1016/j.actphy.2025.100130
Hui Zhang , Zijian Zhao , Yajing Wang , Kai Ni , Yanfei Wang , Liang Zhu , Jianyun Liu , Xiaoyu Zhao
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.
{"title":"Structurally engineered solvent-free LiFePO4 electrodes via hot-pressing with efficient ion transport pathways for lithium extraction from brine","authors":"Hui Zhang , Zijian Zhao , Yajing Wang , Kai Ni , Yanfei Wang , Liang Zhu , Jianyun Liu , 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 LiFePO<sub>4</sub> 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<sup>−2</sup>, delivered a lithium extraction capacity of 4.13 mg cm<sup>−2</sup> 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":"2025-07-14","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}
Pub Date : 2025-07-09DOI: 10.1016/j.actphy.2025.100129
Shan Zhao , Xu Liu , Haotian Guo , Zonglin Liu , Pengfei Wang , Jie Shu , Tingfeng Yi
<div><div>P2-type layered transition metal oxides (P2-Na<sub><em>x</em></sub>TMO<sub>2</sub>) have emerged as promising cathodes for sodium-ion batteries (SIBs) owing to their superior cycling stability and excellent rate capability. However, their practical application is significantly hindered by two major challenges. Firstly, irreversible phase transitions occur during high-voltage operation, which disrupt the structural integrity and deteriorate electrochemical performance. Secondly, their inherently low theoretical specific capacity fails to meet modern energy demands. To tackle these challenges, this study proposes a novel synergistic strategy that integrates high-entropy engineering with a biphasic P2/O3 structural design. An innovative cathode material, Na<sub>0.70</sub>Ni<sub>0.25</sub>Mn<sub>0.35</sub>Co<sub>0.15</sub>Fe<sub>0.05</sub>Ti<sub>0.20</sub>O<sub>2</sub> (denoted as Na<sub>0.70</sub>NMCFT), was successfully synthesized via a high-temperature solid-state reaction. This material design critically incorporates five distinct transition metal cations into the transition metal (TM) layer, constructing a stabilized high-entropy configuration. Careful optimization of both the five TM elements and the sodium content was essential to precisely regulate the synthesis and formation of the desired integrated P2/O3 biphasic structure within this high-entropy host. Comprehensive structural characterization unequivocally confirms the successful construction of this tailored architecture. X-ray diffraction (XRD) and transmission electron microscopy (TEM) collectively confirm the successful construction of the P2/O3 biphasic architecture. The high-entropy engineering stabilizes the P2 phase through configurational entropy, effectively suppressing irreversible phase transitions and Na<sup>+</sup>/vacancy ordering during cycling, as evidenced by smoother charge/discharge profiles and <em>ex-situ</em> XRD analysis under high potentials. Meanwhile, the introduced O3 phase compensates for capacity shortages and improves cycling stability, working in tandem with the P2 phase. Critically, the interaction between the two phases enables a highly reversible transition between P2/O3-P2/P3, further enhancing the overall performance. Under the combined action of the high-entropy and biphasic strategies, Na<sub>0.70</sub>NMCFT exhibits optimal electrochemical performance. It delivers an initial discharge capacity of 102.08 mAh∙g<sup>−1</sup> at 1<em>C</em>, retaining 88.15 % after 200 cycles, demonstrating exceptional cycling stability. Moreover, even at 10<em>C</em>, Na<sub>0.70</sub>NMCFT still has an initial discharge specific capacity of 85.67 mAh∙g<sup>−1</sup> and a capacity retention of up to 70 % after 1000 cycles. Kinetic analyses further reveal that Na<sub>0.70</sub>NMCFT possesses the lowest charge transfer resistance and the highest sodium-ion diffusion coefficient among the materials studied. In conclusion, this work demonstrates that the ratio
{"title":"Synergistic design of high-entropy P2/O3 biphasic cathodes for high-performance sodium-ion batteries","authors":"Shan Zhao , Xu Liu , Haotian Guo , Zonglin Liu , Pengfei Wang , Jie Shu , Tingfeng Yi","doi":"10.1016/j.actphy.2025.100129","DOIUrl":"10.1016/j.actphy.2025.100129","url":null,"abstract":"<div><div>P2-type layered transition metal oxides (P2-Na<sub><em>x</em></sub>TMO<sub>2</sub>) have emerged as promising cathodes for sodium-ion batteries (SIBs) owing to their superior cycling stability and excellent rate capability. However, their practical application is significantly hindered by two major challenges. Firstly, irreversible phase transitions occur during high-voltage operation, which disrupt the structural integrity and deteriorate electrochemical performance. Secondly, their inherently low theoretical specific capacity fails to meet modern energy demands. To tackle these challenges, this study proposes a novel synergistic strategy that integrates high-entropy engineering with a biphasic P2/O3 structural design. An innovative cathode material, Na<sub>0.70</sub>Ni<sub>0.25</sub>Mn<sub>0.35</sub>Co<sub>0.15</sub>Fe<sub>0.05</sub>Ti<sub>0.20</sub>O<sub>2</sub> (denoted as Na<sub>0.70</sub>NMCFT), was successfully synthesized via a high-temperature solid-state reaction. This material design critically incorporates five distinct transition metal cations into the transition metal (TM) layer, constructing a stabilized high-entropy configuration. Careful optimization of both the five TM elements and the sodium content was essential to precisely regulate the synthesis and formation of the desired integrated P2/O3 biphasic structure within this high-entropy host. Comprehensive structural characterization unequivocally confirms the successful construction of this tailored architecture. X-ray diffraction (XRD) and transmission electron microscopy (TEM) collectively confirm the successful construction of the P2/O3 biphasic architecture. The high-entropy engineering stabilizes the P2 phase through configurational entropy, effectively suppressing irreversible phase transitions and Na<sup>+</sup>/vacancy ordering during cycling, as evidenced by smoother charge/discharge profiles and <em>ex-situ</em> XRD analysis under high potentials. Meanwhile, the introduced O3 phase compensates for capacity shortages and improves cycling stability, working in tandem with the P2 phase. Critically, the interaction between the two phases enables a highly reversible transition between P2/O3-P2/P3, further enhancing the overall performance. Under the combined action of the high-entropy and biphasic strategies, Na<sub>0.70</sub>NMCFT exhibits optimal electrochemical performance. It delivers an initial discharge capacity of 102.08 mAh∙g<sup>−1</sup> at 1<em>C</em>, retaining 88.15 % after 200 cycles, demonstrating exceptional cycling stability. Moreover, even at 10<em>C</em>, Na<sub>0.70</sub>NMCFT still has an initial discharge specific capacity of 85.67 mAh∙g<sup>−1</sup> and a capacity retention of up to 70 % after 1000 cycles. Kinetic analyses further reveal that Na<sub>0.70</sub>NMCFT possesses the lowest charge transfer resistance and the highest sodium-ion diffusion coefficient among the materials studied. In conclusion, this work demonstrates that the ratio","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"42 1","pages":"Article 100129"},"PeriodicalIF":13.5,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334186","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 : 2025-07-04DOI: 10.1016/j.actphy.2025.100128
Binbin Liu , Yang Chen , Tianci Jia , Chen Chen, Zhanghao Wu, Yuhui Liu, Yuhang Zhai, Tianshu Ma, Changlei Wang
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 (VOC) 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 VOC of 1.344 V, corresponding to a minimal voltage deficit of 0.426 V, which is among the lowest reported VOC-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.
全钙钛矿串联太阳能电池（TSCs）通过增强整个太阳光谱的光子收集和抑制热化效应，证明了克服单结效率限制的非凡潜力，实现了超过44%的理论功率转换效率。宽带隙钙钛矿太阳能电池（WBG PSCs）是串联光伏发电的关键，在过去十年中取得了指数级的进展。然而，这些器件遭受严重的开路电压（VOC）缺陷，主要是由于界面重组和载流子输运损失。造成这些损失的主要原因是在表面钝化过程中不受控制地形成绝缘二维（2D）钙钛矿相。在这里，我们引入4-羟基苯基乙基碘化铵（p-OHPEAI）作为多功能分子添加剂来解决这个关键的权衡。与传统的苯基碘化铵（PEAI）不同，它通过垂直分子取向形成绝缘的二维相和反电场，阻碍电荷的提取，而p-OHPEAI中的羟基（-OH）通过氨基（-NH3）和-OH基团之间的协同相互作用，使钙钛矿表面上的平行分子吸附成为可能。这种结构有效地消除了绝缘二维钙钛矿相的形成，钝化了不协调的卤化物和铅空位，减少了非辐射复合。此外，p-OHPEAI的极性在钙钛矿/电子传输层（ETL）界面产生偶极矩，优化能级排列并促进电子提取。通过将p-OHPEAI加入到1.77 eV WBG PSCs中，我们获得了1.344 V的VOC，对应于0.426 V的最小电压亏缺，这是报道的带隙范围为1.75至1.80 eV的倒转WBG PSCs的最低VOC亏缺值之一。优化后的器件的功率转换效率（PCE）为19.24%，与传统的peai钝化电池相比表现出优异的性能。当集成到全钙钛矿tsc中时，该策略使PCE达到28.50%（认证效率为28.19%）。此外，该器件表现出优异的操作稳定性，在连续照明350小时后保持90%以上的初始效率，突出了羟基驱动钝化方法的稳健性。在钝化分子中引入羟基提供了一种平衡缺陷抑制和电荷传输的通用策略，弥合了高压和高效载流子提取之间的差距。
{"title":"Hydroxyl-functionalized molecular engineering mitigates 2D phase barriers for efficient wide-bandgap and all-perovskite tandem solar cells","authors":"Binbin Liu , Yang Chen , Tianci Jia , Chen Chen, Zhanghao Wu, Yuhui Liu, Yuhang Zhai, Tianshu Ma, 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><sub>OC</sub>) 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 (-NH<sub>3</sub>) 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><sub>OC</sub> of 1.344 V, corresponding to a minimal voltage deficit of 0.426 V, which is among the lowest reported <em>V</em><sub>OC</sub>-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":"2025-07-04","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}
Pub Date : 2025-07-01DOI: 10.1016/j.actphy.2025.100127
Lei Wang , Panpan Zhang , Zhiyuan Guo , Jing Wang , Jie Ma , Zhi-yong Ji
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 Li1.6Mn1.6O4, 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.
{"title":"Electrochemical lithium extraction by the faradaic materials: advances, challenges and enhancement approaches","authors":"Lei Wang , Panpan Zhang , Zhiyuan Guo , Jing Wang , Jie Ma , 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<sup>+</sup> and Mg<sup>2+</sup>), 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 LiFePO<sub>4</sub>, LiMn<sub>2</sub>O<sub>4</sub>, layered nickel cobalt manganese oxides, Li<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, and Li<sub>1.6</sub>Mn<sub>1.6</sub>O<sub>4</sub>, 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":"2025-07-01","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}
Pub Date : 2025-06-28DOI: 10.1016/j.actphy.2025.100126
Xiaorui Chen , Xuan Luo , Tongming Su , Xinling Xie , Liuyun Chen , Yuejing Bin , Zuzeng Qin , Hongbing Ji
The reaction of CO2 catalytic hydrogenation to dimethyl ether (DME) usually relies on a Cu-containing metal oxide/molecular sieve system; however, the migration of copper species to molecular sieves is unavoidable during the reaction, leading to the loss of Cu0 sites and acidic sites. In this work, a Cu/x%Ga-γ-Al2O3 bifunctional catalyst was synthesized via the coprecipitation method. Ga was doped into the γ-Al2O3 lattice at a low concentration, forming interfacial active sites with surface Cu0 species to achieve the hydrogenation of CO2 to DME. Experimental studies combined with DFT calculations demonstrate that the catalyst remains stable for 180 h and that the Ga-doped Cu/γ-Al2O3 interface sites exhibit catalytic effects on CO2 hydrogenation to CH3OH and CH3OH dehydration to produce DME. The doping of Ga increases the specific surface area of the catalyst, reduces the particle size of Cu0, enhances the number of acidic and basic sites on the catalyst, and promotes the adsorption of H2 and CO2. In addition, a new reaction pathway for DME synthesis was proposed. This work removes the dehydrated component of a traditional Cu-based bifunctional catalyst, enabling two reactions to occur at the same active sites, thus providing a new strategy for the design of novel dimethyl ether synthesis bifunctional catalysts.
{"title":"Ga-doped Cu/γ-Al2O3 bifunctional interface sites promote the direct hydrogenation of CO2 to DME","authors":"Xiaorui Chen , Xuan Luo , Tongming Su , Xinling Xie , Liuyun Chen , Yuejing Bin , Zuzeng Qin , Hongbing Ji","doi":"10.1016/j.actphy.2025.100126","DOIUrl":"10.1016/j.actphy.2025.100126","url":null,"abstract":"<div><div>The reaction of CO<sub>2</sub> catalytic hydrogenation to dimethyl ether (DME) usually relies on a Cu-containing metal oxide/molecular sieve system; however, the migration of copper species to molecular sieves is unavoidable during the reaction, leading to the loss of Cu<sup>0</sup> sites and acidic sites. In this work, a Cu/<em>x</em>%Ga-γ-Al<sub>2</sub>O<sub>3</sub> bifunctional catalyst was synthesized <em>via</em> the coprecipitation method. Ga was doped into the γ-Al<sub>2</sub>O<sub>3</sub> lattice at a low concentration, forming interfacial active sites with surface Cu<sup>0</sup> species to achieve the hydrogenation of CO<sub>2</sub> to DME. Experimental studies combined with DFT calculations demonstrate that the catalyst remains stable for 180 h and that the Ga-doped Cu/γ-Al<sub>2</sub>O<sub>3</sub> interface sites exhibit catalytic effects on CO<sub>2</sub> hydrogenation to CH<sub>3</sub>OH and CH<sub>3</sub>OH dehydration to produce DME. The doping of Ga increases the specific surface area of the catalyst, reduces the particle size of Cu<sup>0</sup>, enhances the number of acidic and basic sites on the catalyst, and promotes the adsorption of H<sub>2</sub> and CO<sub>2</sub>. In addition, a new reaction pathway for DME synthesis was proposed. This work removes the dehydrated component of a traditional Cu-based bifunctional catalyst, enabling two reactions to occur at the same active sites, thus providing a new strategy for the design of novel dimethyl ether synthesis bifunctional catalysts.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 10","pages":"Article 100126"},"PeriodicalIF":10.8,"publicationDate":"2025-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535388","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 : 2025-06-17DOI: 10.1016/j.actphy.2025.100121
Bowen Liu , Jianjun Zhang , Han Li , Bei Cheng , Chuanbiao Bie
Complete mineralization of persistent organic pollutants in wastewater remains a formidable challenge. Here, we report the rational design of a ZIF-8-derived ZnO/polyaniline (PANI) S-scheme heterojunction synthesized via in situ oxidative polymerization. Advanced characterizations confirm the S-scheme charge transfer mechanism within the ZnO/PANI heterojunction. The optimized composite achieves complete phenol mineralization within 60 min while concurrently generating H2O2 at a rate of 0.75 mmol∙L−1·h−1 under simulated solar irradiation. Mechanistic studies verify that the S-scheme heterojunction retains strong redox potentials, driving the formation of reactive oxygen species for H2O2 production and phenol degradation. This work establishes a universal design paradigm for MOF-derived inorganic/organic S-scheme heterojunctions, effectively coupling solar-driven energy conversion with environmental remediation.
{"title":"MOF-derived ZnO/PANI S-scheme heterojunction for efficient photocatalytic phenol mineralization coupled with H2O2 generation","authors":"Bowen Liu , Jianjun Zhang , Han Li , Bei Cheng , Chuanbiao Bie","doi":"10.1016/j.actphy.2025.100121","DOIUrl":"10.1016/j.actphy.2025.100121","url":null,"abstract":"<div><div>Complete mineralization of persistent organic pollutants in wastewater remains a formidable challenge. Here, we report the rational design of a ZIF-8-derived ZnO/polyaniline (PANI) S-scheme heterojunction synthesized <em>via in situ</em> oxidative polymerization. Advanced characterizations confirm the S-scheme charge transfer mechanism within the ZnO/PANI heterojunction. The optimized composite achieves complete phenol mineralization within 60 min while concurrently generating H<sub>2</sub>O<sub>2</sub> at a rate of 0.75 mmol∙L<sup>−1</sup>·h<sup>−1</sup> under simulated solar irradiation. Mechanistic studies verify that the S-scheme heterojunction retains strong redox potentials, driving the formation of reactive oxygen species for H<sub>2</sub>O<sub>2</sub> production and phenol degradation. This work establishes a universal design paradigm for MOF-derived inorganic/organic S-scheme heterojunctions, effectively coupling solar-driven energy conversion with environmental remediation.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 10","pages":"Article 100121"},"PeriodicalIF":10.8,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144330018","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 : 2025-06-17DOI: 10.1016/j.actphy.2025.100122
Ziyang Long , Quanzheng Li , Chengliang Zhang , Haifeng Shi
Modulating the internal electric field (IEF) remains a critical challenge for S-scheme heterojunction photocatalysts. The BiVO4/WO3−x S-scheme heterojunctions were successfully prepared to purify the wastewater environment where TC and Cr (VI) coexist under visible light illumination. The BiVO4/WO3−x with 10 wt% WO3−x (BVO/WO3−x-10) demonstrated superior photocatalytic efficiency, which could degrade 78.5 % of TC and reduce 85.3 % of Cr(VI) in 60 min. The photocatalytic activity of BVO/WO3−x−10 displayed enhanced removal efficiency in the mixed system. The removal ability of TC and Cr (Ⅵ) was increased by 1.29 and 1.32 times, respectively. Based on IR thermography measurements, the elevated reaction system temperatures were ascribed to the photothermal effect of WO3−x. Oxygen vacancies (OVs) could amplify the energy band difference between WO3−x and BiVO4, which strengthens the IEF and accelerates the separation of carriers. A detailed degradation pathway and intermediate toxicity were carried out using the mung bean experiment and the results of the LC−MS. In general, this work provided new insights for regulating IEF to enhance the degradation efficiency in mixed wastewater and the carriers separation in the S-scheme heterojunction of the photothermal-catalytic system.
{"title":"BiVO4/WO3−x S-scheme heterojunctions with amplified internal electric field for boosting photothermal-catalytic activity","authors":"Ziyang Long , Quanzheng Li , Chengliang Zhang , Haifeng Shi","doi":"10.1016/j.actphy.2025.100122","DOIUrl":"10.1016/j.actphy.2025.100122","url":null,"abstract":"<div><div>Modulating the internal electric field (IEF) remains a critical challenge for S-scheme heterojunction photocatalysts. The BiVO<sub>4</sub>/WO<sub>3−<em>x</em></sub> S-scheme heterojunctions were successfully prepared to purify the wastewater environment where TC and Cr (VI) coexist under visible light illumination. The BiVO<sub>4</sub>/WO<sub>3−<em>x</em></sub> with 10 wt% WO<sub>3−<em>x</em></sub> (BVO/WO<sub>3−<em>x</em></sub>-10) demonstrated superior photocatalytic efficiency, which could degrade 78.5 % of TC and reduce 85.3 % of Cr(VI) in 60 min. The photocatalytic activity of BVO/WO<sub>3−<em>x</em></sub>−10 displayed enhanced removal efficiency in the mixed system. The removal ability of TC and Cr (Ⅵ) was increased by 1.29 and 1.32 times, respectively. Based on IR thermography measurements, the elevated reaction system temperatures were ascribed to the photothermal effect of WO<sub>3−<em>x</em></sub>. Oxygen vacancies (OVs) could amplify the energy band difference between WO<sub>3−<em>x</em></sub> and BiVO<sub>4</sub>, which strengthens the IEF and accelerates the separation of carriers. A detailed degradation pathway and intermediate toxicity were carried out using the mung bean experiment and the results of the LC−MS. In general, this work provided new insights for regulating IEF to enhance the degradation efficiency in mixed wastewater and the carriers separation in the S-scheme heterojunction of the photothermal-catalytic system.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 10","pages":"Article 100122"},"PeriodicalIF":10.8,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144330019","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 : 2025-06-14DOI: 10.1016/j.actphy.2025.100120
Qi Wang , Yuqing Liu , Jiefei Wang , Yuan-Yuan Ma , Jing Du , Zhan-Gang Han
Electrocatalytic hydrodechlorination (EHDC) is a promising technology for degrading chlorinated aromatic hydrocarbons (CAHs), offering high efficiency, minimal secondary pollution, and mild operating conditions. Its effectiveness relies on three critical steps: atomic hydrogen (H∗) generation, C-Cl bond cleavage, and adsorption/desorption of CAHs/products. Developing high-performance electrocatalysts is essential to optimize energy efficiency and cost-effectiveness. It is urgent to summarize research progress on design strategies for catalysts and establish fundamental principles. In this review, we first summarize commonly deployed measurement methods and metrics for assessing catalyst activity and stability in EHDC. Then, a series of strategies for enhancing the production of H∗, facilitating the cleavage of C-Cl bonds, and optimizing the adsorption and desorption kinetics of CAHs and their intermediates/products on the catalyst surface are summarized. These strategies include the loading of catalysts on carbon-based/transition-based support to enhance the dispersion of Pd; constructing heterostructures or forming alloys to modulate the electronic structure of active metal nanocatalysts and optimize its binding affinities with reactants and intermediates; and modulating the microenvironment to modify the interface hydrophilicity/hydrophobicity of catalyst to increase reaction rates or improve stability of catalysts. Additionally, the applications of electrocatalysts for EHDC in recent years, such as Pd-based supported electrocatalysts, Pd-based heterostructure electrocatalysts, Pd-based alloy electrocatalysts, and noble-metal-free electrocatalysts are discussed, as well as the influence of catalyst composition on performance. It is noted that the EHDC efficiency of CAHs is influenced not only by the catalyst but also significantly correlated with the structure of CAHs. Thus, the effects of CAHs structures on EHDC performance are also discussed. Studies demonstrate that weak adsorption between the electrode and CAHs is more conducive to EHDC reactions. The number and position of chlorine functional groups, steric hindrance, and the properties of other functional groups in the substrate molecule can also influence EHDC performance. Finally, the challenges and future prospects of EHDC are highlighted, including improving the catalytic performance of non-noble catalysts, employing advanced in situ and operando characterization techniques, and optimizing DFT calculations to more closely align with real catalytic conditions, all aiming to inspire new investigations and advancements in the field of EHDC of CAHs.
{"title":"Catalysts for electrocatalytic dechlorination of chlorinated aromatic hydrocarbons: synthetic strategies, applications, and challenges","authors":"Qi Wang , Yuqing Liu , Jiefei Wang , Yuan-Yuan Ma , Jing Du , Zhan-Gang Han","doi":"10.1016/j.actphy.2025.100120","DOIUrl":"10.1016/j.actphy.2025.100120","url":null,"abstract":"<div><div>Electrocatalytic hydrodechlorination (EHDC) is a promising technology for degrading chlorinated aromatic hydrocarbons (CAHs), offering high efficiency, minimal secondary pollution, and mild operating conditions. Its effectiveness relies on three critical steps: atomic hydrogen (H∗) generation, C-Cl bond cleavage, and adsorption/desorption of CAHs/products. Developing high-performance electrocatalysts is essential to optimize energy efficiency and cost-effectiveness. It is urgent to summarize research progress on design strategies for catalysts and establish fundamental principles. In this review, we first summarize commonly deployed measurement methods and metrics for assessing catalyst activity and stability in EHDC. Then, a series of strategies for enhancing the production of H∗, facilitating the cleavage of C-Cl bonds, and optimizing the adsorption and desorption kinetics of CAHs and their intermediates/products on the catalyst surface are summarized. These strategies include the loading of catalysts on carbon-based/transition-based support to enhance the dispersion of Pd; constructing heterostructures or forming alloys to modulate the electronic structure of active metal nanocatalysts and optimize its binding affinities with reactants and intermediates; and modulating the microenvironment to modify the interface hydrophilicity/hydrophobicity of catalyst to increase reaction rates or improve stability of catalysts. Additionally, the applications of electrocatalysts for EHDC in recent years, such as Pd-based supported electrocatalysts, Pd-based heterostructure electrocatalysts, Pd-based alloy electrocatalysts, and noble-metal-free electrocatalysts are discussed, as well as the influence of catalyst composition on performance. It is noted that the EHDC efficiency of CAHs is influenced not only by the catalyst but also significantly correlated with the structure of CAHs. Thus, the effects of CAHs structures on EHDC performance are also discussed. Studies demonstrate that weak adsorption between the electrode and CAHs is more conducive to EHDC reactions. The number and position of chlorine functional groups, steric hindrance, and the properties of other functional groups in the substrate molecule can also influence EHDC performance. Finally, the challenges and future prospects of EHDC are highlighted, including improving the catalytic performance of non-noble catalysts, employing advanced in situ and operando characterization techniques, and optimizing DFT calculations to more closely align with real catalytic conditions, all aiming to inspire new investigations and advancements in the field of EHDC of CAHs.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 10","pages":"Article 100120"},"PeriodicalIF":10.8,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472381","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 : 2025-06-12DOI: 10.1016/j.actphy.2025.100115
Hengrui Zhang, Xijun Xu, Xun-Lu Li, Xiangwen Gao
With the rapid development of renewable energy and electric vehicles, batteries, as the core components of electrochemical energy storage systems, have become a global focus in both scientific research and industrial sectors due to their critical impact on system efficiency and safety. However, the complex multi-physics reactions within batteries make traditional mathematical models inadequate for comprehensively revealing their mechanisms. The key to solving this problem lies in introducing data-driven approaches, which have laid a solid foundation for battery research and development through extensive accumulation of experimental data and extraction of effective information. Generative artificial intelligence (GAI), leveraging its powerful latent pattern learning and data generation capabilities, has already found widespread applications in protein structure prediction, material inverse design, and data augmentation, demonstrating its broad application prospects. Applying GAI to battery research workflows with diverse battery data resources could provide innovative solutions to challenges in battery research. In this perspective, we introduce the core principles and latest advancements of generative models (GMs), including Generative Adversarial Network (GAN), Variational Auto-Encoder (VAE), and Diffusion Model (DM), which can learn the latent distribution of the input samples to generate new data by sampling from it. Applications of GAI in battery research are then reviewed. For battery materials design, by learning material compositions, structures, and properties, GM can generate novel candidate materials with desired properties through conditional constraints, significantly extending the chemical space to be explored. For electrode microstructure characterization, GM can serve as a bridge for interconversion and integration of different image data, enhance the quality of microscopic characterization, and generate realistic synthetic data. For battery state estimation, GM can perform data augmentation and feature extraction on battery datasets, which benefits the model performance for battery state estimation. Lastly, we discuss the challenges and future development directions in terms of data governance and model design, including data quality and diversity, data standardization and sharing, usability of synthetic data, interpretability of GM, and foundational models for battery research. For the innovation and advancement of battery technology, this perspective offers theoretical references and practical guidelines for implementing GAI as an effective tool in battery research workflows by discussing its status and prospects in this field.
{"title":"Applications of generative artificial intelligence in battery research: Current status and prospects","authors":"Hengrui Zhang, Xijun Xu, Xun-Lu Li, Xiangwen Gao","doi":"10.1016/j.actphy.2025.100115","DOIUrl":"10.1016/j.actphy.2025.100115","url":null,"abstract":"<div><div>With the rapid development of renewable energy and electric vehicles, batteries, as the core components of electrochemical energy storage systems, have become a global focus in both scientific research and industrial sectors due to their critical impact on system efficiency and safety. However, the complex multi-physics reactions within batteries make traditional mathematical models inadequate for comprehensively revealing their mechanisms. The key to solving this problem lies in introducing data-driven approaches, which have laid a solid foundation for battery research and development through extensive accumulation of experimental data and extraction of effective information. Generative artificial intelligence (GAI), leveraging its powerful latent pattern learning and data generation capabilities, has already found widespread applications in protein structure prediction, material inverse design, and data augmentation, demonstrating its broad application prospects. Applying GAI to battery research workflows with diverse battery data resources could provide innovative solutions to challenges in battery research. In this perspective, we introduce the core principles and latest advancements of generative models (GMs), including Generative Adversarial Network (GAN), Variational Auto-Encoder (VAE), and Diffusion Model (DM), which can learn the latent distribution of the input samples to generate new data by sampling from it. Applications of GAI in battery research are then reviewed. For battery materials design, by learning material compositions, structures, and properties, GM can generate novel candidate materials with desired properties through conditional constraints, significantly extending the chemical space to be explored. For electrode microstructure characterization, GM can serve as a bridge for interconversion and integration of different image data, enhance the quality of microscopic characterization, and generate realistic synthetic data. For battery state estimation, GM can perform data augmentation and feature extraction on battery datasets, which benefits the model performance for battery state estimation. Lastly, we discuss the challenges and future development directions in terms of data governance and model design, including data quality and diversity, data standardization and sharing, usability of synthetic data, interpretability of GM, and foundational models for battery research. For the innovation and advancement of battery technology, this perspective offers theoretical references and practical guidelines for implementing GAI as an effective tool in battery research workflows by discussing its status and prospects in this field.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 10","pages":"Article 100115"},"PeriodicalIF":10.8,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144472367","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