Pub Date : 2024-12-26DOI: 10.1016/j.actphy.2024.100042
Jian Li , Yu Zhang , Rongrong Yan , Kaiyuan Sun , Xiaoqing Liu , Zishang Liang , Yinan Jiao , Hui Bu , Xin Chen , Jinjin Zhao , Jianlin Shi
<div><div>Metal halide perovskites have emerged as highly promising materials in optoelectronics, owing to their unique multidimensional crystal structures that impart exceptional optical and electronic properties. These materials exhibit remarkable fluorescence imaging and tracking capabilities, as well as efficient photoelectric conversion, making them suitable for a broad range of applications. Nevertheless, despite their significant potential, their poor water stability has posed a major challenge, particularly in biomedical fields such as drug delivery systems, biological imaging, and photoelectrocatalytic oncotherapy. This limitation has hindered their practical use in medical treatments and diagnostics. In this study, we address the water stability issue by successfully synthesizing CsSn<sub>0.5</sub>Pb<sub>0.5</sub>Br<sub>3</sub> perovskite nanocrystals (PeNCs) and conjugating them with methotrexate-chitosan-folic acid (MTX-CS-FA), resulting in innovative green light-emitting PeNCs@MTX-CS-FA nanoparticles. These nanoparticles exhibited remarkable water stability, maintaining their structural and functional integrity for up to 228 days, a significant improvement that enables their application in complex biological environments. Under visible light illumination, the nanoparticles demonstrated a dual-action therapeutic mechanism. The perovskites effectively generated electrons and reactive oxygen species (ROS), inducing oxidative stress in tumor cells. At the same time, photogenerated holes oxidized glutathione (GSH), a molecule that is typically overexpressed in tumor cells to protect against oxidative damage. By depleting GSH, the nanoparticles weakened the tumor cells' defense mechanisms, thereby enhancing the oxidative damage caused by ROS. In addition, methotrexate (MTX), a chemotherapeutic agent integrated into the system, inhibited dihydrofolate reductase (DHFR) activity. This inhibition disrupted tumor cell metabolism, particularly nucleotide synthesis, leading to lipid peroxidation and subsequent cell death. Together, these mechanisms generated a potent, synergistic therapeutic effect. The therapeutic efficacy of the PeNCs@MTX-CS-FA nanoparticles was validated through in vivo antitumor experiments in mice. A total dose of 2.4 mg of nanoparticles resulted in a 63.68 % reduction in tumor volume and a 63.26 % decrease in tumor weight, demonstrating significant tumor growth suppression. Biological safety evaluations further confirmed the nanoparticles' biocompatibility. Notably, they were excreted from the mice in their fluorescent form without decomposition, ensuring minimal long-term toxicity. This safe excretion pathway underscores the feasibility of repeated use of these nanoparticles in clinical applications. Overall, this study highlights the transformative potential of metal halide perovskites in cancer treatment. By overcoming the water stability limitations that have previously constrained their biomedical applications, the
{"title":"Highly efficient, targeted, and traceable perovskite nanocrystals for photoelectrocatalytic oncotherapy","authors":"Jian Li , Yu Zhang , Rongrong Yan , Kaiyuan Sun , Xiaoqing Liu , Zishang Liang , Yinan Jiao , Hui Bu , Xin Chen , Jinjin Zhao , Jianlin Shi","doi":"10.1016/j.actphy.2024.100042","DOIUrl":"10.1016/j.actphy.2024.100042","url":null,"abstract":"<div><div>Metal halide perovskites have emerged as highly promising materials in optoelectronics, owing to their unique multidimensional crystal structures that impart exceptional optical and electronic properties. These materials exhibit remarkable fluorescence imaging and tracking capabilities, as well as efficient photoelectric conversion, making them suitable for a broad range of applications. Nevertheless, despite their significant potential, their poor water stability has posed a major challenge, particularly in biomedical fields such as drug delivery systems, biological imaging, and photoelectrocatalytic oncotherapy. This limitation has hindered their practical use in medical treatments and diagnostics. In this study, we address the water stability issue by successfully synthesizing CsSn<sub>0.5</sub>Pb<sub>0.5</sub>Br<sub>3</sub> perovskite nanocrystals (PeNCs) and conjugating them with methotrexate-chitosan-folic acid (MTX-CS-FA), resulting in innovative green light-emitting PeNCs@MTX-CS-FA nanoparticles. These nanoparticles exhibited remarkable water stability, maintaining their structural and functional integrity for up to 228 days, a significant improvement that enables their application in complex biological environments. Under visible light illumination, the nanoparticles demonstrated a dual-action therapeutic mechanism. The perovskites effectively generated electrons and reactive oxygen species (ROS), inducing oxidative stress in tumor cells. At the same time, photogenerated holes oxidized glutathione (GSH), a molecule that is typically overexpressed in tumor cells to protect against oxidative damage. By depleting GSH, the nanoparticles weakened the tumor cells' defense mechanisms, thereby enhancing the oxidative damage caused by ROS. In addition, methotrexate (MTX), a chemotherapeutic agent integrated into the system, inhibited dihydrofolate reductase (DHFR) activity. This inhibition disrupted tumor cell metabolism, particularly nucleotide synthesis, leading to lipid peroxidation and subsequent cell death. Together, these mechanisms generated a potent, synergistic therapeutic effect. The therapeutic efficacy of the PeNCs@MTX-CS-FA nanoparticles was validated through in vivo antitumor experiments in mice. A total dose of 2.4 mg of nanoparticles resulted in a 63.68 % reduction in tumor volume and a 63.26 % decrease in tumor weight, demonstrating significant tumor growth suppression. Biological safety evaluations further confirmed the nanoparticles' biocompatibility. Notably, they were excreted from the mice in their fluorescent form without decomposition, ensuring minimal long-term toxicity. This safe excretion pathway underscores the feasibility of repeated use of these nanoparticles in clinical applications. Overall, this study highlights the transformative potential of metal halide perovskites in cancer treatment. By overcoming the water stability limitations that have previously constrained their biomedical applications, the ","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100042"},"PeriodicalIF":10.8,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143369068","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 : 2024-12-26DOI: 10.1016/j.actphy.2024.100041
Xueting Cao, Shuangshuang Cha, Ming Gong
The interfacial electrical double layer (EDL) is the interfacial space filled with a complex and dynamic reaction network formed by catalyst's surface atoms, reactants, intermediates, products, solvent molecules, ions, and other components. EDL has a profound impact on electrocatalytic reactions, affecting both the thermodynamics and kinetics of these processes. Manipulating the composition and structure of the EDL microenvironment sets an additional level of tuning toward the electrocatalysis, to the traditional catalyst optimization. It resembles the delicate manipulation of the environment around the active sites by protein scaffold in enzymes. However, the rational optimization of the EDL demands a deep understanding of its structure and dynamics. Problems lie in the complexities of interfacial EDL, which include complicated multi-body interactions, few molecular-level characterization techniques, and scarce EDL modification strategies.
In this tutorial, we delve into the intricacies of the interfacial EDL in electrocatalytic reactions and seek to provide those who are new to this field a thorough summary of the theory, characterization, history, recent progress within the regime of EDL for electrocatalysis. We begin by discussing the theoretical models that describe the structure and properties of EDL, including 4 classical EDL models, their applications in electrocatalytic analysis and modifications, and relevant calculation modulation methods. These models are arranged chronologically, such that a historical summary of how the EDL theory evolves from simple models to complicated details is provided. We then provide an overview of cutting-edge techniques in electrochemical measurement methods, in situ spectroscopic characterization techniques, and scanning probe microscopy methods. Specifically, we aim to summarize the advantages and disadvantages of each technique, with an emphasis on their capability of probing the EDL region. The summary table can provide junior students with a quick overview and a useful tool for selecting the appropriate techniques toward addressing the EDL properties for electrocatalysis. Furthermore, by combining the theory and characterization techniques, we list several pivotal studies from the past five years emphasizing the “electrode side interfacial modification” approach and the “solution side interfacial modification” approach, toward modulating the EDL to optimize the electrocatalytic properties. These examples not only show the recent progress in this field and offer fundamental details about how researchers in this field address the problems from the aspect of EDL. With these combined theory, characterization and research samples, we hope that the newcomers can gain interest in this field, sense the enormous opportunities and understand the general principles of EDL toward electrocatalysis.
{"title":"Interfacial electrical double layer in electrocatalytic reactions: Fundamentals, characterizations and applications","authors":"Xueting Cao, Shuangshuang Cha, Ming Gong","doi":"10.1016/j.actphy.2024.100041","DOIUrl":"10.1016/j.actphy.2024.100041","url":null,"abstract":"<div><div>The interfacial electrical double layer (EDL) is the interfacial space filled with a complex and dynamic reaction network formed by catalyst's surface atoms, reactants, intermediates, products, solvent molecules, ions, and other components. EDL has a profound impact on electrocatalytic reactions, affecting both the thermodynamics and kinetics of these processes. Manipulating the composition and structure of the EDL microenvironment sets an additional level of tuning toward the electrocatalysis, to the traditional catalyst optimization. It resembles the delicate manipulation of the environment around the active sites by protein scaffold in enzymes. However, the rational optimization of the EDL demands a deep understanding of its structure and dynamics. Problems lie in the complexities of interfacial EDL, which include complicated multi-body interactions, few molecular-level characterization techniques, and scarce EDL modification strategies.</div><div>In this tutorial, we delve into the intricacies of the interfacial EDL in electrocatalytic reactions and seek to provide those who are new to this field a thorough summary of the theory, characterization, history, recent progress within the regime of EDL for electrocatalysis. We begin by discussing the theoretical models that describe the structure and properties of EDL, including 4 classical EDL models, their applications in electrocatalytic analysis and modifications, and relevant calculation modulation methods. These models are arranged chronologically, such that a historical summary of how the EDL theory evolves from simple models to complicated details is provided. We then provide an overview of cutting-edge techniques in electrochemical measurement methods, <em>in situ</em> spectroscopic characterization techniques, and scanning probe microscopy methods. Specifically, we aim to summarize the advantages and disadvantages of each technique, with an emphasis on their capability of probing the EDL region. The summary table can provide junior students with a quick overview and a useful tool for selecting the appropriate techniques toward addressing the EDL properties for electrocatalysis. Furthermore, by combining the theory and characterization techniques, we list several pivotal studies from the past five years emphasizing the “electrode side interfacial modification” approach and the “solution side interfacial modification” approach, toward modulating the EDL to optimize the electrocatalytic properties. These examples not only show the recent progress in this field and offer fundamental details about how researchers in this field address the problems from the aspect of EDL. With these combined theory, characterization and research samples, we hope that the newcomers can gain interest in this field, sense the enormous opportunities and understand the general principles of EDL toward electrocatalysis.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100041"},"PeriodicalIF":10.8,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143102963","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 : 2024-12-24DOI: 10.1016/j.actphy.2024.100039
Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang
Photocatalytic nitric oxide (NO) conversion technology has the characteristics of high efficiency, economy, and environment friendly to remove NO using g-C3N4. Introducing new adsorption sites on the surface of g-C3N4 through microstructure control can alter the structure-activity relationship between g-C3N4 and gas molecules, thereby improving photocatalytic NO conversion activity and inhibiting NO2 generation. However, few review articles have focused on the microscopic effects of microstructural changes in g-C3N4 based materials on the adsorption and activation of NO and O2. This has important guiding significance for material design work in the field of NO conversion and strategies to fundamentally improve NO conversion activity and selectivity. Therefore, our work systematically summarizes the strategy of introducing adsorption and activation sites through microstructure control, and emphasizes the role of these sites in the photocatalytic NO conversion process. The aim is to clarify the influence of adsorption and activation sites on adsorption behavior and the correlation between these sites and reaction paths. Finally, the development trend and future prospects of increasing the level of g-C3N4 adsorption and activation in the field of photocatalytic NO conversion are introduced, which is expected to provide an important reference for the development and practical application of g-C3N4-based photocatalytic materials.
{"title":"Recent progress of microstructure-regulated g-C3N4 in photocatalytic NO conversion: The pivotal roles of adsorption/activation sites","authors":"Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang","doi":"10.1016/j.actphy.2024.100039","DOIUrl":"10.1016/j.actphy.2024.100039","url":null,"abstract":"<div><div>Photocatalytic nitric oxide (NO) conversion technology has the characteristics of high efficiency, economy, and environment friendly to remove NO using g-C<sub>3</sub>N<sub>4</sub>. Introducing new adsorption sites on the surface of g-C<sub>3</sub>N<sub>4</sub> through microstructure control can alter the structure-activity relationship between g-C<sub>3</sub>N<sub>4</sub> and gas molecules, thereby improving photocatalytic NO conversion activity and inhibiting NO<sub>2</sub> generation. However, few review articles have focused on the microscopic effects of microstructural changes in g-C<sub>3</sub>N<sub>4</sub> based materials on the adsorption and activation of NO and O<sub>2</sub>. This has important guiding significance for material design work in the field of NO conversion and strategies to fundamentally improve NO conversion activity and selectivity. Therefore, our work systematically summarizes the strategy of introducing adsorption and activation sites through microstructure control, and emphasizes the role of these sites in the photocatalytic NO conversion process. The aim is to clarify the influence of adsorption and activation sites on adsorption behavior and the correlation between these sites and reaction paths. Finally, the development trend and future prospects of increasing the level of g-C<sub>3</sub>N<sub>4</sub> adsorption and activation in the field of photocatalytic NO conversion are introduced, which is expected to provide an important reference for the development and practical application of g-C<sub>3</sub>N<sub>4</sub>-based photocatalytic materials.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100039"},"PeriodicalIF":10.8,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143102413","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 : 2024-12-17DOI: 10.1016/j.actphy.2024.100040
Lingbang Qiu , Jiangmin Jiang , Libo Wang , Lang Bai , Fei Zhou , Gaoyu Zhou , Quanchao Zhuang , Yanhua Cui
<div><div>As a primary energy storage device, the thermal battery offers advantages such as high specific energy and high-power density. However, developing new cathode materials with high specific capacity and thermal stability to meet the evolving needs of thermal batteries remains a significant challenge. Moreover, the high discharge temperatures of thermal batteries and the instability of the molten salt electrolyte system complicate the electrochemical <em>in situ</em> characterization of these systems. In this context, <em>in situ</em> electrochemical impedance spectroscopy (EIS) has become widely employed in electrochemistry and represents a promising technique for <em>in situ</em> monitoring of thermal battery systems. Niobium-tungsten oxides, which possess a Wadsley-Roth crystal shear structure, exhibit excellent rate capability and cyclic stability as anode materials for lithium-ion batteries. Among them, Nb<sub>12</sub>WO<sub>33</sub> demonstrates remarkable lithium storage performance due to its unique 3D tunneling structure, which provides rapid de-intercalation channels for Li<sup>+</sup> ions. Given its excellent thermal and electrochemical stability, this study proposes the use of Nb<sub>12</sub>WO<sub>33</sub> as a cathode material for thermal batteries for the first time. Electrochemical impedance spectroscopy (EIS) at room temperature was employed to investigate the variations in the material's internal electronic conductivity impedance. The EIS Nyquist plots of the Nb<sub>12</sub>WO<sub>33</sub> electrode reveal a distinctive phenomenon of three semicircles in the high- and mid-frequency regions within the operating potential range. This behavior is primarily attributed to the electron conduction within the Nb<sub>12</sub>WO<sub>33</sub> electrode. The resistance associated with electronic conduction (<em>R</em><sub>E</sub>) exhibits a pattern of initial increase followed by a decrease. This phenomenon is explained by the valence transition of the Nb element from +5 to +4 occurring around 1.7 V. This step is more facile than the subsequent steps at 2.0 V and 1.2 V, resulting in the generation of a larger number of metastable electrons. Consequently, the internal channels become populated with electrons, leading to a significant increase in <em>R</em><sub>E</sub>. The thermal battery constructed with Nb<sub>12</sub>WO<sub>33</sub> as the cathode material was discharged at 500 °C and a current density of 500 mA g<sup>−1</sup> (with a cut-off voltage of 1.5 V), achieving a high specific capacity of 436.8 mA h g<sup>−1</sup> and an average polarized internal resistance of 0.52 Ω during pulse discharge. Therefore, Nb<sub>12</sub>WO<sub>33</sub> holds great potential as a cathode material for high-capacity, thermally stable thermal batteries. This study paves the way for the use of other niobium-tungsten oxides as cathode materials for thermal batteries and establishes a precedent for <em>in situ</em> EIS testing and anal
{"title":"In situ electrochemical impedance spectroscopy monitoring of the high-temperature double-discharge mechanism of Nb12WO33 cathode material for long-life thermal batteries","authors":"Lingbang Qiu , Jiangmin Jiang , Libo Wang , Lang Bai , Fei Zhou , Gaoyu Zhou , Quanchao Zhuang , Yanhua Cui","doi":"10.1016/j.actphy.2024.100040","DOIUrl":"10.1016/j.actphy.2024.100040","url":null,"abstract":"<div><div>As a primary energy storage device, the thermal battery offers advantages such as high specific energy and high-power density. However, developing new cathode materials with high specific capacity and thermal stability to meet the evolving needs of thermal batteries remains a significant challenge. Moreover, the high discharge temperatures of thermal batteries and the instability of the molten salt electrolyte system complicate the electrochemical <em>in situ</em> characterization of these systems. In this context, <em>in situ</em> electrochemical impedance spectroscopy (EIS) has become widely employed in electrochemistry and represents a promising technique for <em>in situ</em> monitoring of thermal battery systems. Niobium-tungsten oxides, which possess a Wadsley-Roth crystal shear structure, exhibit excellent rate capability and cyclic stability as anode materials for lithium-ion batteries. Among them, Nb<sub>12</sub>WO<sub>33</sub> demonstrates remarkable lithium storage performance due to its unique 3D tunneling structure, which provides rapid de-intercalation channels for Li<sup>+</sup> ions. Given its excellent thermal and electrochemical stability, this study proposes the use of Nb<sub>12</sub>WO<sub>33</sub> as a cathode material for thermal batteries for the first time. Electrochemical impedance spectroscopy (EIS) at room temperature was employed to investigate the variations in the material's internal electronic conductivity impedance. The EIS Nyquist plots of the Nb<sub>12</sub>WO<sub>33</sub> electrode reveal a distinctive phenomenon of three semicircles in the high- and mid-frequency regions within the operating potential range. This behavior is primarily attributed to the electron conduction within the Nb<sub>12</sub>WO<sub>33</sub> electrode. The resistance associated with electronic conduction (<em>R</em><sub>E</sub>) exhibits a pattern of initial increase followed by a decrease. This phenomenon is explained by the valence transition of the Nb element from +5 to +4 occurring around 1.7 V. This step is more facile than the subsequent steps at 2.0 V and 1.2 V, resulting in the generation of a larger number of metastable electrons. Consequently, the internal channels become populated with electrons, leading to a significant increase in <em>R</em><sub>E</sub>. The thermal battery constructed with Nb<sub>12</sub>WO<sub>33</sub> as the cathode material was discharged at 500 °C and a current density of 500 mA g<sup>−1</sup> (with a cut-off voltage of 1.5 V), achieving a high specific capacity of 436.8 mA h g<sup>−1</sup> and an average polarized internal resistance of 0.52 Ω during pulse discharge. Therefore, Nb<sub>12</sub>WO<sub>33</sub> holds great potential as a cathode material for high-capacity, thermally stable thermal batteries. This study paves the way for the use of other niobium-tungsten oxides as cathode materials for thermal batteries and establishes a precedent for <em>in situ</em> EIS testing and anal","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100040"},"PeriodicalIF":10.8,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143102412","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 : 2024-12-04DOI: 10.3866/PKU.WHXB202406014
Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang
Sodium ion batteries (SIBs), due to their abundant resources, low raw material costs, excellent performance in low-temperature conditions, and fast charging capabilities, offer promising prospects for power grid energy storage and low-speed transportation. They serve as a complementary alternative to lithium-ion batteries. The cathode material is crucial for overall battery performance, acting as a bottleneck for enhancing the specific energy of SIBs and a significant factor influencing costs. Low-cost iron-based polyanionic cathode materials have garnered attention in basic research and industrialization due to their inherent advantages: excellent structural stability, high safety levels, and minimal volume strain during charge-discharge cycles. These advantages are pivotal for practical implementations in electric vehicles, large-scale energy storage systems, portable electronics, and related applications. However, challenges such as capacity decay and structural stability during prolonged cycling may limit their industrial applicability. Therefore, enhancing material cycling life and battery system stability are critical concerns. Additionally, researchers are focused on discovering new iron-based polyanionic cathode materials with high specific capacity, operating voltage, and conductivity. This review comprehensively covers recent advancements in iron-based polyanionic cathode materials for SIBs, encompassing iron-based phosphates, fluorophosphates, pyrophosphates, sulfates, and mixed polyanionic compounds. The analysis systematically explores crystal structures, preparation methods, sodium storage mechanisms, and modification strategies for various iron-based polyanionic materials, elucidating the structure-activity relationship between chemical composition, structural regulation techniques, and performance enhancement. Moreover, the article discusses challenges encountered during the transition from laboratory-scale research to large-scale industrial applications of iron-based polyanionic cathode materials, along with corresponding solutions. These insights aim to offer theoretical and technical guidance for developing novel, low-cost cathode materials with high specific energy densities and advancing the industrialization of SIBs.
{"title":"Research progress of iron-based polyanionic cathode materials for sodium-ion batteries","authors":"Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang","doi":"10.3866/PKU.WHXB202406014","DOIUrl":"10.3866/PKU.WHXB202406014","url":null,"abstract":"<div><div>Sodium ion batteries (SIBs), due to their abundant resources, low raw material costs, excellent performance in low-temperature conditions, and fast charging capabilities, offer promising prospects for power grid energy storage and low-speed transportation. They serve as a complementary alternative to lithium-ion batteries. The cathode material is crucial for overall battery performance, acting as a bottleneck for enhancing the specific energy of SIBs and a significant factor influencing costs. Low-cost iron-based polyanionic cathode materials have garnered attention in basic research and industrialization due to their inherent advantages: excellent structural stability, high safety levels, and minimal volume strain during charge-discharge cycles. These advantages are pivotal for practical implementations in electric vehicles, large-scale energy storage systems, portable electronics, and related applications. However, challenges such as capacity decay and structural stability during prolonged cycling may limit their industrial applicability. Therefore, enhancing material cycling life and battery system stability are critical concerns. Additionally, researchers are focused on discovering new iron-based polyanionic cathode materials with high specific capacity, operating voltage, and conductivity. This review comprehensively covers recent advancements in iron-based polyanionic cathode materials for SIBs, encompassing iron-based phosphates, fluorophosphates, pyrophosphates, sulfates, and mixed polyanionic compounds. The analysis systematically explores crystal structures, preparation methods, sodium storage mechanisms, and modification strategies for various iron-based polyanionic materials, elucidating the structure-activity relationship between chemical composition, structural regulation techniques, and performance enhancement. Moreover, the article discusses challenges encountered during the transition from laboratory-scale research to large-scale industrial applications of iron-based polyanionic cathode materials, along with corresponding solutions. These insights aim to offer theoretical and technical guidance for developing novel, low-cost cathode materials with high specific energy densities and advancing the industrialization of SIBs.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 4","pages":"Article 100035"},"PeriodicalIF":10.8,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093640","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 : 2024-12-03DOI: 10.3866/PKU.WHXB202402016
Qin Li , Huihui Zhang , Huajun Gu , Yuanyuan Cui , Ruihua Gao , Wei-Lin Dai
Against the backdrop of energy scarcities and ecological concerns, the process of photocatalytic hydrogen evolution emerges as a critical method for transforming solar energy into chemical energy. Central to this technology is the crafting of photocatalysts that are not only efficient and durable but also economically viable. The key to creating photocatalysts that boast superior hydrogen production capabilities lies in enhancing the separation and transfer of photo-generated electrons and holes. This study introduces a binary heterojunction photocatalyst, featuring a combination of Cd0.5Zn0.5S and Ti3C2 MXene, synthesized via an in situ hydrothermal method. In the composite, slender Cd0.5Zn0.5S nanorods are uniformly coated over the surface of single layer Ti3C2 nanosheets, forming a Schottky heterojunction at the material interface. This structure enhances the separation efficiency of photo-generated electrons and holes, thereby improving the utilization of light. With 0.5 wt % (mass fraction) of Ti3C2 MXene incorporated, we observed a peak photocatalytic H2 generation rate of 15.56 mmol g−1 h−1, outperforming the baseline Cd0.5Zn0.5S by 2.56 times. Notably, the photocatalytic efficiency remained largely unchanged after five cycles. This composite achieved the highest apparent quantum efficiency (AQE) of 18.4 % when exposed to 350 nm UV light. Various characterization techniques, including in situ X-ray photoelectron spectroscopy (XPS) and femtosecond transient absorption (fs-TA) spectroscopy, along with density functional theory (DFT) calculations, have further substantiated that the formation of a Schottky heterojunction at the interface is crucial for enhancing the photocatalytic hydrogen evolution performance of the composite material. This paper demonstrates the effectiveness of the novel carbon based material MXene as a co-catalyst for improving the performance of photocatalysts and offers a viable approach for the construction of MXene-containing photocatalytic hydrogen evolution catalysts.
{"title":"In situ growth of Cd0.5Zn0.5S nanorods on Ti3C2 MXene nanosheet for efficient visible-light-driven photocatalytic hydrogen evolution","authors":"Qin Li , Huihui Zhang , Huajun Gu , Yuanyuan Cui , Ruihua Gao , Wei-Lin Dai","doi":"10.3866/PKU.WHXB202402016","DOIUrl":"10.3866/PKU.WHXB202402016","url":null,"abstract":"<div><div>Against the backdrop of energy scarcities and ecological concerns, the process of photocatalytic hydrogen evolution emerges as a critical method for transforming solar energy into chemical energy. Central to this technology is the crafting of photocatalysts that are not only efficient and durable but also economically viable. The key to creating photocatalysts that boast superior hydrogen production capabilities lies in enhancing the separation and transfer of photo-generated electrons and holes. This study introduces a binary heterojunction photocatalyst, featuring a combination of Cd<sub>0.5</sub>Zn<sub>0.5</sub>S and Ti<sub>3</sub>C<sub>2</sub> MXene, synthesized <em>via</em> an <em>in situ</em> hydrothermal method. In the composite, slender Cd<sub>0.5</sub>Zn<sub>0.5</sub>S nanorods are uniformly coated over the surface of single layer Ti<sub>3</sub>C<sub>2</sub> nanosheets, forming a Schottky heterojunction at the material interface. This structure enhances the separation efficiency of photo-generated electrons and holes, thereby improving the utilization of light. With 0.5 wt % (mass fraction) of Ti<sub>3</sub>C<sub>2</sub> MXene incorporated, we observed a peak photocatalytic H<sub>2</sub> generation rate of 15.56 mmol g<sup>−1</sup> h<sup>−1</sup>, outperforming the baseline Cd<sub>0.5</sub>Zn<sub>0.5</sub>S by 2.56 times. Notably, the photocatalytic efficiency remained largely unchanged after five cycles. This composite achieved the highest apparent quantum efficiency (AQE) of 18.4 % when exposed to 350 nm UV light. Various characterization techniques, including <em>in situ</em> X-ray photoelectron spectroscopy (XPS) and femtosecond transient absorption (fs-TA) spectroscopy, along with density functional theory (DFT) calculations, have further substantiated that the formation of a Schottky heterojunction at the interface is crucial for enhancing the photocatalytic hydrogen evolution performance of the composite material. This paper demonstrates the effectiveness of the novel carbon based material MXene as a co-catalyst for improving the performance of photocatalysts and offers a viable approach for the construction of MXene-containing photocatalytic hydrogen evolution catalysts.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 4","pages":"Article 100031"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093638","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 : 2024-12-03DOI: 10.3866/PKU.WHXB202408015
Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang
Direct epoxidation of propylene (DEP) by molecular oxygen is an ideal way to synthesize propylene oxide (PO), yet it remains quite challenging. We demonstrated here that the PO formation rate and selectivity could be enhanced simultaneously through photo-thermo-catalysis over the CuOx/TiO2 catalyst. At 180 °C, by introducing light, the PO formation rate increased more than 20-fold (from 8.2 to 180.6 μmol g−1 h−1) and the corresponding selectivity improved more than 3-fold (from 8 % to 27 %), breaking the traditional perception that the semiconductors exhibit very low reactivity for this reaction. Kinetic study results showed that the apparent activation energy for PO formation could sharply decrease under light irradiation (from 95 to 40 kJ mol−1). In situ electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were applied to characterize the dynamics of the valence state of the copper oxide species and the activation intermediates of molecular oxygen. Evidence for the activation of oxygen, which could direct to the PO formation pathway, was captured. The light-driven electrons could promote the formation of active Cu+, which could form the side-on μ-peroxo Cu(II)2 structure, weaken the O–O bond, and improve the PO formation rate and selectivity. This work paves a new way for designing semiconductor-supported photocatalysts for DEP reactions with molecular oxygen.
{"title":"Light-enhanced direct epoxidation of propylene by molecular oxygen over CuOx/TiO2 catalyst","authors":"Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang","doi":"10.3866/PKU.WHXB202408015","DOIUrl":"10.3866/PKU.WHXB202408015","url":null,"abstract":"<div><div>Direct epoxidation of propylene (DEP) by molecular oxygen is an ideal way to synthesize propylene oxide (PO), yet it remains quite challenging. We demonstrated here that the PO formation rate and selectivity could be enhanced simultaneously through photo-thermo-catalysis over the CuO<em><sub>x</sub></em>/TiO<sub>2</sub> catalyst. At 180 °C, by introducing light, the PO formation rate increased more than 20-fold (from 8.2 to 180.6 μmol g<sup>−1</sup> h<sup>−1</sup>) and the corresponding selectivity improved more than 3-fold (from 8 % to 27 %), breaking the traditional perception that the semiconductors exhibit very low reactivity for this reaction. Kinetic study results showed that the apparent activation energy for PO formation could sharply decrease under light irradiation (from 95 to 40 kJ mol<sup>−1</sup>). <em>In situ</em> electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were applied to characterize the dynamics of the valence state of the copper oxide species and the activation intermediates of molecular oxygen. Evidence for the activation of oxygen, which could direct to the PO formation pathway, was captured. The light-driven electrons could promote the formation of active Cu<sup>+</sup>, which could form the side-on μ-peroxo Cu(II)<sub>2</sub> structure, weaken the O–O bond, and improve the PO formation rate and selectivity. This work paves a new way for designing semiconductor-supported photocatalysts for DEP reactions with molecular oxygen.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 4","pages":"Article 100038"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093656","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 : 2024-12-03DOI: 10.3866/PKU.WHXB202404024
Tianqi Bai , Kun Huang , Fachen Liu , Ruochen Shi , Wencai Ren , Songfeng Pei , Peng Gao , Zhongfan Liu
The rapid advancement in the integration density of electronic components has led to a pressing need for effective thermal management solutions. Among the promising materials in this regard, graphene stands out due to its exceptional thermal conductivity properties. Currently, the production of ultra-high thermally conductive thick graphene sheets primarily involves the reduction of graphene oxide. However, despite significant progress, the impact of defects on thermal properties remains inadequately understood, limiting the achievement of thermal conductivity exceeding 1500 W m−1 K−1. During the preparation process of reduced graphene oxide-based graphene sheets, hole structures are inevitably formed, reducing the overall density and thus decreasing thermal conductivity. However, the influencing factors on thermal diffusivity, one of the determining factors of thermal conductivity, have not been reported. Thus, we defined the intrinsic thermal diffusivity specific to materials with internal holes and further investigated the correlation between the intrinsic thermal diffusivity of thick graphene sheets and microstructure through various electron microscopy characterization, thermal diffusivity measurements, and simulations. We aim to elucidate the factors and mechanisms affecting the thermal diffusivity and hence thermal conductivity. Our research reveals subtle insights, particularly regarding the impact of holes of different sizes and quantities on thermal diffusivity. Notably, our simulation results show that a real dense-small-holes structure in graphene sheets can reduce thermal diffusivity by 39.4 %, more than twice the reduction caused by a single-large-hole structure (16.1 %). Statistical conclusions obtained through three-dimensional reconstruction also perfectly match these computational results. We emphasize that the presence of dense-small-holes structures disrupt the original high-speed heat transfer paths more severely, while the effect of single-large-hole structures are relatively weaker, primarily reducing overall density and thus thermal conductivity. Additionally, we found that the out-of-plane crystallinity has a significant impact on thermal diffusivity, further enhancing our understanding of microstructural factors affecting thermal diffusivity. By elucidating these mechanisms, our findings make significant contributions to the technological advancement of producing ultra-high thermally conductive thick graphene sheets. A deeper understanding of the interaction between microstructure and thermal performance brings hope for the development of next-generation electronic device thermal management solutions. Through continued research in this field, we anticipate further improvements in the performance and efficiency of graphene thermal management systems, ultimately driving innovation in electronic device design and manufacturing.
{"title":"Nanoscale mechanism of microstructure-dependent thermal diffusivity in thick graphene sheets","authors":"Tianqi Bai , Kun Huang , Fachen Liu , Ruochen Shi , Wencai Ren , Songfeng Pei , Peng Gao , Zhongfan Liu","doi":"10.3866/PKU.WHXB202404024","DOIUrl":"10.3866/PKU.WHXB202404024","url":null,"abstract":"<div><div>The rapid advancement in the integration density of electronic components has led to a pressing need for effective thermal management solutions. Among the promising materials in this regard, graphene stands out due to its exceptional thermal conductivity properties. Currently, the production of ultra-high thermally conductive thick graphene sheets primarily involves the reduction of graphene oxide. However, despite significant progress, the impact of defects on thermal properties remains inadequately understood, limiting the achievement of thermal conductivity exceeding 1500 W m<sup>−1</sup> K<sup>−1</sup>. During the preparation process of reduced graphene oxide-based graphene sheets, hole structures are inevitably formed, reducing the overall density and thus decreasing thermal conductivity. However, the influencing factors on thermal diffusivity, one of the determining factors of thermal conductivity, have not been reported. Thus, we defined the intrinsic thermal diffusivity specific to materials with internal holes and further investigated the correlation between the intrinsic thermal diffusivity of thick graphene sheets and microstructure through various electron microscopy characterization, thermal diffusivity measurements, and simulations. We aim to elucidate the factors and mechanisms affecting the thermal diffusivity and hence thermal conductivity. Our research reveals subtle insights, particularly regarding the impact of holes of different sizes and quantities on thermal diffusivity. Notably, our simulation results show that a real dense-small-holes structure in graphene sheets can reduce thermal diffusivity by 39.4 %, more than twice the reduction caused by a single-large-hole structure (16.1 %). Statistical conclusions obtained through three-dimensional reconstruction also perfectly match these computational results. We emphasize that the presence of dense-small-holes structures disrupt the original high-speed heat transfer paths more severely, while the effect of single-large-hole structures are relatively weaker, primarily reducing overall density and thus thermal conductivity. Additionally, we found that the out-of-plane crystallinity has a significant impact on thermal diffusivity, further enhancing our understanding of microstructural factors affecting thermal diffusivity. By elucidating these mechanisms, our findings make significant contributions to the technological advancement of producing ultra-high thermally conductive thick graphene sheets. A deeper understanding of the interaction between microstructure and thermal performance brings hope for the development of next-generation electronic device thermal management solutions. Through continued research in this field, we anticipate further improvements in the performance and efficiency of graphene thermal management systems, ultimately driving innovation in electronic device design and manufacturing.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 3","pages":"Article 100025"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143104725","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 : 2024-12-03DOI: 10.3866/PKU.WHXB202406007
Yikai Wang , Xiaolin Jiang , Haoming Song , Nan Wei , Yifan Wang , Xinjun Xu , Cuihong Li , Hao Lu , Yahui Liu , Zhishan Bo
Interlayer materials play a crucial role in achieving high efficiency in organic solar cells (OSCs). However, slight increases in film thickness often lead to significant charge accumulation and recombination, presenting a challenge for large-scale OSC device fabrication. Therefore, there is a pressing need for interlayer materials that are insensitive to variations in thickness. In this study, we synthesized a cost-effective cyano-modified perylene diimide (PDI) derivative, PDINBrCN, as an interlayer material. Compared to the analogous PDINBr, the introduction of cyano groups lowers the Lowest unoccupied molecular orbital (LUMO) energy level of the molecule, enhancing electron injection and charge transport efficiency. Additionally, PDINBrCN demonstrates excellent solubility in 2,2,2-trifluoroethanol (TFE) and effectively modifies the electrode work function, facilitating device fabrication through orthogonal solvent processing. When utilized as the cathode interlayer in D18:L8-BO devices, PDINBrCN achieved a high power conversion efficiency (PCE) of 18.83 % with a film thickness of 10 nm. Importantly, PDINBrCN maintained a PCE of 17.90 % even when the film thickness was increased to 50 nm. In contrast, the analogous PDI derivatives PDINBr and the star cathode interlayer material anthra [2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H, 9H)-tetrone (PDINN) achieved PCEs of 17.17 % and 17.06 %, respectively, at the same film thickness. Notably, PDINBrCN maintained a PCE of over 16 % even with an interlayer thickness of 80 nm, marking one of the best results for small molecule PDI derivatives as cathode interlayer materials at this thickness. Our findings demonstrate that PDINBrCN exhibits excellent processability, electrode work function adjustment capability, and crucially, thickness-insensitive properties. Therefore, PDINBrCN holds promise as an efficient and cost-effective cathode interlayer material, with potential for future commercial applications in OSCs.
{"title":"Thickness-insensitive, cyano-modified perylene diimide derivative as a cathode interlayer material for high-efficiency organic solar cells","authors":"Yikai Wang , Xiaolin Jiang , Haoming Song , Nan Wei , Yifan Wang , Xinjun Xu , Cuihong Li , Hao Lu , Yahui Liu , Zhishan Bo","doi":"10.3866/PKU.WHXB202406007","DOIUrl":"10.3866/PKU.WHXB202406007","url":null,"abstract":"<div><div>Interlayer materials play a crucial role in achieving high efficiency in organic solar cells (OSCs). However, slight increases in film thickness often lead to significant charge accumulation and recombination, presenting a challenge for large-scale OSC device fabrication. Therefore, there is a pressing need for interlayer materials that are insensitive to variations in thickness. In this study, we synthesized a cost-effective cyano-modified perylene diimide (PDI) derivative, <strong>PDINBrCN</strong>, as an interlayer material. Compared to the analogous <strong>PDINBr</strong>, the introduction of cyano groups lowers the Lowest unoccupied molecular orbital (LUMO) energy level of the molecule, enhancing electron injection and charge transport efficiency. Additionally, <strong>PDINBrCN</strong> demonstrates excellent solubility in 2,2,2-trifluoroethanol (TFE) and effectively modifies the electrode work function, facilitating device fabrication through orthogonal solvent processing. When utilized as the cathode interlayer in D18:L8-BO devices, <strong>PDINBrCN</strong> achieved a high power conversion efficiency (PCE) of 18.83 % with a film thickness of 10 nm. Importantly, <strong>PDINBrCN</strong> maintained a PCE of 17.90 % even when the film thickness was increased to 50 nm. In contrast, the analogous PDI derivatives <strong>PDINBr</strong> and the star cathode interlayer material anthra [2,1,9-def:6,5,10-d'e'f']diisoquinoline-1,3,8,10(2H, 9H)-tetrone (PDINN) achieved PCEs of 17.17 % and 17.06 %, respectively, at the same film thickness. Notably, <strong>PDINBrCN</strong> maintained a PCE of over 16 % even with an interlayer thickness of 80 nm, marking one of the best results for small molecule PDI derivatives as cathode interlayer materials at this thickness. Our findings demonstrate that <strong>PDINBrCN</strong> exhibits excellent processability, electrode work function adjustment capability, and crucially, thickness-insensitive properties. Therefore, <strong>PDINBrCN</strong> holds promise as an efficient and cost-effective cathode interlayer material, with potential for future commercial applications in OSCs.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 3","pages":"Article 100027"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143104727","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 : 2024-12-03DOI: 10.3866/PKU.WHXB202408004
Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu
The strong metal-support interaction (SMSI) is a widely recognized concept in heterogeneous catalysis, known for significantly enhancing catalyst stability and potentially modulating catalytic performance. However, because the SMSI effect is generally reversible, it tends to diminish under redox conditions opposite to those used for its construction. Consequently, its application is typically limited to conditions that are the same or similar to those under which it was formed. Herein, we report the application of oxidative SMSI (O-SMSI) constructed on hydroxyapatite-supported Rh catalyst (Rh/HAP) in a reductive reaction, the hydrogenation of furfuryl alcohol. In situ diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption and electron microscopy measurements reveal that high-temperature oxidation treatment at 500 °C induced the occurrence of O-SMSI on the Rh/HAP catalyst, accompanied by the encapsulation of Rh particles by the support. Upon the O-SMSI, the Rh species were effectively stabilized on the support surface, with significant suppression of sintering and leaching during liquid-phase reactions. As a result, the catalyst showed stable furfuryl alcohol conversion and cyclopentanone selectivity during recycling tests. Furthermore, it was found that the O-SMSI and the associated encapsulation behavior on the Rh/HAP system were only partially reversible rather than completely reversible. Even after high-temperature reduction at up to 600 °C, a portion of the SMSI effect remains, ensuring the stability of the catalysts in reductive reactions. This discovery greatly expands the application scope of SMSI catalysts and provides a new way to prepare stable hydrogenation catalysts.
{"title":"Stabilized Rh/hydroxyapatite catalyst for furfuryl alcohol hydrogenation: Application of oxidative strong metal-support interactions in reducing conditions","authors":"Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu","doi":"10.3866/PKU.WHXB202408004","DOIUrl":"10.3866/PKU.WHXB202408004","url":null,"abstract":"<div><div>The strong metal-support interaction (SMSI) is a widely recognized concept in heterogeneous catalysis, known for significantly enhancing catalyst stability and potentially modulating catalytic performance. However, because the SMSI effect is generally reversible, it tends to diminish under redox conditions opposite to those used for its construction. Consequently, its application is typically limited to conditions that are the same or similar to those under which it was formed. Herein, we report the application of oxidative SMSI (O-SMSI) constructed on hydroxyapatite-supported Rh catalyst (Rh/HAP) in a reductive reaction, the hydrogenation of furfuryl alcohol. <em>In situ</em> diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption and electron microscopy measurements reveal that high-temperature oxidation treatment at 500 °C induced the occurrence of O-SMSI on the Rh/HAP catalyst, accompanied by the encapsulation of Rh particles by the support. Upon the O-SMSI, the Rh species were effectively stabilized on the support surface, with significant suppression of sintering and leaching during liquid-phase reactions. As a result, the catalyst showed stable furfuryl alcohol conversion and cyclopentanone selectivity during recycling tests. Furthermore, it was found that the O-SMSI and the associated encapsulation behavior on the Rh/HAP system were only partially reversible rather than completely reversible. Even after high-temperature reduction at up to 600 °C, a portion of the SMSI effect remains, ensuring the stability of the catalysts in reductive reactions. This discovery greatly expands the application scope of SMSI catalysts and provides a new way to prepare stable hydrogenation catalysts.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 4","pages":"Article 100036"},"PeriodicalIF":10.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143093635","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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