IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-02-01 DOI: 10.3866/PKU.WHXB202310029

Mengfei He , Chao Chen , Yue Tang , Si Meng , Zunfa Wang , Liyu Wang , Jiabao Xing , Xinyu Zhang , Jiahui Huang , Jiangbo Lu , Hongmei Jing , Xiangyu Liu , Hua Xu

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) exhibit diverse structures, encompassing a broad spectrum of electronic types ranging from metal, semiconductor, to insulator and topological insulator. They hold immense potential for both Moore and more-than-Moore device applications. Among them, manganese telluride (MnTe), an emerging nonlayered 2D material, has garnered considerable attention due to its exceptional properties and significant application potential in next-generation electronic and optoelectronic devices. However, the controllable synthesis of ultra-thin 2D MnTe remains a great challenge, which hindering the comprehensive exploration of its fundamental properties and potential applications. In this study, we present the synthesis of large-area MnTe nanosheets through chemical vapor deposition growth, showcasing its thickness-dependent properties and device applications. By increasing the growth temperature from 500 to 750 °C, the MnTe nanosheets’ thickness transitions from thin-layer to a thick flake, the domain size increases from 10 to 125 μm, the morphology changes from triangle to hexagon, culminating in a highly symmetrical round shape. Structural characterization and second harmonic generation measurements reveal that the obtained MnTe nanosheets exhibit high crystallization quality and superior second-order optical nonlinearity. The field effect transistor (FET) constructed with thin-layer MnTe demonstrates a p-type semiconductor characteristic, transitioning to a semimetal feature as the thickness increases to a thick flake. Leveraging these thickness-dependent electrical conduction transition features, we explore diverse applications of MnTe with varying thicknesses. The semiconductive thin-layer MnTe, serving as the photosensitive channel in a device, achieves superior photoresponse, showcasing considerable potential for photodetection appliations. The semimetallic thick-layer MnTe, acting as the contact electrode in a MoS₂ FET, significantly enhances device performance, with carrier mobility increasing from 12.76 cm² V⁻¹ s⁻¹ (Au contact) to 47.34 cm² V⁻¹ s⁻¹ (MnTe contact). This work lays the foundation for the controllable synthesis of nonlayered 2D MnTe and provides insights into its prospective development for constructing innovative electronic and optoelectronic devices.

{"title":"Epitaxial growth of nonlayered 2D MnTe nanosheets with thickness-tunable conduction for p-type field effect transistor and superior contact electrode","authors":"Mengfei He , Chao Chen , Yue Tang , Si Meng , Zunfa Wang , Liyu Wang , Jiabao Xing , Xinyu Zhang , Jiahui Huang , Jiangbo Lu , Hongmei Jing , Xiangyu Liu , Hua Xu","doi":"10.3866/PKU.WHXB202310029","DOIUrl":"10.3866/PKU.WHXB202310029","url":null,"abstract":"<div><div>Two-dimensional (2D) transition-metal dichalcogenides (TMDs) exhibit diverse structures, encompassing a broad spectrum of electronic types ranging from metal, semiconductor, to insulator and topological insulator. They hold immense potential for both Moore and more-than-Moore device applications. Among them, manganese telluride (MnTe), an emerging nonlayered 2D material, has garnered considerable attention due to its exceptional properties and significant application potential in next-generation electronic and optoelectronic devices. However, the controllable synthesis of ultra-thin 2D MnTe remains a great challenge, which hindering the comprehensive exploration of its fundamental properties and potential applications. In this study, we present the synthesis of large-area MnTe nanosheets through chemical vapor deposition growth, showcasing its thickness-dependent properties and device applications. By increasing the growth temperature from 500 to 750 °C, the MnTe nanosheets’ thickness transitions from thin-layer to a thick flake, the domain size increases from 10 to 125 μm, the morphology changes from triangle to hexagon, culminating in a highly symmetrical round shape. Structural characterization and second harmonic generation measurements reveal that the obtained MnTe nanosheets exhibit high crystallization quality and superior second-order optical nonlinearity. The field effect transistor (FET) constructed with thin-layer MnTe demonstrates a p-type semiconductor characteristic, transitioning to a semimetal feature as the thickness increases to a thick flake. Leveraging these thickness-dependent electrical conduction transition features, we explore diverse applications of MnTe with varying thicknesses. The semiconductive thin-layer MnTe, serving as the photosensitive channel in a device, achieves superior photoresponse, showcasing considerable potential for photodetection appliations. The semimetallic thick-layer MnTe, acting as the contact electrode in a MoS<sub>2</sub> FET, significantly enhances device performance, with carrier mobility increasing from 12.76 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup> (Au contact) to 47.34 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup> (MnTe contact). This work lays the foundation for the controllable synthesis of nonlayered 2D MnTe and provides insights into its prospective development for constructing innovative electronic and optoelectronic devices.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 2","pages":"Article 100016"},"PeriodicalIF":10.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143141050","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}

引用次数: 0

Insights into the greatly improved catalytic performance of N-doped BiOBr for CO2 photoreduction

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-28 DOI: 10.1016/j.actphy.2025.100055

Xianghai Song , Xiaoying Liu , Zhixiang Ren , Xiang Liu , Mei Wang , Yuanfeng Wu , Weiqiang Zhou , Zhi Zhu , Pengwei Huo

Photocatalytic carbon dioxide (CO₂) reduction represents a hopeful approach to addressing global energy and environmental issues. The quest for catalysts that demonstrate both high activity and selectivity for CO₂ conversion has attracted significant attention. In this study, ultrathin N-doped BiOBr was synthesized using a simple straightforward method. Systematic experimental results indicated that N-doping reduced the thickness of the BiOBr nanosheets and increased their specific surface area. Moreover, the efficiency of photogenerated charge carrier migration and the CO₂ adsorption capacity were significantly enhanced, contributing to improved CO₂ photoreduction performance. Experimental results showed that the 2N-BiOBr exhibited the best catalytic performance, with a CO evolution rate of 18.28 μmol·g⁻¹·h⁻¹ and nearly 100% CO selectivity in water, which was three times higher than that of pure BiOBr. The potential photocatalytic mechanism was investigated using in situ FTIR analysis and DFT simulations. Mechanistic studies revealed that N atoms replaced O atoms as adsorption centers, enhancing the strong adsorption selectivity towards CO₂ over O–H in BiOBr and facilitating the formation of key reaction intermediates. This study provides new perspectives on the creation and developmen of effective photocatalytic materials, offering theoretical support for the application of photocatalytic technology in energy and environmental science.

{"title":"Insights into the greatly improved catalytic performance of N-doped BiOBr for CO2 photoreduction","authors":"Xianghai Song , Xiaoying Liu , Zhixiang Ren , Xiang Liu , Mei Wang , Yuanfeng Wu , Weiqiang Zhou , Zhi Zhu , Pengwei Huo","doi":"10.1016/j.actphy.2025.100055","DOIUrl":"10.1016/j.actphy.2025.100055","url":null,"abstract":"<div><div>Photocatalytic carbon dioxide (CO<sub>2</sub>) reduction represents a hopeful approach to addressing global energy and environmental issues. The quest for catalysts that demonstrate both high activity and selectivity for CO<sub>2</sub> conversion has attracted significant attention. In this study, ultrathin N-doped BiOBr was synthesized using a simple straightforward method. Systematic experimental results indicated that N-doping reduced the thickness of the BiOBr nanosheets and increased their specific surface area. Moreover, the efficiency of photogenerated charge carrier migration and the CO<sub>2</sub> adsorption capacity were significantly enhanced, contributing to improved CO<sub>2</sub> photoreduction performance. Experimental results showed that the 2N-BiOBr exhibited the best catalytic performance, with a CO evolution rate of 18.28 μmol·g<sup>−1</sup>·h<sup>−1</sup> and nearly 100% CO selectivity in water, which was three times higher than that of pure BiOBr. The potential photocatalytic mechanism was investigated using <em>in situ</em> FTIR analysis and DFT simulations. Mechanistic studies revealed that N atoms replaced O atoms as adsorption centers, enhancing the strong adsorption selectivity towards CO<sub>2</sub> over O–H in BiOBr and facilitating the formation of key reaction intermediates. This study provides new perspectives on the creation and developmen of effective photocatalytic materials, offering theoretical support for the application of photocatalytic technology in energy and environmental science.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 6","pages":"Article 100055"},"PeriodicalIF":10.8,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428894","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}

引用次数: 0

Soft template-induced deep pore structure of Cu/Al2O3 for promoting plasma-catalyzed CO2 hydrogenation to DME

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-25 DOI: 10.1016/j.actphy.2025.100054

Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji

Plasma-activated heterogeneous catalysis is a promising strategy for catalytic CO₂ hydrogenation under mild conditions. In this study, pore structures with deep pore channels were constructed on Al₂O₃-x via a soft template method, and Cu/Al₂O₃-x was prepared by an impregnation method, with Al₂O₃-x serving as the support for plasma-catalyzed CO₂ hydrogenation to dimethyl ether (DME). Cu/Al₂O₃-0.75/HZSM-5 demonstrated a high performance and discharge efficiency for plasma-catalyzed CO₂ hydrogenation. The CO₂ conversion and DME yield for plasma-catalyzed CO₂ hydrogenation on Cu/Al₂O₃-0.75/HZSM-5 reached 21.98% and 9.83%, respectively, with selectivities for CO, CH₃OH, and DME on Cu/Al₂O₃-0.75/HZSM-5 of 25.39%, 29.89%, and 44.72%, respectively. The deep pore structures on Al₂O₃-x serve as Cu loading sites, and the confinement effect of the pores enhances the metal-support interaction and Cu metal dispersion. More abundant and stronger Brønsted basic and Lewis acidic sites facilitate the activation and hydrogenation of CO₂. Notably, the electric field formed by Cu sites anchored in the deep pore channel structures is conducive to guiding the activated plasma CO₂ intermediates into the difficult-to-access pores for hydrogenation. Hydrogenation of the plasma-activated CO₂ intermediates in the deep pore channels is crucial for improving plasma-catalyzed CO₂ hydrogenation to DME.

{"title":"Soft template-induced deep pore structure of Cu/Al2O3 for promoting plasma-catalyzed CO2 hydrogenation to DME","authors":"Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji","doi":"10.1016/j.actphy.2025.100054","DOIUrl":"10.1016/j.actphy.2025.100054","url":null,"abstract":"<div><div>Plasma-activated heterogeneous catalysis is a promising strategy for catalytic CO<sub>2</sub> hydrogenation under mild conditions. In this study, pore structures with deep pore channels were constructed on Al<sub>2</sub>O<sub>3</sub>-<em>x via</em> a soft template method, and Cu/Al<sub>2</sub>O<sub>3</sub>-<em>x</em> was prepared by an impregnation method, with Al<sub>2</sub>O<sub>3</sub>-<em>x</em> serving as the support for plasma-catalyzed CO<sub>2</sub> hydrogenation to dimethyl ether (DME). Cu/Al<sub>2</sub>O<sub>3</sub>-0.75/HZSM-5 demonstrated a high performance and discharge efficiency for plasma-catalyzed CO<sub>2</sub> hydrogenation. The CO<sub>2</sub> conversion and DME yield for plasma-catalyzed CO<sub>2</sub> hydrogenation on Cu/Al<sub>2</sub>O<sub>3</sub>-0.75/HZSM-5 reached 21.98% and 9.83%, respectively, with selectivities for CO, CH<sub>3</sub>OH, and DME on Cu/Al<sub>2</sub>O<sub>3</sub>-0.75/HZSM-5 of 25.39%, 29.89%, and 44.72%, respectively. The deep pore structures on Al<sub>2</sub>O<sub>3</sub>-<em>x</em> serve as Cu loading sites, and the confinement effect of the pores enhances the metal-support interaction and Cu metal dispersion. More abundant and stronger Brønsted basic and Lewis acidic sites facilitate the activation and hydrogenation of CO<sub>2</sub>. Notably, the electric field formed by Cu sites anchored in the deep pore channel structures is conducive to guiding the activated plasma CO<sub>2</sub> intermediates into the difficult-to-access pores for hydrogenation. Hydrogenation of the plasma-activated CO<sub>2</sub> intermediates in the deep pore channels is crucial for improving plasma-catalyzed CO<sub>2</sub> hydrogenation to DME.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 6","pages":"Article 100054"},"PeriodicalIF":10.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428895","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}

引用次数: 0

Modulating reactive oxygen species in O, S co-doped C3N4 to enhance photocatalytic degradation of microplastics

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-21 DOI: 10.1016/j.actphy.2025.100052

Yadan Luo , Hao Zheng , Xin Li , Fengmin Li , Hua Tang , Xilin She

Photocatalytic microplastic (MP) degradation via reactive oxygen species (ROS) is a considered environmentally friendly and sustainable approach for eliminating MP pollution in aquatic environments. However, it faces challenges due to the low migration and rapid recombination efficiency of charge carriers in photocatalysts. Herein, oxygen and sulfur co-doped carbon nitride (OSCN) nanosheets were synthesized through thermal polymerization coupled with a thermosolvent process. The O and S co-doping can reduce the bandgap and improve the light response of carbon nitride (C₃N₄). Meanwhile, O/S dopants effectively improve the delocalization of electron distribution, leading to increased carrier separation capacity, thereby promoting the formation of ROS and enhancing photocatalytic performance. Compared to C₃N₄, OSCN demonstrated significantly higher photocatalytic degradation and mineralization rates for MPs, including polyethylene (PE, traditional petroleum-based MPs) and polylactic acid (PLA, biodegradable bio-based MPs). Specifically, the mass loss of PE and PLA increased by 32.8 % and 34.1 %, respectively. Notably, ^•OH and ¹O₂ generated by OSCN synergistically catalyzed the degradation of PE, while ^•OH was the primary radical triggering the photolysis and hydrolysis of PLA. This study holds significant implications for the application of photocatalysis technology in the remediation of MP pollution in aquatic environments.

{"title":"Modulating reactive oxygen species in O, S co-doped C3N4 to enhance photocatalytic degradation of microplastics","authors":"Yadan Luo , Hao Zheng , Xin Li , Fengmin Li , Hua Tang , Xilin She","doi":"10.1016/j.actphy.2025.100052","DOIUrl":"10.1016/j.actphy.2025.100052","url":null,"abstract":"<div><div>Photocatalytic microplastic (MP) degradation <em>via</em> reactive oxygen species (ROS) is a considered environmentally friendly and sustainable approach for eliminating MP pollution in aquatic environments. However, it faces challenges due to the low migration and rapid recombination efficiency of charge carriers in photocatalysts. Herein, oxygen and sulfur co-doped carbon nitride (OSCN) nanosheets were synthesized through thermal polymerization coupled with a thermosolvent process. The O and S co-doping can reduce the bandgap and improve the light response of carbon nitride (C<sub>3</sub>N<sub>4</sub>). Meanwhile, O/S dopants effectively improve the delocalization of electron distribution, leading to increased carrier separation capacity, thereby promoting the formation of ROS and enhancing photocatalytic performance. Compared to C<sub>3</sub>N<sub>4</sub>, OSCN demonstrated significantly higher photocatalytic degradation and mineralization rates for MPs, including polyethylene (PE, traditional petroleum-based MPs) and polylactic acid (PLA, biodegradable bio-based MPs). Specifically, the mass loss of PE and PLA increased by 32.8 % and 34.1 %, respectively. Notably, <sup>•</sup>OH and <sup>1</sup>O<sub>2</sub> generated by OSCN synergistically catalyzed the degradation of PE, while <sup>•</sup>OH was the primary radical triggering the photolysis and hydrolysis of PLA. This study holds significant implications for the application of photocatalysis technology in the remediation of MP pollution in aquatic environments.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 6","pages":"Article 100052"},"PeriodicalIF":10.8,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428896","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}

引用次数: 0

Adjusting the electronic structure of Keggin-type polyoxometalates to construct S-scheme heterojunction for photocatalytic hydrogen evolution

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-20 DOI: 10.1016/j.actphy.2025.100051

Xinyu Miao , Hao Yang , Jie He , Jing Wang , Zhiliang Jin

The sluggish electron migration rate and pronounced electron-hole recombination, pose significant obstacles to achieving high photocatalytic efficiency. The utilization of multiple catalysts for the construction of heterojunctions can effectively enhance charge separation. A series of Keggin-type hollow dodecahedral polyoxometalates were prepared via hydrothermal synthesis, and their molecular orbitals were modified through the addition of metal elements. The incorporation of metal elements modulated the electronic structure of polyoxometalates, effectively enhancing the electron aggregation capability of polyoxometalates. Single-component catalysts often face serious hole-electron recombination. In order to solve this problem, the scheme of constructing heterojunction is proposed to improve the electron transport efficiency. By immobilizing ZnCdS nanoparticles onto the polyoxometalate surface, the heterojunction architecture was engineered to significantly enhance the interfacial charge transfer capability. Density Functional Theory (DFT) calculations and the experimental results indicate that the modulation of metallic components renders the polyoxometalate a more favorable energy-level orbital. The catalytic mechanism of ZnCdS and KMoP S-scheme heterojunction was also verified. The formation of S-scheme heterojunctions further improves the electron transfer efficiency compared to other traditional heterojunctions, achieving efficient utilization of photo generated electrons and holes. Additionally, the S-scheme heterojunction shifts the catalystʼs d-band center closer to the Fermi level, thereby improving electrical conductivity. This article provides a new approach for energy level regulation of polyoxometalates and the design of S-scheme heterojunctions.

{"title":"Adjusting the electronic structure of Keggin-type polyoxometalates to construct S-scheme heterojunction for photocatalytic hydrogen evolution","authors":"Xinyu Miao , Hao Yang , Jie He , Jing Wang , Zhiliang Jin","doi":"10.1016/j.actphy.2025.100051","DOIUrl":"10.1016/j.actphy.2025.100051","url":null,"abstract":"<div><div>The sluggish electron migration rate and pronounced electron-hole recombination, pose significant obstacles to achieving high photocatalytic efficiency. The utilization of multiple catalysts for the construction of heterojunctions can effectively enhance charge separation. A series of Keggin-type hollow dodecahedral polyoxometalates were prepared <em>via</em> hydrothermal synthesis, and their molecular orbitals were modified through the addition of metal elements. The incorporation of metal elements modulated the electronic structure of polyoxometalates, effectively enhancing the electron aggregation capability of polyoxometalates. Single-component catalysts often face serious hole-electron recombination. In order to solve this problem, the scheme of constructing heterojunction is proposed to improve the electron transport efficiency. By immobilizing ZnCdS nanoparticles onto the polyoxometalate surface, the heterojunction architecture was engineered to significantly enhance the interfacial charge transfer capability. Density Functional Theory (DFT) calculations and the experimental results indicate that the modulation of metallic components renders the polyoxometalate a more favorable energy-level orbital. The catalytic mechanism of ZnCdS and KMoP S-scheme heterojunction was also verified. The formation of S-scheme heterojunctions further improves the electron transfer efficiency compared to other traditional heterojunctions, achieving efficient utilization of photo generated electrons and holes. Additionally, the S-scheme heterojunction shifts the catalystʼs <em>d</em>-band center closer to the Fermi level, thereby improving electrical conductivity. This article provides a new approach for energy level regulation of polyoxometalates and the design of S-scheme heterojunctions.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 6","pages":"Article 100051"},"PeriodicalIF":10.8,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143428898","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}

引用次数: 0

Rationally designed ZnFe1.2Co0.8O4/BiVO4 S-scheme heterojunction with spin-polarization for the elimination of antibiotic

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-14 DOI: 10.1016/j.actphy.2025.100050

Jinwang Wu , Qijing Xie , Chengliang Zhang , Haifeng Shi

Recently, the regulation of electronic spin polarization has attracted considerable interest as an effective strategy to mitigate the rapid recombination of photo-generated charges. However, current research predominantly targets individual photocatalysts, where the efficiency of charge separation still has significant room for improvement. Herein, a ZnFe_1.2Co_0.8O₄ (ZFCO) and BiVO₄ (BVO) S-scheme heterojunction was developed, which synergistically promoted charge separation through the S-scheme heterojunction and spin polarization, and further enhanced the photocatalytic performance in removing organic pollutants under an external magnetic field. Experimental results revealed that under sole light irradiation, ZB-1.5 (ZFCO : BVO = 3 : 2) demonstrated optimal performance, with a reaction rate constant (k) for tetracycline (TC) degradation of 0.0146 min⁻¹. Under light irradiation and magnetic field conditions, the reaction rate constant (k) of ZB-1.5 for TC degradation increased to 0.0175 min⁻¹, indicating enhanced photocatalytic performance. DFT calculations indicated that ZFCO exhibited the spin polarization. Photoluminescence measurements demonstrated that the S-scheme heterojunction structure improved the charge separation efficiency. In addition, possible degradation pathways and toxicity were assessed, indicating successful detoxification. This work provides some useful insights into utilizing S-scheme heterojunctions to develop photocatalysts with efficient separation of photo-generated charges.

{"title":"Rationally designed ZnFe1.2Co0.8O4/BiVO4 S-scheme heterojunction with spin-polarization for the elimination of antibiotic","authors":"Jinwang Wu , Qijing Xie , Chengliang Zhang , Haifeng Shi","doi":"10.1016/j.actphy.2025.100050","DOIUrl":"10.1016/j.actphy.2025.100050","url":null,"abstract":"<div><div>Recently, the regulation of electronic spin polarization has attracted considerable interest as an effective strategy to mitigate the rapid recombination of photo-generated charges. However, current research predominantly targets individual photocatalysts, where the efficiency of charge separation still has significant room for improvement. Herein, a ZnFe<sub>1.2</sub>Co<sub>0.8</sub>O<sub>4</sub> (ZFCO) and BiVO<sub>4</sub> (BVO) S-scheme heterojunction was developed, which synergistically promoted charge separation through the S-scheme heterojunction and spin polarization, and further enhanced the photocatalytic performance in removing organic pollutants under an external magnetic field. Experimental results revealed that under sole light irradiation, ZB-1.5 (ZFCO : BVO = 3 : 2) demonstrated optimal performance, with a reaction rate constant (<em>k</em>) for tetracycline (TC) degradation of 0.0146 min<sup>−1</sup>. Under light irradiation and magnetic field conditions, the reaction rate constant (<em>k</em>) of ZB-1.5 for TC degradation increased to 0.0175 min<sup>−1</sup>, indicating enhanced photocatalytic performance. DFT calculations indicated that ZFCO exhibited the spin polarization. Photoluminescence measurements demonstrated that the S-scheme heterojunction structure improved the charge separation efficiency. In addition, possible degradation pathways and toxicity were assessed, indicating successful detoxification. This work provides some useful insights into utilizing S-scheme heterojunctions to develop photocatalysts with efficient separation of photo-generated charges.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100050"},"PeriodicalIF":10.8,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143102411","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}

引用次数: 0

Research on Cu-based and Pt-based catalysts for hydrogen production through methanol steam reforming

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-13 DOI: 10.1016/j.actphy.2025.100049

Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu

Methanol steam reforming (MSR) is a critical pathway for on-board hydrogen production from methanol, playing a significant role in clean energy applications. The catalytic performance in MSR reactions directly influences hydrogen yield and byproduct composition, with Cu-based and Pt-based catalysts extensively studied for their high efficiency. The catalytic mechanism primarily involves the cleavage of C–H and O–H bonds in methanol and water molecules. The activity of Cu-based catalysts depends on the ratio and synergistic interaction of Cu⁰ and Cu⁺ active sites, while Pt-based catalysts operate through Pt⁰, Pt^δ+ or Pt²⁺ active sites, in conjunction with oxygen vacancies. However, the electron transfer and interaction mechanisms between active metals and supports remain contentious, impacting the metal oxidation states, adsorption sites, and reaction pathway selectivity. This is particularly evident in the pathways for methanol dehydrogenation and intermediate product formation (e.g., formaldehyde, formic acid, and methyl formate), which lack a unified understanding. This review systematically examines the unitary and synergistic roles of Cu⁰ and Cu⁺ sites, explores the direct and synergistic pathways of Pt-based catalysts, and analyzes the effects of additives such as In₂O₃ on Pt site modulation and oxygen vacancy generation. By integrating catalytic performance evaluations with mechanistic insights, strategies are proposed to enhance catalyst activity and stability. This comprehensive review not only advances the understanding of MSR mechanisms but also provides a theoretical foundation and research direction for the development of high-performance catalysts for on-board hydrogen production.

{"title":"Research on Cu-based and Pt-based catalysts for hydrogen production through methanol steam reforming","authors":"Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu","doi":"10.1016/j.actphy.2025.100049","DOIUrl":"10.1016/j.actphy.2025.100049","url":null,"abstract":"<div><div>Methanol steam reforming (MSR) is a critical pathway for on-board hydrogen production from methanol, playing a significant role in clean energy applications. The catalytic performance in MSR reactions directly influences hydrogen yield and byproduct composition, with Cu-based and Pt-based catalysts extensively studied for their high efficiency. The catalytic mechanism primarily involves the cleavage of C–H and O–H bonds in methanol and water molecules. The activity of Cu-based catalysts depends on the ratio and synergistic interaction of Cu<sup>0</sup> and Cu<sup>+</sup> active sites, while Pt-based catalysts operate through Pt<sup>0</sup>, Pt<sup>δ+</sup> or Pt<sup>2+</sup> active sites, in conjunction with oxygen vacancies. However, the electron transfer and interaction mechanisms between active metals and supports remain contentious, impacting the metal oxidation states, adsorption sites, and reaction pathway selectivity. This is particularly evident in the pathways for methanol dehydrogenation and intermediate product formation (e.g., formaldehyde, formic acid, and methyl formate), which lack a unified understanding. This review systematically examines the unitary and synergistic roles of Cu<sup>0</sup> and Cu<sup>+</sup> sites, explores the direct and synergistic pathways of Pt-based catalysts, and analyzes the effects of additives such as In<sub>2</sub>O<sub>3</sub> on Pt site modulation and oxygen vacancy generation. By integrating catalytic performance evaluations with mechanistic insights, strategies are proposed to enhance catalyst activity and stability. This comprehensive review not only advances the understanding of MSR mechanisms but also provides a theoretical foundation and research direction for the development of high-performance catalysts for on-board hydrogen production.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100049"},"PeriodicalIF":10.8,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427747","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}

引用次数: 0

Pt single-atom-functionalized 2D Al-TCPP MOF nanosheets for enhanced photodynamic antimicrobial therapy

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-09 DOI: 10.1016/j.actphy.2025.100046

Shiyang He , Dandan Chu , Zhixin Pang , Yuhang Du , Jiayi Wang , Yuhong Chen , Yumeng Su , Jianhua Qin , Xiangrong Pan , Zhan Zhou , Jingguo Li , Lufang Ma , Chaoliang Tan

The pressing challenges posed by infectious diseases caused by pathogenic microbial infections have necessitated the development of advanced antimicrobial strategies. Among the promising avenues, photodynamic therapy (PDT) has emerged as a promising approach due to its non-invasive and targeted nature. Although it has been widely used in antibacterial therapy, there are still obstacles in precisely regulating the structure of photosensitizers to achieve satisfactory photodynamic performance. Herein, Pt single-atoms (SAs) are deposited on two-dimensional (2D) Al-TCPP metal-organic framework (MOF) nanosheets, creating Pt/Al-TCPP as the photosensitizer to boost reactive oxygen species (ROS) production for enhanced photodynamic antimicrobial therapy. By integrating Pt SAs onto 2D Al-TCPP MOF nanosheets, we not only improve the dispersion and stability of Pt atoms but also harness the synergistic effect between the MOF's crystal porous structure and Pt SAs, optimizing its light-trapping ability. This unique structure enhances the bridging unit between Pt SA and the porphyrin linker, facilitating efficient charge transfer and separation during illumination, ultimately boosting ROS production. In addition to the inherent photodynamic performance of Pt SAs, they can also increase the adsorption of oxygen, facilitate electron transfer, and improve charge separation, thus enhancing photodynamic ROS generation efficiency. Therefore, the Pt/Al-TCPP photosensitizer shows much greater efficacy in generating ROS under a 660 nm laser irradiation compared to Al-TCPP. Both in vitro and in vivo experiments demonstrate that the Pt/Al-TCPP nanosheets can effectively eliminate bacteria and promote wound healing in a short time at low doses under laser irradiation. This study underscores the advantages of integrating Pt SAs with Pt/Al-TCPP nanosheets and offers a highly effective photosensitizer for bacterial infections. The results pave the way for novel strategies in the antibacterial realm, highlighting the potential of Pt/Al-TCPP nanosheets as a promising therapeutic agent for efficient wound healing.

{"title":"Pt single-atom-functionalized 2D Al-TCPP MOF nanosheets for enhanced photodynamic antimicrobial therapy","authors":"Shiyang He , Dandan Chu , Zhixin Pang , Yuhang Du , Jiayi Wang , Yuhong Chen , Yumeng Su , Jianhua Qin , Xiangrong Pan , Zhan Zhou , Jingguo Li , Lufang Ma , Chaoliang Tan","doi":"10.1016/j.actphy.2025.100046","DOIUrl":"10.1016/j.actphy.2025.100046","url":null,"abstract":"<div><div>The pressing challenges posed by infectious diseases caused by pathogenic microbial infections have necessitated the development of advanced antimicrobial strategies. Among the promising avenues, photodynamic therapy (PDT) has emerged as a promising approach due to its non-invasive and targeted nature. Although it has been widely used in antibacterial therapy, there are still obstacles in precisely regulating the structure of photosensitizers to achieve satisfactory photodynamic performance. Herein, Pt single-atoms (SAs) are deposited on two-dimensional (2D) Al-TCPP metal-organic framework (MOF) nanosheets, creating Pt/Al-TCPP as the photosensitizer to boost reactive oxygen species (ROS) production for enhanced photodynamic antimicrobial therapy. By integrating Pt SAs onto 2D Al-TCPP MOF nanosheets, we not only improve the dispersion and stability of Pt atoms but also harness the synergistic effect between the MOF's crystal porous structure and Pt SAs, optimizing its light-trapping ability. This unique structure enhances the bridging unit between Pt SA and the porphyrin linker, facilitating efficient charge transfer and separation during illumination, ultimately boosting ROS production. In addition to the inherent photodynamic performance of Pt SAs, they can also increase the adsorption of oxygen, facilitate electron transfer, and improve charge separation, thus enhancing photodynamic ROS generation efficiency. Therefore, the Pt/Al-TCPP photosensitizer shows much greater efficacy in generating ROS under a 660 nm laser irradiation compared to Al-TCPP. Both <em>in vitro</em> and <em>in vivo</em> experiments demonstrate that the Pt/Al-TCPP nanosheets can effectively eliminate bacteria and promote wound healing in a short time at low doses under laser irradiation. This study underscores the advantages of integrating Pt SAs with Pt/Al-TCPP nanosheets and offers a highly effective photosensitizer for bacterial infections. The results pave the way for novel strategies in the antibacterial realm, highlighting the potential of Pt/Al-TCPP nanosheets as a promising therapeutic agent for efficient wound healing.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100046"},"PeriodicalIF":10.8,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164819","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}

引用次数: 0

High-precision and reliable thermal conductivity measurement for graphene films based on an improved steady-state electric heating method

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-09 DOI: 10.1016/j.actphy.2025.100045

Jiahao Lu , Xin Ming , Yingjun Liu , Yuanyuan Hao , Peijuan Zhang , Songhan Shi , Yi Mao , Yue Yu , Shengying Cai , Zhen Xu , Chao Gao

The graphene film with high thermal conductivity has garnered considerable attention in recent years as an ideal material for dissipating heat in high-power electronic devices. Thermal conductivity is a crucial parameter for evaluating its fundamental performance. High-precision measurement holds significant importance for understanding its basic properties, fabrication optimization, and industrial applications. However, it is difficult to simultaneously achieve efficient, accurate, and reliable measurements with existing commercial thermal conductivity testing methods. The development of a convenient, high-precision, and reliable measurement approach remains a great challenge. Here, we introduce a thermal conductivity testing methodology with superior accuracy and excellent efficiency based on an improved steady-state electric heating method, refined through the optimization of heat transfer principles, experimental operation, and data analysis, supported by finite element simulation. The accuracy of measurements is affected by four factors: heat loss calibration, sample size, device design, and data treatment. The experimental results show that the heat loss caused by heat radiation and heat convection affects the temperature distribution and the measurements of the sample, which should be strictly controlled by sample size and temperature rise. Reasonable screening and preprocessing of data are also necessary to improve measurement accuracy. Through the comparative analysis of the temperature distribution and thermal conductivity measurements of samples under different conditions, we propose feasible operational guidance and a standardized testing protocol to minimize measurement error. The measurement error is less than 3.0%, and uncertainty is reduced to 0.5%. Simulation results confirm that the response time of this method is down to milliseconds, correlating well with the experiment, which can effectively improve test efficiency. Considering the combined merits of high accuracy, repeatability, and fast response, the improved steady-state electric heating method offers useful guidance for the accurate evaluation of the thermal conductivity of materials and crucial technical support for research and application in thermal management.

{"title":"High-precision and reliable thermal conductivity measurement for graphene films based on an improved steady-state electric heating method","authors":"Jiahao Lu , Xin Ming , Yingjun Liu , Yuanyuan Hao , Peijuan Zhang , Songhan Shi , Yi Mao , Yue Yu , Shengying Cai , Zhen Xu , Chao Gao","doi":"10.1016/j.actphy.2025.100045","DOIUrl":"10.1016/j.actphy.2025.100045","url":null,"abstract":"<div><div>The graphene film with high thermal conductivity has garnered considerable attention in recent years as an ideal material for dissipating heat in high-power electronic devices. Thermal conductivity is a crucial parameter for evaluating its fundamental performance. High-precision measurement holds significant importance for understanding its basic properties, fabrication optimization, and industrial applications. However, it is difficult to simultaneously achieve efficient, accurate, and reliable measurements with existing commercial thermal conductivity testing methods. The development of a convenient, high-precision, and reliable measurement approach remains a great challenge. Here, we introduce a thermal conductivity testing methodology with superior accuracy and excellent efficiency based on an improved steady-state electric heating method, refined through the optimization of heat transfer principles, experimental operation, and data analysis, supported by finite element simulation. The accuracy of measurements is affected by four factors: heat loss calibration, sample size, device design, and data treatment. The experimental results show that the heat loss caused by heat radiation and heat convection affects the temperature distribution and the measurements of the sample, which should be strictly controlled by sample size and temperature rise. Reasonable screening and preprocessing of data are also necessary to improve measurement accuracy. Through the comparative analysis of the temperature distribution and thermal conductivity measurements of samples under different conditions, we propose feasible operational guidance and a standardized testing protocol to minimize measurement error. The measurement error is less than 3.0%, and uncertainty is reduced to 0.5%. Simulation results confirm that the response time of this method is down to milliseconds, correlating well with the experiment, which can effectively improve test efficiency. Considering the combined merits of high accuracy, repeatability, and fast response, the improved steady-state electric heating method offers useful guidance for the accurate evaluation of the thermal conductivity of materials and crucial technical support for research and application in thermal management.</div></div>","PeriodicalId":6964,"journal":{"name":"物理化学学报","volume":"41 5","pages":"Article 100045"},"PeriodicalIF":10.8,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143102410","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}

引用次数: 0

Corrigendum to “Mechanistic insights into water-mediated CO2 electrochemical reduction reactions on Cu@C2N catalysts: A Theoretical study” [Acta Physico-Chimica Sinica (2024) 40, 2303040]

IF 10.8 2区化学 Q1 CHEMISTRY, PHYSICAL

物理化学学报

Pub Date : 2025-01-06 DOI: 10.1016/j.actphy.2024.100043

Hanyu Xu , Xuedan Song , Qing Zhang , Chang Yu , Jieshan Qiu

引用次数: 0

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