Pub Date : 2024-11-21DOI: 10.1021/acs.jpcc.4c07062
Xueming Yang
Published as part of <i>The Journal of Physical Chemistry C</i> special issue “Xueming Yang Festschrift”. I was born in October, 1962, in the countryside not far from Hangzhou in Zhejiang Province, China. The area is famous for its lakes, rivers and canals and called “water town in southern China”, where most people live near rivers and lakes. The main mode of transportation in my hometown when I was a kid was by boat, so I learned early in my life about boat rowing and swimming in the rivers. My home village was located near a small river and not far from the Grand Beijing-Hangzhou Canal. Even though the village was only about 40 km away from Hangzhou, I never went to this beautiful and poetic city before I went to college. I started my elementary school in the spring of 1969, which is very close to my home village, only a 10 min walk. I spent five and a half years in the school. My elementary school years were during the Cultural Revolution period. I did not have much pressure from my family or from society to do well in the school. The most interesting thing that I remember from elementary school was the class before lunch, in which the teacher told stories from novels. During that period, I was also fascinated about stories told by an elderly blind gentleman, who often came to visit his relatives in the village. He was a famous fortune teller in the local area and seemed more knowledgeable than most people around. His stories made my countryside life more colorful as a young kid. After finishing elementary school, I went to middle school in the small town nearby, Xiashe, about a 40 min walk from my home. For a young kid, walking every day from home to school in the morning was a challenge. This is especially hard during the winter times and rainy days, when the roads were muddy and slippery. During those years, my father was the alarm clock in the morning to keep me going to middle school on time every day. I do not recall that I ever missed a single day of class during the four years in junior and senior high school. I am not so sure what really made me so persistent in going to school, maybe the little hope in my heart. In middle school, I started to have my first science classes, including mathematics, physics, and chemistry. However, English was not even in the curriculum in my high school years, so I started to learn English in college. In addition to the basic science classes, we also learned practical knowledge and skills that were more related to countryside life, such as how electric motors work, how to repair electric motors, and how to run farming tractors and to repair them. I also had a class that taught us how to do accounting for the collective village farm. These practical knowledge classes turned out to be very useful in the countryside. With the knowledge learned on these topics, it helped me to find problems such as why the electric motor-driven water pump was not working (when turning in the wrong direction). Looking back
{"title":"Autobiography of Xueming Yang","authors":"Xueming Yang","doi":"10.1021/acs.jpcc.4c07062","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07062","url":null,"abstract":"Published as part of <i>The Journal of Physical Chemistry C</i> special issue “Xueming Yang Festschrift”. I was born in October, 1962, in the countryside not far from Hangzhou in Zhejiang Province, China. The area is famous for its lakes, rivers and canals and called “water town in southern China”, where most people live near rivers and lakes. The main mode of transportation in my hometown when I was a kid was by boat, so I learned early in my life about boat rowing and swimming in the rivers. My home village was located near a small river and not far from the Grand Beijing-Hangzhou Canal. Even though the village was only about 40 km away from Hangzhou, I never went to this beautiful and poetic city before I went to college. I started my elementary school in the spring of 1969, which is very close to my home village, only a 10 min walk. I spent five and a half years in the school. My elementary school years were during the Cultural Revolution period. I did not have much pressure from my family or from society to do well in the school. The most interesting thing that I remember from elementary school was the class before lunch, in which the teacher told stories from novels. During that period, I was also fascinated about stories told by an elderly blind gentleman, who often came to visit his relatives in the village. He was a famous fortune teller in the local area and seemed more knowledgeable than most people around. His stories made my countryside life more colorful as a young kid. After finishing elementary school, I went to middle school in the small town nearby, Xiashe, about a 40 min walk from my home. For a young kid, walking every day from home to school in the morning was a challenge. This is especially hard during the winter times and rainy days, when the roads were muddy and slippery. During those years, my father was the alarm clock in the morning to keep me going to middle school on time every day. I do not recall that I ever missed a single day of class during the four years in junior and senior high school. I am not so sure what really made me so persistent in going to school, maybe the little hope in my heart. In middle school, I started to have my first science classes, including mathematics, physics, and chemistry. However, English was not even in the curriculum in my high school years, so I started to learn English in college. In addition to the basic science classes, we also learned practical knowledge and skills that were more related to countryside life, such as how electric motors work, how to repair electric motors, and how to run farming tractors and to repair them. I also had a class that taught us how to do accounting for the collective village farm. These practical knowledge classes turned out to be very useful in the countryside. With the knowledge learned on these topics, it helped me to find problems such as why the electric motor-driven water pump was not working (when turning in the wrong direction). Looking back ","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-21DOI: 10.1021/acs.jpcc.4c06639
Guorong Weng, Anastassia N. Alexandrova
Topological insulators (TIs) of the Bi2Se3 family exhibit a topological phase transition from three-dimensional (3D) to two-dimensional (2D) TIs in thin films with decreasing thickness. Understanding the driving force of this transition is critical for the applications of TIs in nanodevices. Herein, we investigate the finite-size effects on bulk band inversion and the structural relaxation effects on the surface states within the Bi2Se3 family via first-principles calculations. Thin films exposing the three lowest-energy surfaces are modeled by 2D slabs with tunable thicknesses. We propose that the thickness dependence of the topological phase originates from electron confinement created by surface cuts. The increase in film thickness then counteracts these confinement effects, resulting in a monotonically decreasing band gap evaluated at the spin–orbit decoupled level. This dependence of the bulk gap on the thickness is found to be consistent for various surface slabs. We utilize this relationship to predict the required thickness for maintaining the 3D TI phase and 2D surface states. Our findings underscore the importance of electron delocalization in determining the topological phase of TI thin films. In addition, the actual manifestation of topological surface states on the side surfaces is affected significantly by the coexisting dangling bonds produced by surface cuts. Therefore, surface relaxation plays a crucial role in disentangling the trivial and nontrivial surface states.
Bi2Se3 家族的拓扑绝缘体（TIs）在厚度不断减小的薄膜中表现出从三维（3D）到二维（2D）TIs 的拓扑相变。了解这种转变的驱动力对于拓扑结构在纳米器件中的应用至关重要。在此，我们通过第一原理计算研究了有限尺寸对体带反转的影响以及对 Bi2Se3 家族表面态的结构弛豫影响。暴露于三个最低能量表面的薄膜由厚度可调的二维板块建模。我们认为拓扑相的厚度依赖性源于表面切割产生的电子约束。薄膜厚度的增加会抵消这些约束效应，从而导致在自旋轨道解耦水平上评估的带隙单调递减。我们发现，带隙对厚度的这种依赖关系在各种表面板中都是一致的。我们利用这种关系来预测维持三维 TI 相和二维表面态所需的厚度。我们的研究结果强调了电子脱ocalization 在决定 TI 薄膜拓扑相方面的重要性。此外，拓扑表面态在侧表面的实际表现受到表面切割产生的共存悬空键的显著影响。因此，表面松弛在区分微不足道的表面态和非微不足道的表面态方面起着至关重要的作用。
{"title":"Understanding the Finite Size and Surface Relaxation Effects on the Surface States of Bi2Se3 Family Topological Insulators","authors":"Guorong Weng, Anastassia N. Alexandrova","doi":"10.1021/acs.jpcc.4c06639","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06639","url":null,"abstract":"Topological insulators (TIs) of the Bi<sub>2</sub>Se<sub>3</sub> family exhibit a topological phase transition from three-dimensional (3D) to two-dimensional (2D) TIs in thin films with decreasing thickness. Understanding the driving force of this transition is critical for the applications of TIs in nanodevices. Herein, we investigate the finite-size effects on bulk band inversion and the structural relaxation effects on the surface states within the Bi<sub>2</sub>Se<sub>3</sub> family via first-principles calculations. Thin films exposing the three lowest-energy surfaces are modeled by 2D slabs with tunable thicknesses. We propose that the thickness dependence of the topological phase originates from electron confinement created by surface cuts. The increase in film thickness then counteracts these confinement effects, resulting in a monotonically decreasing band gap evaluated at the spin–orbit decoupled level. This dependence of the bulk gap on the thickness is found to be consistent for various surface slabs. We utilize this relationship to predict the required thickness for maintaining the 3D TI phase and 2D surface states. Our findings underscore the importance of electron delocalization in determining the topological phase of TI thin films. In addition, the actual manifestation of topological surface states on the side surfaces is affected significantly by the coexisting dangling bonds produced by surface cuts. Therefore, surface relaxation plays a crucial role in disentangling the trivial and nontrivial surface states.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"14 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678981","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-20DOI: 10.1021/acs.jpcc.4c05812
Sergey P. Polyutov, Daniil E. Khrennikov, Artem S. Kostyukov, Maxim A. Visotin, Lasse K. Sørensen, Valeriy S. Gerasimov, Alexander E. Ershov, Sergey V. Karpov, Hans Ågren
This work delves into the processes leading to the evolution of nanofocusing plasmonic probes utilized in applications like tip-enhanced Raman spectroscopy, primarily under temperature growth. We identify stable crystallographic configurations of possible plasmonic tips that can withstand external influence, retain their original shape, and preserve their performance to enhance the local electromagnetic field under heat exposure. Employing molecular dynamics simulations, we study the behavior of plasmonic probes in the shape of sharp-edged gold nanotetrahedra as a case study. This makes it possible to observe the evolution of the shape and its impact on the light-concentrating performance of such probes. We identify the origin of shape instability and demonstrate that the migration of surface atoms from the tip area serves as the primary driver of shape variability in highly nonspherical plasmonic nanoparticles. By modeling the optical characteristics of the plasmonic probes utilizing the atomic discrete interaction model and finite element methods, we track alterations in the local electromagnetic field close to the apex of these gold nanotetrahedra at the plasmon resonance wavelength in the process of evolution. This analysis provides insight into the evolution of the field enhancement factor as the plasmonic tips degrade over time.
{"title":"Temperature Evolution of Plasmonic Probes for Tip-Enhanced Raman Scattering","authors":"Sergey P. Polyutov, Daniil E. Khrennikov, Artem S. Kostyukov, Maxim A. Visotin, Lasse K. Sørensen, Valeriy S. Gerasimov, Alexander E. Ershov, Sergey V. Karpov, Hans Ågren","doi":"10.1021/acs.jpcc.4c05812","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05812","url":null,"abstract":"This work delves into the processes leading to the evolution of nanofocusing plasmonic probes utilized in applications like tip-enhanced Raman spectroscopy, primarily under temperature growth. We identify stable crystallographic configurations of possible plasmonic tips that can withstand external influence, retain their original shape, and preserve their performance to enhance the local electromagnetic field under heat exposure. Employing molecular dynamics simulations, we study the behavior of plasmonic probes in the shape of sharp-edged gold nanotetrahedra as a case study. This makes it possible to observe the evolution of the shape and its impact on the light-concentrating performance of such probes. We identify the origin of shape instability and demonstrate that the migration of surface atoms from the tip area serves as the primary driver of shape variability in highly nonspherical plasmonic nanoparticles. By modeling the optical characteristics of the plasmonic probes utilizing the atomic discrete interaction model and finite element methods, we track alterations in the local electromagnetic field close to the apex of these gold nanotetrahedra at the plasmon resonance wavelength in the process of evolution. This analysis provides insight into the evolution of the field enhancement factor as the plasmonic tips degrade over time.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"13 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The recently emerging single-atom catalysts (SACs) are proposed as promising candidates for the catalytic oxidation of NO in the field of NO pollutant reduction from coal-fired power stations. However, due to the lack of theoretical model guidance, achieving efficient catalytic oxidation of NO at room temperature still remains a major concern. Thus, in this study, the reaction pathways for the catalytic oxidation of NO by OOH radicals on eight TM–N4–C (TM = Sc, Cr, Mn, Fe, Co, Ni, Cu, and Zn) were investigated based on density functional theory calculations. Based on the Bronsted–Evans–Polanyi linear relationship and microkinetic simulations, the activity volcano plot model for the catalytic oxidation of NO by OOH has been successfully established and validated. The Fe–N4–C and Mn–N4–C catalysts showed higher reactivities among these catalysts. The energy barriers for the rate-determining steps of these two catalysts were 0.14 and 0.30 eV, respectively, illustrating that catalytic oxidation of NO is feasible at room temperature. Significantly, a tri-activity volcano plot was constructed based on the unified activity descriptor of O adsorption energy for guiding the design of SACs in H2O2 catalytic oxidation of NO. The pathway of catalytic oxidation NO by OOH radicals is the dominant route in the system of SACs for the catalytic oxidation of NO by H2O2. The analysis of Bader charge and electronegativity revealed a linear correlation between the structural properties of the catalysts and the catalytic activity descriptor, which can be used to quickly predict the reactivity of SACs with different coordination environments. This work provides a new pathway for the current NO oxidation and guides future work on catalyst screening and experimental preparation.
最近出现的单原子催化剂（SAC）被认为是燃煤发电站氮氧化物减排领域中氮氧化物催化氧化的理想候选催化剂。然而，由于缺乏理论模型的指导，在室温下实现 NO 的高效催化氧化仍是一个主要问题。因此，本研究基于密度泛函理论计算，研究了 OOH 自由基在八种 TM-N4-C（TM = Sc、Cr、Mn、Fe、Co、Ni、Cu 和 Zn）上催化氧化 NO 的反应途径。基于布朗斯特-埃文斯-波兰尼线性关系和微动力学模拟，成功建立并验证了 OOH 催化氧化 NO 的活性火山图模型。在这些催化剂中，Fe-N4-C 和 Mn-N4-C 催化剂的反应活性较高。这两种催化剂决定速率步骤的能量势垒分别为 0.14 和 0.30 eV，说明 NO 催化氧化在室温下是可行的。值得注意的是，根据 O 吸附能这一统一的活性描述符，构建了三活性火山图，用于指导 H2O2 催化氧化 NO 的 SAC 的设计。在 H2O2 催化氧化 NO 的 SACs 体系中，OOH 自由基催化氧化 NO 的途径是主要途径。通过对巴德尔电荷和电负性的分析，发现催化剂的结构特性与催化活性描述符之间存在线性相关，可用于快速预测具有不同配位环境的 SAC 的反应活性。这项工作为当前的氮氧化物氧化提供了一条新途径，并为今后的催化剂筛选和实验制备工作提供了指导。
{"title":"Probing into the Catalytic Activity of Single-Atom Catalysts for NO Oxidation by H2O2 via the Tri-activity Volcano Plot","authors":"Weijie Yang, Xiang Li, Ruiyang Shi, Mingye Huang, Liugang Chen, Yixiao Sun, Yanfeng Liu, Zhengyang Gao","doi":"10.1021/acs.jpcc.4c06149","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06149","url":null,"abstract":"The recently emerging single-atom catalysts (SACs) are proposed as promising candidates for the catalytic oxidation of NO in the field of NO pollutant reduction from coal-fired power stations. However, due to the lack of theoretical model guidance, achieving efficient catalytic oxidation of NO at room temperature still remains a major concern. Thus, in this study, the reaction pathways for the catalytic oxidation of NO by OOH radicals on eight TM–N<sub>4</sub>–C (TM = Sc, Cr, Mn, Fe, Co, Ni, Cu, and Zn) were investigated based on density functional theory calculations. Based on the Bronsted–Evans–Polanyi linear relationship and microkinetic simulations, the activity volcano plot model for the catalytic oxidation of NO by OOH has been successfully established and validated. The Fe–N<sub>4</sub>–C and Mn–N<sub>4</sub>–C catalysts showed higher reactivities among these catalysts. The energy barriers for the rate-determining steps of these two catalysts were 0.14 and 0.30 eV, respectively, illustrating that catalytic oxidation of NO is feasible at room temperature. Significantly, a tri-activity volcano plot was constructed based on the unified activity descriptor of O adsorption energy for guiding the design of SACs in H<sub>2</sub>O<sub>2</sub> catalytic oxidation of NO. The pathway of catalytic oxidation NO by OOH radicals is the dominant route in the system of SACs for the catalytic oxidation of NO by H<sub>2</sub>O<sub>2</sub>. The analysis of Bader charge and electronegativity revealed a linear correlation between the structural properties of the catalysts and the catalytic activity descriptor, which can be used to quickly predict the reactivity of SACs with different coordination environments. This work provides a new pathway for the current NO oxidation and guides future work on catalyst screening and experimental preparation.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"29 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-20DOI: 10.1021/acs.jpcc.4c06727
Hisayoshi Kobayashi, Shin-Ichi Naya, Hiroaki Tada
Hydrogen peroxide (H2O2) is not only a clean oxidant widely used in industry but also a promising energy carrier. There is a strong demand to develop an environmentally friendly and sustainable method for producing H2O2 as an alternative to the current energy-consuming anthraquinone autoxidation process. We recently found that Au nanoparticle-loaded ZrO2 (Au/ZrO2) rich in oxygen vacancy (Ov) or surface OH-rich exhibits much higher catalytic activity than Au/ZrO2 poor in Ov or surface OH for the production of H2O2 from O2 and HCOOH at ambient temperature and pressure. To clarify the reason, possible reaction pathways were evaluated by density functional theory calculations. The results indicated that a Langmuir–Hinshelwood-type reaction proceeds near the Au NP-ZrO2(Ov)-liquid three-phase interfaces to yield H2O2 via the two-electron oxygen reduction reaction (2e–-ORR) due to the cooperation of Ov and water. On the other hand, H2O is preferentially formed via 4e–-ORR when either Ov or water is lacking. The Ov generated on the ZrO2 surface near the Au NPs induces the efficient reductive activation of O2 by electron transfer from the defect-derived midgap levels to O2 through Au NPs. On the other hand, the preferential adsorption of H2O on the Ov sites inhibits the O–O bond cleavage of O2 leading to 4e–-ORR. This study provided important insight into the mechanism of the Au/metal oxide-catalyzed ORR in an aqueous medium, which was previously poorly understood.
过氧化氢（H2O2）不仅是一种广泛应用于工业领域的清洁氧化剂，也是一种前景广阔的能源载体。人们强烈要求开发一种环境友好且可持续的方法来生产 H2O2，以替代目前耗能的蒽醌自氧化工艺。我们最近发现，在常温常压下，富含氧空位（Ov）或表面富含 OH 的金纳米粒子负载 ZrO2（Au/ZrO2）比富含 Ov 或表面 OH 的 Au/ZrO2 在从 O2 和 HCOOH 生成 H2O2 方面表现出更高的催化活性。为了弄清原因，我们通过密度泛函理论计算评估了可能的反应途径。结果表明，在 Au NP-ZrO2(Ov)-液三相界面附近，由于 Ov 和水的作用，一个 Langmuir-Hinshelwood 型反应通过双电子氧还原反应（2e-ORR）生成 H2O2。另一方面，在缺乏 Ov 或水的情况下，H2O 会优先通过 4e--ORR 生成。在氧化锆表面靠近金纳米粒子处产生的 Ov 通过电子传递从缺陷衍生的中隙水平经金纳米粒子传导至 O2，从而诱导 O2 的高效还原活化。另一方面，H2O优先吸附在Ov位点上，抑制了O2的O-O键裂解，导致4e--ORR。这项研究为水性介质中金/金属氧化物催化 ORR 的机理提供了重要的见解，而此前人们对这一机理知之甚少。
{"title":"Role of Oxygen Vacancies and Water in Hydrogen Peroxide Production from Oxygen and Formic Acid Catalyzed by Zirconia-Supported Gold Nanoparticle","authors":"Hisayoshi Kobayashi, Shin-Ichi Naya, Hiroaki Tada","doi":"10.1021/acs.jpcc.4c06727","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06727","url":null,"abstract":"Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) is not only a clean oxidant widely used in industry but also a promising energy carrier. There is a strong demand to develop an environmentally friendly and sustainable method for producing H<sub>2</sub>O<sub>2</sub> as an alternative to the current energy-consuming anthraquinone autoxidation process. We recently found that Au nanoparticle-loaded ZrO<sub>2</sub> (Au/ZrO<sub>2</sub>) rich in oxygen vacancy (O<sub>v</sub>) or surface OH-rich exhibits much higher catalytic activity than Au/ZrO<sub>2</sub> poor in O<sub>v</sub> or surface OH for the production of H<sub>2</sub>O<sub>2</sub> from O<sub>2</sub> and HCOOH at ambient temperature and pressure. To clarify the reason, possible reaction pathways were evaluated by density functional theory calculations. The results indicated that a Langmuir–Hinshelwood-type reaction proceeds near the Au NP-ZrO<sub>2</sub>(O<sub>v</sub>)-liquid three-phase interfaces to yield H<sub>2</sub>O<sub>2</sub> via the two-electron oxygen reduction reaction (2e<sup>–</sup>-ORR) due to the cooperation of O<sub>v</sub> and water. On the other hand, H<sub>2</sub>O is preferentially formed via 4e<sup>–</sup>-ORR when either O<sub>v</sub> or water is lacking. The O<sub>v</sub> generated on the ZrO<sub>2</sub> surface near the Au NPs induces the efficient reductive activation of O<sub>2</sub> by electron transfer from the defect-derived midgap levels to O<sub>2</sub> through Au NPs. On the other hand, the preferential adsorption of H<sub>2</sub>O on the O<sub>v</sub> sites inhibits the O–O bond cleavage of O<sub>2</sub> leading to 4e<sup>–</sup>-ORR. This study provided important insight into the mechanism of the Au/metal oxide-catalyzed ORR in an aqueous medium, which was previously poorly understood.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"33 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-20DOI: 10.1021/acs.jpcc.4c04507
Cairui Men, Li Shao, Xuan Li, Yuantao He, Yan Li, Shuo Tian, Meng Wei, Honggang Ye, Yinxiao Du
Potassium-ion batteries (KIBs) have drawn considerable research interest due to their excellent safety and the rich reserve of K. Although there have been great breakthroughs in KIB technology, exploring promising anode materials of KIBs is still a challenge. The development of high-performance two-dimensional anode materials is crucial for applications of KIBs. Here, by first-principles calculations, we find out a desirable anode material, a metallic δ5 borophene monolayer with a low diffusion barrier of 0.117 eV, a low average open-circuit voltage of 0.416 V, and a high storage capacity of 1549.37 mA h g–1. Such crucial characteristics make δ5 borophene a promising candidate for anode materials of KIBs.
钾离子电池（KIBs）因其卓越的安全性和丰富的钾储量而引起了广泛的研究兴趣。虽然钾离子电池技术已经取得了重大突破，但探索有前景的钾离子电池负极材料仍然是一项挑战。开发高性能的二维阳极材料对 KIB 的应用至关重要。在这里，我们通过第一性原理计算，发现了一种理想的阳极材料--金属δ5 硼吩单分子层，它具有 0.117 eV 的低扩散势垒、0.416 V 的低平均开路电压和 1549.37 mA h g-1 的高存储容量。这些关键特性使得δ5 硼吩有希望成为 KIB 负极材料的候选材料。
{"title":"Two-Dimensional δ5 Borophene Monolayer with High Specific Capacity for K-Ion Batteries: A First-Principles Study","authors":"Cairui Men, Li Shao, Xuan Li, Yuantao He, Yan Li, Shuo Tian, Meng Wei, Honggang Ye, Yinxiao Du","doi":"10.1021/acs.jpcc.4c04507","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c04507","url":null,"abstract":"Potassium-ion batteries (KIBs) have drawn considerable research interest due to their excellent safety and the rich reserve of K. Although there have been great breakthroughs in KIB technology, exploring promising anode materials of KIBs is still a challenge. The development of high-performance two-dimensional anode materials is crucial for applications of KIBs. Here, by first-principles calculations, we find out a desirable anode material, a metallic δ<sub>5</sub> borophene monolayer with a low diffusion barrier of 0.117 eV, a low average open-circuit voltage of 0.416 V, and a high storage capacity of 1549.37 mA h g<sup>–1</sup>. Such crucial characteristics make δ<sub>5</sub> borophene a promising candidate for anode materials of KIBs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"23 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, we investigated the photoelectric properties of nanosized anatase (∼55 and ∼4 nm) under high pressure, utilizing in situ Raman spectroscopy, photocurrent measurements, and theoretical calculations up to 27.6(5) GPa. Our findings reveal that 55 nm anatase shows a significant photocurrent increase of 2.4 times compared to ambient conditions before transitioning to the columbite phase at around 5.5(1) GPa. After this transition, the photocurrent gradually decreased up to 19.8(4) GPa. Notably, the columbite phase exhibited superior optoelectronic performance compared to the baddeleyite phase observed at approximately 15.5(3) GPa. For ∼4 nm anatase, an exceptional photocurrent increase of approximately 131 times was observed at 5.4(1) GPa compared to 1.5(0) GPa, with only a slight decrease between 5.4(1) and 27.6(5) GPa, and maintained a high level even after pressure release. The observed variations in photocurrent are attributed to changes in resistance, band gap, and absorption coefficient, each influencing the material’s response differently across various pressure ranges. These results underscore the potential of pressure-induced modulation to dramatically enhance the photoelectric properties of nanosized anatase, especially in ∼4 nm anatase. The ability to control the crystal structure and UV light response through pressure offers a promising strategy for improving the performance of TiO2-based ultraviolet photodetectors, making them more effective for advanced photoelectric applications.
{"title":"Pressure Effects on the Optoelectronic Property of Nanocrystalline Anatase with Different Sizes","authors":"Kaixiang Liu, Lidong Dai, Wen Liang, Shengyun Luo, Guangcan Luo, Jing Zhang, Qinghong Li, Tengfei Wang, Xiaohui Yang, Jialiang Dong, Rongrong Wang, Yong Meng","doi":"10.1021/acs.jpcc.4c06154","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06154","url":null,"abstract":"In this study, we investigated the photoelectric properties of nanosized anatase (∼55 and ∼4 nm) under high pressure, utilizing in situ Raman spectroscopy, photocurrent measurements, and theoretical calculations up to 27.6(5) GPa. Our findings reveal that 55 nm anatase shows a significant photocurrent increase of 2.4 times compared to ambient conditions before transitioning to the columbite phase at around 5.5(1) GPa. After this transition, the photocurrent gradually decreased up to 19.8(4) GPa. Notably, the columbite phase exhibited superior optoelectronic performance compared to the baddeleyite phase observed at approximately 15.5(3) GPa. For ∼4 nm anatase, an exceptional photocurrent increase of approximately 131 times was observed at 5.4(1) GPa compared to 1.5(0) GPa, with only a slight decrease between 5.4(1) and 27.6(5) GPa, and maintained a high level even after pressure release. The observed variations in photocurrent are attributed to changes in resistance, band gap, and absorption coefficient, each influencing the material’s response differently across various pressure ranges. These results underscore the potential of pressure-induced modulation to dramatically enhance the photoelectric properties of nanosized anatase, especially in ∼4 nm anatase. The ability to control the crystal structure and UV light response through pressure offers a promising strategy for improving the performance of TiO<sub>2</sub>-based ultraviolet photodetectors, making them more effective for advanced photoelectric applications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"101 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
(√3 × √3)R30 honeycomb superstructure ultrathin Ce–Ti–O film was prepared and confirmed using scanning tunneling microscopy (STM) and low-energy electron diffraction. The structural model of (√3 × √3)R30 honeycomb superstructure ultrathin film is determined using ab initio calculation and photoelectron holography. In the density functional theory (DFT) calculations, the (√3 × √3)R30 honeycomb superstructural model was calculated in two different conditions. The photoelectron holograms of Ti2+ and Ti3+ were separated from Ti 2p photoelectron spectra of (√3 × √3)R30 honeycomb superstructure, using a display-type retarding field analyzer. From the different forward-focusing peaks on the photoelectron holograms of Ti2+ and Ti3+, the vertical height between Ti divalent atoms and O atoms is higher than that between Ti trivalent atoms and O atoms. Also, the distance and direction of O and Ce atoms above Ti could be found. As a result, the simulated photoelectron holograms and the simulated STM image of the calculated Ce–Ti–O honeycomb superstructural model agree with the experimental photoelectron holograms and the experimental STM images.
(利用扫描隧道显微镜（STM）和低能电子衍射法制备并确认了（√3 × √3）R30 蜂窝超结构超薄 Ce-Ti-O 薄膜。利用 ab initio 计算和光电子全息法确定了 (√3 × √3)R30 蜂窝超结构超薄薄膜的结构模型。在密度泛函理论（DFT）计算中，在两种不同条件下计算了 (√3 × √3)R30 蜂窝超结构模型。利用显示型阻滞场分析仪从 (√3 × √3)R30 蜂窝上层结构的 Ti 2p 光电光谱中分离出 Ti2+ 和 Ti3+ 的光电子全息图。从 Ti2+ 和 Ti3+ 光电子全息图上不同的正向聚焦峰来看，Ti 二价原子与 O 原子间的垂直高度高于 Ti 三价原子与 O 原子间的垂直高度。此外，还可以发现 O 原子和 Ce 原子在 Ti 上方的距离和方向。因此，计算出的 Ce-Ti-O 蜂窝超结构模型的模拟光电子全息图和模拟 STM 图像与实验光电子全息图和实验 STM 图像一致。
{"title":"Schematic Structural Analysis of Honeycomb Structure Ultrathin Ce–Ti–O Films on Pt(111) Using Photoelectron Holography and Ab Initio Calculation","authors":"Xu Li, Shougo Yamada, Yuya Yamada, Momoko Yoshida, Yusuke Hashimoto, Tomohiro Matsushita, Weiliang Ma, Emilie Gaudry, Junji Yuhara","doi":"10.1021/acs.jpcc.4c05269","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05269","url":null,"abstract":"(√3 × √3)R30 honeycomb superstructure ultrathin Ce–Ti–O film was prepared and confirmed using scanning tunneling microscopy (STM) and low-energy electron diffraction. The structural model of (√3 × √3)R30 honeycomb superstructure ultrathin film is determined using ab initio calculation and photoelectron holography. In the density functional theory (DFT) calculations, the (√3 × √3)R30 honeycomb superstructural model was calculated in two different conditions. The photoelectron holograms of Ti<sup>2+</sup> and Ti<sup>3+</sup> were separated from Ti 2p photoelectron spectra of (√3 × √3)R30 honeycomb superstructure, using a display-type retarding field analyzer. From the different forward-focusing peaks on the photoelectron holograms of Ti<sup>2+</sup> and Ti<sup>3+</sup>, the vertical height between Ti divalent atoms and O atoms is higher than that between Ti trivalent atoms and O atoms. Also, the distance and direction of O and Ce atoms above Ti could be found. As a result, the simulated photoelectron holograms and the simulated STM image of the calculated Ce–Ti–O honeycomb superstructural model agree with the experimental photoelectron holograms and the experimental STM images.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"74 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The prospects of lead-free halide double perovskites in optoelectronic applications are often limited by their indirect bandgap, polaronic carrier transport, and intrinsic electronic defect levels. This work demonstrates a nearly 10-fold enhancement in self-trapped exciton emission intensity for Cs2AgBiBr6 thin films at room temperature following mild hydrogen plasma treatment. Analyzing the emission line widths at varying temperatures indicates that carrier–phonon coupling remains similarly prevalent. However, time-resolved photoluminescence and transient absorption measurements show that defect-mediated recombination is greatly suppressed in hydrogenated Cs2AgBiBr6 films. Based on photoelectron spectroscopy results, we propose that hydrogens can effectively compensate for deep-level Ag-on-Bi antisite defects, consequently shifting the Fermi level toward the conduction band edge. Below the cubic-to-tetragonal structural phase transition temperature, however, hydrogens act instead as nonradiative recombination centers. Taken together, this study highlights the potential of combining hydrogen plasma treatment with B-site disorder engineering to improve the functional characteristics of lead-free halide double perovskites.
无铅卤化物双包晶石在光电应用中的前景往往受到其间接带隙、极性载流子传输和内在电子缺陷水平的限制。这项研究表明，在室温下，经过温和的氢等离子处理后，Cs2AgBiBr6 薄膜的自俘获激子发射强度提高了近 10 倍。对不同温度下发射线宽的分析表明，载流子-声子耦合仍然同样普遍。然而，时间分辨光致发光和瞬态吸收测量表明，在氢化 Cs2AgBiBr6 薄膜中，缺陷介导的重组被大大抑制。根据光电子能谱分析结果，我们认为氢元素可以有效地补偿深层的锑镓反斜长石缺陷，从而使费米级向导带边缘移动。然而，在立方到四方结构相变温度以下，氢反而成为非辐射重组中心。综上所述，本研究强调了将氢等离子处理与 B 位无序工程相结合以改善无铅卤化物双包晶功能特性的潜力。
{"title":"Hydrogen Plasma Treatment Compensates for the Intrinsic Defects in Cs2AgBiBr6 Thin Films","authors":"Heng-Chi Chu, Chieh-Ming Hung, Hsin-Chen Huang, Shih-Chang Weng, Bi-Hsuan Lin, Song Yang, Yu-Hao Wu, Kai-Hsin Chang, Jing-Jong Shyue, Pi-Tai Chou, Chang-Ming Jiang","doi":"10.1021/acs.jpcc.4c05773","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05773","url":null,"abstract":"The prospects of lead-free halide double perovskites in optoelectronic applications are often limited by their indirect bandgap, polaronic carrier transport, and intrinsic electronic defect levels. This work demonstrates a nearly 10-fold enhancement in self-trapped exciton emission intensity for Cs<sub>2</sub>AgBiBr<sub>6</sub> thin films at room temperature following mild hydrogen plasma treatment. Analyzing the emission line widths at varying temperatures indicates that carrier–phonon coupling remains similarly prevalent. However, time-resolved photoluminescence and transient absorption measurements show that defect-mediated recombination is greatly suppressed in hydrogenated Cs<sub>2</sub>AgBiBr<sub>6</sub> films. Based on photoelectron spectroscopy results, we propose that hydrogens can effectively compensate for deep-level Ag-on-Bi antisite defects, consequently shifting the Fermi level toward the conduction band edge. Below the cubic-to-tetragonal structural phase transition temperature, however, hydrogens act instead as nonradiative recombination centers. Taken together, this study highlights the potential of combining hydrogen plasma treatment with B-site disorder engineering to improve the functional characteristics of lead-free halide double perovskites.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"14 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-19DOI: 10.1021/acs.jpcc.4c05878
William B. Carpenter, Abhijit A. Lavania, Allison H. Squires, W. E. Moerner
Today, biomolecular nanoparticles are prevalent as diagnostic tools and molecular delivery carriers, and it is particularly useful to examine individuals within a sample population to quantify the variations between objects and directly observe the molecular dynamics involving these objects. Using interferometric scattering as a highly sensitive label-free detection scheme, we recently developed the interferometric scattering anti-Brownian electrokinetic (ISABEL) trap to hold a single nanoparticle in solution for extended optical observation. In this perspective, we describe how we implemented this trap, how it extends the capabilities of previous ABEL traps, and how we have begun to study individual carboxysomes, a fascinating biological carbon fixation nanocompartment. By monitoring single nanocompartments for seconds to minutes in the ISABEL trap using simultaneous interferometric scattering and fluorescence spectroscopy, we have demonstrated single-compartment mass measurements, cargo-loading trends, and redox sensing inside individual particles. These experiments benefit from rich multiplexed correlative measurements utilizing both scattering and fluorescence with many exciting future capabilities within reach.
如今，生物分子纳米粒子作为诊断工具和分子输送载体已十分普遍，对样本群体中的个体进行检测，以量化对象之间的变化并直接观察涉及这些对象的分子动力学尤其有用。利用干涉散射作为一种高灵敏度的无标记检测方案，我们最近开发出了干涉散射反布朗电动力（ISABEL）阱，可将单个纳米粒子固定在溶液中进行长时间的光学观测。在本文中，我们将介绍如何实现这种捕集器，它如何扩展了以前的 ABEL 捕集器的功能，以及我们如何开始研究单个羧基体--一种迷人的生物碳固定纳米区室。通过使用同步干涉散射和荧光光谱技术对 ISABEL 捕集器中的单个纳米小室进行数秒至数分钟的监测，我们展示了单个小室的质量测量、货物装载趋势以及单个颗粒内部的氧化还原传感。这些实验得益于利用散射和荧光进行的丰富的多路复用相关测量，未来有望实现许多令人兴奋的功能。
{"title":"Label-Free Anti-Brownian Trapping of Single Nanoparticles in Solution","authors":"William B. Carpenter, Abhijit A. Lavania, Allison H. Squires, W. E. Moerner","doi":"10.1021/acs.jpcc.4c05878","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c05878","url":null,"abstract":"Today, biomolecular nanoparticles are prevalent as diagnostic tools and molecular delivery carriers, and it is particularly useful to examine individuals within a sample population to quantify the variations between objects and directly observe the molecular dynamics involving these objects. Using interferometric scattering as a highly sensitive label-free detection scheme, we recently developed the interferometric scattering anti-Brownian electrokinetic (ISABEL) trap to hold a single nanoparticle in solution for extended optical observation. In this perspective, we describe how we implemented this trap, how it extends the capabilities of previous ABEL traps, and how we have begun to study individual carboxysomes, a fascinating biological carbon fixation nanocompartment. By monitoring single nanocompartments for seconds to minutes in the ISABEL trap using simultaneous interferometric scattering and fluorescence spectroscopy, we have demonstrated single-compartment mass measurements, cargo-loading trends, and redox sensing inside individual particles. These experiments benefit from rich multiplexed correlative measurements utilizing both scattering and fluorescence with many exciting future capabilities within reach.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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