The Journal of Physical Chemistry Letters最新文献_第2页

Unusual Hydrophobic Property of Blue Fluorescent Amino Acid 4-Cyanotryptophan. 蓝色荧光氨基酸 4-Cyanotryptophan 的非同寻常的疏水性。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-15 DOI: 10.1021/acs.jpclett.4c02842

Manxi Wang, Bo Zhuang, Kailin Tang, Ran-Ran Feng, Feng Gai

{"title":"Unusual Hydrophobic Property of Blue Fluorescent Amino Acid 4-Cyanotryptophan.","authors":"Manxi Wang, Bo Zhuang, Kailin Tang, Ran-Ran Feng, Feng Gai","doi":"10.1021/acs.jpclett.4c02842","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02842","url":null,"abstract":"It is a common belief that the negative heat capacity change (ΔCp) associated with protein folding, which is a manifestation of the hydrophobic effect, results from a decrease in the solvent accessible hydrophobic surface area. Herein, we investigate the conformational energy landscape and dynamics of a tetrapeptide composed of two glycine and two 4-cyanotryptophan residues using time-resolved fluorescence spectroscopy, molecular dynamics simulations, and density functional theory calculations and find that, contrary to this expectation, the hydrophobic association of two 4-cyanotryptophan side chains leads to a positive ΔCp (approximately 543 J K-1 mol-1). Furthermore, we find that promoting one of the 4-cyanotryptophans to its excited electronic state strengthens this self-association. Taken together, our results provide not only insight into how modification of an aromatic amino acid can affect its hydrophobicity but also a potential strategy for designing protein sequences that can fold (unfold) at high (low) temperatures.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"11723-11729"},"PeriodicalIF":4.8,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637934","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

Cu-Supported ZnO under Conditions of CO₂ Reduction to Methanol: Why 0.2 ML Coverage? 二氧化碳还原成甲醇条件下的铜支撑氧化锌：为什么是 0.2 ML 覆盖率？

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-15 DOI: 10.1021/acs.jpclett.4c02908

Robert H Lavroff, Edison Cummings, Kaustubh Sawant, Zisheng Zhang, Philippe Sautet, Anastassia N Alexandrova

{"title":"Cu-Supported ZnO under Conditions of CO2 Reduction to Methanol: Why 0.2 ML Coverage?","authors":"Robert H Lavroff, Edison Cummings, Kaustubh Sawant, Zisheng Zhang, Philippe Sautet, Anastassia N Alexandrova","doi":"10.1021/acs.jpclett.4c02908","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02908","url":null,"abstract":"By hydrogenating carbon dioxide to value-added products such as methanol, heterogeneous catalysts can lower greenhouse gas emissions and generate alternative liquid fuels. The most common commercial catalyst for the reduction of CO2 to methanol is Cu/ZnO/Al2O3, where ZnO improves conversion and selectivity toward methanol. The structure of this catalyst is thought to be Zn oxy(hydroxyl) overlayers on the nanometer scale on Cu. In the presence of CO2 and H2 under reaction conditions, the Cu substrate itself can be restructured and/or partially oxidized at its interface with ZnO, or the Zn might be reduced, possibly completely to a CuZn alloy, making the exact structure and stoichiometry of the active site a topic of active debate. In this study, we examine Zn3 clusters on Cu(100) and Cu(111), as a subnano model of the catalyst. We use a grand canonical genetic algorithm to sample the system structure and stoichiometry under catalytic conditions: T of 550 K, initial partial pressures of H2 of 4.5 atm and CO2 of 0.5 atm, and 1% conversion. We uncover a strong dependence of the catalyst stoichiometry on the surface coverage. At the optimal 0.2 ML surface coverage, chains of Zn(OH) form on both Cu surfaces. On Cu(100), the catalyst has many thermally accessible metastable minima, whereas on Cu(111), it does not. No oxidation or reconstruction of the Cu is found. However, at a lower coverage of Zn, Zn3 clusters take on a metallic form on Cu(100), and slightly oxidized Zn3O on Cu(111), while the surface uptakes H to form a variety of low hydrides of Cu. We thus hypothesize that the 0.2 ML Zn coverage is optimal, as found experimentally, because of the stronger yet incomplete oxidation afforded by Zn at this coverage.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"11745-11752"},"PeriodicalIF":4.8,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637930","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

Signature of Proton–Hole Transfer in Hydrogen-Bonded Solids at 10 K 10 K 时氢键固体中质子-空穴传输的特征

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-15 DOI: 10.1021/acs.jpclett.4c02812

Kensei Kitajima, Yoichi Nakai, Masashi Tsuge, Naoki Watanabe

{"title":"Signature of Proton–Hole Transfer in Hydrogen-Bonded Solids at 10 K","authors":"Kensei Kitajima, Yoichi Nakai, Masashi Tsuge, Naoki Watanabe","doi":"10.1021/acs.jpclett.4c02812","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02812","url":null,"abstract":"Although proton transport in water ice is well understood, proton–hole transfer (PHT) involving proton abstraction by anions remains less explored. This study investigates PHT in H2S and NH3 solids at low temperatures, aiming to determine whether these solids exhibit negative charge transport similar to that in ice. In H2S and NH3 solids at 10 K, surface HS– and NH2– anions in hydrogen-bonded systems trigger negative current flow, providing a clear signature of PHT. This negative current is controlled by electron flow and 193 nm ultraviolet irradiation, which generates HS– and NH2– anions on the solid surfaces. In bilayer H2S/H2O and NH3/H2O solids, a significant negative current is observed only in the NH3/H2O solid, which is attributed to the exothermic proton abstraction by NH2– from H2O at the bilayer interface, a process not available for H2S on ice. This study is the first to demonstrate PHT-induced electrochemical behavior in hydrogen-bonded solids other than ice.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"31 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637538","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

Ferroelectric, Switchable Dielectric and Nonlinear Optical Properties in Inorganic-Organic Lead-Free 1D Hybrids Based on Bi(III) and Azetidine: (C₃NH₈)₂[BiCl₅], (C₃NH₈)₂[BiBr₅]. 基于 Bi(III)和氮杂环丁烷的无机-有机无铅一维杂化物：(C3NH8)2[BiCl5]、(C3NH8)2[BiBr5]的铁电性、可切换介电性和非线性光学特性。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-15 DOI: 10.1021/acs.jpclett.4c02695

Magdalena Rok, Bartosz Zarychta, Jan K Zaręba, Aleksandra Krupińska, Błażej Dziuk, Piotr Durlak, Rafał Janicki, Ryszard Jakubas, Grażyna Bator, Wojciech Medycki, Michaela Zamponi, Anna Piecha-Bisiorek

{"title":"Ferroelectric, Switchable Dielectric and Nonlinear Optical Properties in Inorganic-Organic Lead-Free 1D Hybrids Based on Bi(III) and Azetidine: (C3NH8)2[BiCl5], (C3NH8)2[BiBr5].","authors":"Magdalena Rok, Bartosz Zarychta, Jan K Zaręba, Aleksandra Krupińska, Błażej Dziuk, Piotr Durlak, Rafał Janicki, Ryszard Jakubas, Grażyna Bator, Wojciech Medycki, Michaela Zamponi, Anna Piecha-Bisiorek","doi":"10.1021/acs.jpclett.4c02695","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02695","url":null,"abstract":"This study investigates lead-free organic-inorganic hybrids (C3NH8)2[BiCl5] (ABC) and (C3NH8)2[BiBr5] (ABB), focusing on their structural, dielectric, ferroelectric, and optical properties. Both compounds exhibit paraelectric (I) to ferroelectric (II) phase transitions (PTs) at 230/233 K and 228/229 K, respectively, transitioning from orthorhombic (Pnma) to monoclinic (P21) phases, with distorted [BiX6]3- octahedra forming 1D chains. Quasielastic neutron scattering and solid-state 1H NMR studies reveal the localized motion of azetidinium cations. Dielectric measurements of ABC and ABB show step-like permittivity changes by 11-12 units post-transition I → II, demonstrating reversible switching behavior. Absorption studies reveal band gaps of 3.24 eV for ABC and 2.76 eV for ABB, classifying them as insulators. Luminescence spectra at 77K display 578 nm (ABC) and 708 nm (ABB) emissions, attributed to 3P1,0 → 1S0 transitions. Both compounds demonstrate stable second harmonic generation (SHG) switching of the on-off type. The switching performance is evaluated over multiple thermal cycles using the treq metric, which decreases with increasing temperature change rate and indicates that ABB's SHG switching is approximately 30% faster than that of ABC.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"11709-11722"},"PeriodicalIF":4.8,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637931","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

Comment on “Localized and Delocalized States of a Diamine Cation: Resolution of a Controversy” 评论 "二胺阳离子的局部和非局部状态：争议的解决"

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-14 DOI: 10.1021/acs.jpclett.4c0198410.1021/acs.jpclett.4c01984

Gabriel S. Phun, and , Bryan M. Wong*,

{"title":"Comment on “Localized and Delocalized States of a Diamine Cation: Resolution of a Controversy”","authors":"Gabriel S. Phun,  and , Bryan M. Wong*, ","doi":"10.1021/acs.jpclett.4c0198410.1021/acs.jpclett.4c01984","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c01984https://doi.org/10.1021/acs.jpclett.4c01984","url":null,"abstract":"Since its appearance in [Cheng, X.; Zhang, Y.; Jónsson,E.; Jónsson, H.; Weber, P. M. <cite>Nat. Commun.</cite> 2016, 7, 11013] and recent re-investigation in [Gałyńska,M.; Ásgeirsson, V.; Jónsson, H.; Bjornsson, R. <cite>J. Phys. Chem. Lett.</cite>, 2021, 12, 1250−1255], the dimethylpiperazine cation (DMP+) has generated considerable discussion and controversy in the scientific literature over the existence of stable, local energy minima in this molecular system. Specifically, prior assumptions that the Rydberg state and radical cation of DMP are similar have led to significant confusion and debate regarding the accuracy of various quantum chemistry methods and the existence of stable configurations of DMP+ itself. The purpose of this Viewpoint is to highlight recent studies that call into question the main findings in the previously mentioned works as well as present new CCSDT (Coupled-Cluster with Single, Double, and Triple excitations) calculations to finally bring closure to this controversy.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11415–11418 11415–11418"},"PeriodicalIF":4.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c01984","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Magnetic Circular Dichroism of Luminescent Triarylmethyl Radicals. 发光三芳基甲基自由基的磁环二色性。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-14 DOI: 10.1021/acs.jpclett.4c02793

Yohei Hattori, Daiya Suzuki, Wataru Ota, Tohru Sato, Gwénaël Rapenne, Yoshitane Imai

{"title":"Magnetic Circular Dichroism of Luminescent Triarylmethyl Radicals.","authors":"Yohei Hattori, Daiya Suzuki, Wataru Ota, Tohru Sato, Gwénaël Rapenne, Yoshitane Imai","doi":"10.1021/acs.jpclett.4c02793","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02793","url":null,"abstract":"Stable triarylmethyl radicals are the most common carbon radical building blocks and have recently attracted much attention for their luminescent properties. However, magnetic circular dichroism (MCD) discovered by Michael Faraday and magnetic circularly polarized luminescence (MCPL) have not been observed for simple triarylmethyl radicals, probably due to their photodegradability. Here we report the first observation of MCD and MCPL of triarylmethyl radicals in solution using racemic mixtures of (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) and (3,5-difluoro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (F2PyBTM), which are much more photostable than simple triphenylmethyl radical derivatives. Faraday B terms, which are at the origin of magnetic dichroism in nondegenerate systems, were calculated using TD-DFT, and the line shape of MCD spectra was well reproduced. This study provides new circular dichroism properties for luminescent triarylmethyl radicals in solution without separating enantiomers and also clarifies the origin of magnetic circular dichroism properties of stable organic radicals for the first time.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"11696-11700"},"PeriodicalIF":4.8,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142612783","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

Fluctuating Chromatin Facilitates Enhancer–Promoter Communication by Regulating Transcriptional Clustering Dynamics 波动染色质通过调节转录聚类动态促进增强子-启动子交流

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-07 DOI: 10.1021/acs.jpclett.4c0245310.1021/acs.jpclett.4c02453

Tao Zhu, Chunhe Li* and Xiakun Chu*,

引用次数: 0

Nonlinear Optical Properties of the Topological Material Bi2Se3 Family for the Application of an Ultrafast Pulse Laser Based on the Occupied and Unoccupied Band Structures 基于占带和非占带结构的拓扑材料 Bi2Se3 家族的非线性光学特性--用于超快脉冲激光器的应用

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-07 DOI: 10.1021/acs.jpclett.4c0260010.1021/acs.jpclett.4c02600

Yujiu Jiang, Xiaowei Xing, Peng Zhu, Kejian Wang, Zhiyang Zhang, Qi Liu, Zhiwei Wang, Wenjun Liu*, Jinjian Zhou* and Junfeng Han*,

{"title":"Nonlinear Optical Properties of the Topological Material Bi2Se3 Family for the Application of an Ultrafast Pulse Laser Based on the Occupied and Unoccupied Band Structures","authors":"Yujiu Jiang, Xiaowei Xing, Peng Zhu, Kejian Wang, Zhiyang Zhang, Qi Liu, Zhiwei Wang, Wenjun Liu*, Jinjian Zhou* and Junfeng Han*, ","doi":"10.1021/acs.jpclett.4c0260010.1021/acs.jpclett.4c02600","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02600https://doi.org/10.1021/acs.jpclett.4c02600","url":null,"abstract":"The Bi2Se3 family can exhibit many intriguing topological insulator properties, including a narrow bandgap and strong surface states, which show excellent nonlinear optical properties. Thinning bulk Bi2Se3 family materials to create a low-cost photoelectric modulation device and explaining the mechanisms of nonlinear optical differences in different types of materials remain challenges. Based on liquid-phase exfoliation technology and tapered fiber, this work prepared optoelectronic modulation devices for various samples within the Bi2Se3 family, quantitatively compared their nonlinear optical properties, and analyzed the sources of differentiation using the occupied and unoccupied multiband structure theory. The results correspond well to the phenomena observed in the ultrafast laser, which will provide strong support for the design of higher performance photoelectric devices based on topological insulators.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11419–11427 11419–11427"},"PeriodicalIF":4.8,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640896","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

Atomic Layer Deposition of ZnO on CsPbBr3 Perovskite Nanocrystals: Surface-Dependent Mechanistic Insights CsPbBr3 Perovskite 纳米晶体上的氧化锌原子层沉积：表面依赖性机理透视

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-07 DOI: 10.1021/acs.jpclett.4c0273710.1021/acs.jpclett.4c02737

Min Ju Kim, Min Seok Kim, Ju Young Woo* and Seong-Yong Cho*,

{"title":"Atomic Layer Deposition of ZnO on CsPbBr3 Perovskite Nanocrystals: Surface-Dependent Mechanistic Insights","authors":"Min Ju Kim, Min Seok Kim, Ju Young Woo* and Seong-Yong Cho*, ","doi":"10.1021/acs.jpclett.4c0273710.1021/acs.jpclett.4c02737","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02737https://doi.org/10.1021/acs.jpclett.4c02737","url":null,"abstract":"In this study, we investigate the atomic layer deposition (ALD) process on all-inorganic CsPbBr3 perovskite nanocrystals (PNCs) to introduce an inorganic electron transport layer (ETL) in light-emitting diode (LED) devices. Two types of CsPbBr3 PNCs were synthesized with oleate (OA) and oleylammonium (OLA) ligands on the surface. We found that CsPbBr3 PNCs with Cs oleate surfaces experienced severe photoluminescence (PL) quenching after the ALD process, while those with oleylammonium bromide surfaces did not show any significant PL drop. Transmission electron microscopy and X-ray photoelectron spectroscopy revealed that significant Pb metal formation and Ruddlesden–Popper planar faults, linked to uncoordinated Pb2+ ion defects, were generated in CsPbBr3 PNCs terminated with Cs oleate after ALD ZnO. Finally, we fabricated LEDs using PNCs with an ALD ZnO process to introduce inorganic ZnMgO nanoparticles as the ETL. The devices processed with ALD exhibited superior luminance and external quantum efficiency compared to those without the ALD process. This research provides crucial insights into the surface-dependent chemistry of PNCs and the surface-dependent performance of perovskite-based optoelectronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11437–11444 11437–11444"},"PeriodicalIF":4.8,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640900","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

Role of Metal-Oxide Interfaces in Methanol Decomposition: Reaction of Methanol on CeO2/Ag(111) Inverse Model Catalysts 金属氧化物界面在甲醇分解中的作用：甲醇在 CeO2/Ag(111) 反模型催化剂上的反应

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-11-07 DOI: 10.1021/acs.jpclett.4c0287810.1021/acs.jpclett.4c02878

Dongling Zhang, Xu Cao, Xingwang Cheng, Luchao Huang, Yi Tu, Honghe Ding, Jun Hu, Qian Xu* and Junfa Zhu*,

{"title":"Role of Metal-Oxide Interfaces in Methanol Decomposition: Reaction of Methanol on CeO2/Ag(111) Inverse Model Catalysts","authors":"Dongling Zhang, Xu Cao, Xingwang Cheng, Luchao Huang, Yi Tu, Honghe Ding, Jun Hu, Qian Xu* and Junfa Zhu*, ","doi":"10.1021/acs.jpclett.4c0287810.1021/acs.jpclett.4c02878","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02878https://doi.org/10.1021/acs.jpclett.4c02878","url":null,"abstract":"Metal-oxide interfaces play a critical role in catalytic processes, such as methanol adsorption and decomposition reactions. In this work, we investigated methanol reactions on the inverse model CeO2/Ag(111) catalyst surfaces, i.e., submonolayer CeO2 films on Ag(111), under ultrahigh vacuum (UHV) conditions to specially address the role of CeO2–Ag interface in the catalytic methanol decomposition reactions. Using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and synchrotron radiation photoemission spectroscopy (SRPES), we found that, at the submonolayer ceria coverages, the CeO2 nanoislands exhibit a hexagonal CeO2(111) lattice with fully oxidized Ce4+ on Ag(111). At higher ceria coverages, multilayer ceria nanoislands form on the Ag(111) surface instead of a well-ordered film. A combination of temperature-programmed desorption (TPD) and SRPES reveals that methanol adsorbs dissociatively on the CeO2/Ag(111) surfaces at 110 K, resulting in the formation of methoxy groups. These methoxy groups subsequently decompose via two pathways: (i) interaction with lattice oxygen to produce formate species at 230 K, which then decompose to CO, and (ii) direct dehydrogenation of methoxy to formaldehyde. Notably, the surface with submonolayer CeO2 film on Ag(111) demonstrates low-temperature reactivity (440 K) for methoxy dehydrogenation to formaldehyde, which occurs at a much lower temperature, compared to the surface of multilayer CeO2 on Ag(111) surface (530 K). This finding emphasizes that the CeO2–Ag(111) interfaces provide unique active sites for methoxy dehydrogenation reactions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 45","pages":"11405–11414 11405–11414"},"PeriodicalIF":4.8,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142640985","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