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Machine-Learning-Assisted Investigation on Benign Ion Migration in Metal Halide Perovskites
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-04 DOI: 10.1021/acs.jpclett.5c00376
Ning-Jing Hao, Rui Dai, Chuan-Jia Tong
Defect-assisted ion migration is one of the important issues that results in instability and non-radiative losses in hybrid organic–inorganic metal halide perovskite solar cells. In this work, based on the deep potential (DP) model, a long-time-scale molecular dynamics (MD) simulation has been employed to capture the interstitial-assisted iodine migration process. The results indicate that, when interstitial iodine (Ii) begins to migrate, the serious structural distortion becomes mild, weakening the electron–vibration interaction. The deep trap state induced by the iodine trimer undergoes a “deep–shallow–deep” dynamic process, which ultimately leads to an improvement of the carrier lifetime during the interstitial-assisted iodine migration process. Our work confirms that different dynamic processes are strongly correlated in halide perovskites and demonstrates that ion migration, considered to be detrimental, can become benign in a particular case. The reported results provide new fundamental insight to improve the efficiency of CH3NH3PbI3 perovskite solar cells.
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引用次数: 0
Electronic Structures of Iron in Oxide Glasses via 1s3p Resonant Inelastic X-ray Scattering
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-04 DOI: 10.1021/acs.jpclett.4c03568
Yong-Hyun Kim, Jungho Kim, Jung-Fu Lin, Sung Keun Lee
Electronic structures of iron in glasses are essential for unraveling the effect of transition metals on amorphous networks and controlling the electro-optical and transport properties of advanced glasses and amorphous energy-storing materials. The electronic configurations around iron in glasses, however, remain not well understood due to the structural disorders arising from multiple iron species with distinct valence, coordination, and spin states. Here, the first 1s3p resonant inelastic X-ray scattering (RIXS) for oxide glasses identifies hidden electronic configurations for Fe2+ and Fe3+ in amorphous networks. The results allow us to quantify the composition-induced evolution of oxygen ligand–field interactions of high-spin Fe 3d states with varying valence and coordination environments in complex glasses. The distinct electronic structures account for the electronic origins of iron-induced changes in the glass properties. The results offer prospects for a simultaneous probing of valence, coordination, and spin states of transition metals in diverse multicomponent oxide glasses and functional amorphous solids via 1s3p RIXS.
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引用次数: 0
Machine-Learning-Assisted Investigation on Benign Ion Migration in Metal Halide Perovskites 机器学习辅助研究金属卤化物包光体中的良性离子迁移
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-04 DOI: 10.1021/acs.jpclett.5c0037610.1021/acs.jpclett.5c00376
Ning-Jing Hao, Rui Dai and Chuan-Jia Tong*, 

Defect-assisted ion migration is one of the important issues that results in instability and non-radiative losses in hybrid organic–inorganic metal halide perovskite solar cells. In this work, based on the deep potential (DP) model, a long-time-scale molecular dynamics (MD) simulation has been employed to capture the interstitial-assisted iodine migration process. The results indicate that, when interstitial iodine (Ii) begins to migrate, the serious structural distortion becomes mild, weakening the electron–vibration interaction. The deep trap state induced by the iodine trimer undergoes a “deep–shallow–deep” dynamic process, which ultimately leads to an improvement of the carrier lifetime during the interstitial-assisted iodine migration process. Our work confirms that different dynamic processes are strongly correlated in halide perovskites and demonstrates that ion migration, considered to be detrimental, can become benign in a particular case. The reported results provide new fundamental insight to improve the efficiency of CH3NH3PbI3 perovskite solar cells.

缺陷辅助离子迁移是导致有机-无机混合金属卤化物过氧化物太阳能电池不稳定和非辐射损失的重要问题之一。在这项工作中,基于深电位(DP)模型,采用了长时间尺度分子动力学(MD)模拟来捕捉间隙辅助碘迁移过程。结果表明,当间隙碘(Ii)开始迁移时,严重的结构畸变变得温和,削弱了电子振动相互作用。碘三聚体诱导的深阱态经历了一个 "深-浅-深 "的动态过程,最终导致在间隙辅助碘迁移过程中载流子寿命的改善。我们的工作证实了不同的动态过程在卤化物包晶石中具有很强的相关性,并证明了被认为是有害的离子迁移在特定情况下可以变成有益的。报告的结果为提高 CH3NH3PbI3 包晶太阳能电池的效率提供了新的基本见解。
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引用次数: 0
Harnessing the Interface of Water Microdroplets to Accelerate Energy Substance Adenosine Triphosphate Formation
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-04 DOI: 10.1021/acs.jpclett.4c03613
Yuqi Wang, Yun Ju, Jing He, Jing Zhao, Zhiquan Zhou, Jie Jiang, Hong Zhang
Adenosine triphosphate (ATP) as an energy source plays a key role in providing and regulating energy for life activities in all organisms. Abiotic synthesis of ATP in vitro remains a challenge due to thermodynamic and kinetic constraints in water bulk solution. Here, we report that adenosine diphosphate (ADP) in the presence of potassium phosphate (K3PO4) spontaneously generates ATP in water microdroplets under ambient conditions and without catalysts. Dependence of conversion rate on microdroplet size and concentration was determined, which indicated phosphorylation of ADP to ATP occurred at or near the surface of the microdroplets. A weakly acidic environment and a certain concentration of metal ions favored the phosphorylation reaction in the microdroplets. Our results suggest that microdroplets with an energetically favorable microenvironment will be an avenue rich in opportunities for abiotic synthesis of biologically active compounds in the prebiotic era and enzyme-free synthesis.
{"title":"Harnessing the Interface of Water Microdroplets to Accelerate Energy Substance Adenosine Triphosphate Formation","authors":"Yuqi Wang, Yun Ju, Jing He, Jing Zhao, Zhiquan Zhou, Jie Jiang, Hong Zhang","doi":"10.1021/acs.jpclett.4c03613","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03613","url":null,"abstract":"Adenosine triphosphate (ATP) as an energy source plays a key role in providing and regulating energy for life activities in all organisms. Abiotic synthesis of ATP in vitro remains a challenge due to thermodynamic and kinetic constraints in water bulk solution. Here, we report that adenosine diphosphate (ADP) in the presence of potassium phosphate (K<sub>3</sub>PO<sub>4</sub>) spontaneously generates ATP in water microdroplets under ambient conditions and without catalysts. Dependence of conversion rate on microdroplet size and concentration was determined, which indicated phosphorylation of ADP to ATP occurred at or near the surface of the microdroplets. A weakly acidic environment and a certain concentration of metal ions favored the phosphorylation reaction in the microdroplets. Our results suggest that microdroplets with an energetically favorable microenvironment will be an avenue rich in opportunities for abiotic synthesis of biologically active compounds in the prebiotic era and enzyme-free synthesis.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"29 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539159","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
Correction to “Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet Gap” 对 "Heptazine、Cyclazine 和相关化合物 "的更正:倒置的单三元间隙的化学精确估算"
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-03 DOI: 10.1021/acs.jpclett.5c00462
Pierre-François Loos, Filippo Lipparini, Denis Jacquemin
An error was found in he CIS(D), ADC(2) and CC2 results for compound 10. See the SI for details and corrected values. This error does not affect the reference values. However, as can be seen below in Table 1, that replaces the Table 4 of our original work, (1) this tunes the statistics for these three methods, with now very small standard deviation of the errors (SDEs) for both ADC(2) and CC2. The statistics for the singlet and triplet energies can be found in the present SI. See ref (1) for details. For PBE0–2, 6 is a clear outlier due to a strong orbital mixing in the triplet state (see the SI of the original work). Removing it yields MSE, MAE, and SDE of 0.006, 0.046, and 0.056 eV, respectively. Note, however, that removing this challenging compound would improve the statistics of all other double-hybrid functionals. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.5c00462. Computational tests with several codes for 10; corrected statistical values (PDF) Correction to“Heptazine, Cyclazine, and RelatedCompounds: Chemically-Accurate Estimates of the Inverted Singlet–TripletGap” 4 views 0 shares 0 downloads Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. The authors are indebted to Atreyee Majumdar (Tata Institute of Fundamental Research, Hyderabad, India) for pinpointing this problem. This research used resources of the GLiCID Computing Facility (Ligerien Group for Intensive Distributed Computing, 10.60487/glicid, Pays de la Loire, France). This article references 1 other publications. This article has not yet been cited by other publications.
{"title":"Correction to “Heptazine, Cyclazine, and Related Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet Gap”","authors":"Pierre-François Loos, Filippo Lipparini, Denis Jacquemin","doi":"10.1021/acs.jpclett.5c00462","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00462","url":null,"abstract":"An error was found in he CIS(D), ADC(2) and CC2 results for compound <b>10</b>. See the SI for details and corrected values. This error does not affect the reference values. However, as can be seen below in Table 1, that replaces the Table 4 of our original work, (1) this tunes the statistics for these three methods, with now very small standard deviation of the errors (SDEs) for both ADC(2) and CC2. The statistics for the singlet and triplet energies can be found in the present SI. See ref (1) for details. For PBE0–2, <b>6</b> is a clear outlier due to a strong orbital mixing in the triplet state (see the SI of the original work). Removing it yields MSE, MAE, and SDE of 0.006, 0.046, and 0.056 eV, respectively. Note, however, that removing this challenging compound would improve the statistics of all other double-hybrid functionals. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.5c00462. Computational tests with several codes for <b>10</b>; corrected statistical values (PDF) Correction to\u0000“Heptazine, Cyclazine, and Related\u0000Compounds: Chemically-Accurate Estimates of the Inverted Singlet–Triplet\u0000Gap” <span> 4 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. The authors are indebted to Atreyee Majumdar (Tata Institute of Fundamental Research, Hyderabad, India) for pinpointing this problem. This research used resources of the GLiCID Computing Facility (Ligerien Group for Intensive Distributed Computing, 10.60487/glicid, Pays de la Loire, France). This article references 1 other publications. This article has not yet been cited by other publications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"1 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539057","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
Excited State Dynamics Govern Emission Properties of Unique Silsesquioxane-Salphen-Based Zinc Compounds
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-03 DOI: 10.1021/acs.jpclett.4c0340610.1021/acs.jpclett.4c03406
Joanna Szymkowiak, Tomasz Pędziński and Beata Dudziec*, 

This study aims to develop a synthetic protocol for preparing salphen-based hybrid compounds with silsesquioxane T8 cages anchored at the molecule’s periphery. Three types of coordination compounds featuring κ4-N2O2-donating atoms were obtained via a sequence of reactions. These compounds differ in the arene linker between the salphen and silsesquioxane fragments. An individual synthetic pathway was developed for the preparation of aldehydes, followed by a tailored strategy for the synthesis of the final complexes employing both solution-based and mechanochemical methods in the solid state. The latter represents a novel technique in silsesquioxane chemistry. The newly designed ligands were used for the coordination of Zn2+ ions to evaluate their ligation properties and to determine the photophysical properties of the resulting complexes in comparison to their bare ligand molecules. Using absorption and emission spectroscopy, combined with advanced time-resolved spectroscopic methods, we demonstrated that the photochemical efficiency of these compounds is influenced by their tendency to aggregate in solution, which positively affects their photophysical properties and enhances their potential for photodynamic therapy (PDT). Additionally, we explored the ability of these complexes to generate singlet oxygen (1O2) depending on the architecture of the designed ligands. The results indicate that the excited state dynamics plays a crucial role in determining the emission properties of the studied compounds, which may have significant implications for their applications in medicine and materials science.

{"title":"Excited State Dynamics Govern Emission Properties of Unique Silsesquioxane-Salphen-Based Zinc Compounds","authors":"Joanna Szymkowiak,&nbsp;Tomasz Pędziński and Beata Dudziec*,&nbsp;","doi":"10.1021/acs.jpclett.4c0340610.1021/acs.jpclett.4c03406","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03406https://doi.org/10.1021/acs.jpclett.4c03406","url":null,"abstract":"<p >This study aims to develop a synthetic protocol for preparing salphen-based hybrid compounds with silsesquioxane T<sub>8</sub> cages anchored at the molecule’s periphery. Three types of coordination compounds featuring κ<sup>4</sup><i>-N</i><sub><i>2</i></sub><i>O</i><sub><i>2</i></sub>-donating atoms were obtained via a sequence of reactions. These compounds differ in the arene linker between the salphen and silsesquioxane fragments. An individual synthetic pathway was developed for the preparation of aldehydes, followed by a tailored strategy for the synthesis of the final complexes employing both solution-based and mechanochemical methods in the solid state. The latter represents a novel technique in silsesquioxane chemistry. The newly designed ligands were used for the coordination of Zn<sup>2+</sup> ions to evaluate their ligation properties and to determine the photophysical properties of the resulting complexes in comparison to their bare ligand molecules. Using absorption and emission spectroscopy, combined with advanced time-resolved spectroscopic methods, we demonstrated that the photochemical efficiency of these compounds is influenced by their tendency to aggregate in solution, which positively affects their photophysical properties and enhances their potential for photodynamic therapy (PDT). Additionally, we explored the ability of these complexes to generate singlet oxygen (<sup>1</sup>O<sub>2</sub>) depending on the architecture of the designed ligands. The results indicate that the excited state dynamics plays a crucial role in determining the emission properties of the studied compounds, which may have significant implications for their applications in medicine and materials science.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 10","pages":"2571–2580 2571–2580"},"PeriodicalIF":4.8,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpclett.4c03406","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600301","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
Nonthermal Effect of Microwave Irradiation on the Molecular Level: Emergence of Coherent Subterahertz Vibrations of Hydration Water in Reverse Micelles
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-03 DOI: 10.1021/acs.jpclett.5c00161
Hiroshi Murakami
It is believed that the effect of microwave irradiation on samples has a thermal origin. Nevertheless, the nonthermal effect is often proposed and remains controversial because of incomplete experimental results such as the lack of local temperature around reactant molecules. We have conducted a new method of in situ terahertz (THz) time domain spectroscopy under microwave (MW) irradiation at 2.45 GHz for water in nanoscale reverse micelles, allowing one to determine the temperature of this water and its low-frequency vibrations simultaneously. Comparison with the results of temperature-dependent THz spectroscopy without MW irradiation has demonstrated that the water temperature in the reverse micelle is almost the same as the sample’s value measured by a thermographic camera under MW irradiation. In contrast, distinct sub-THz vibrational peaks of hydration water emerge nonthermally. Our findings provide a new aspect for understanding MW effects on the molecular level and may have biological implications.
{"title":"Nonthermal Effect of Microwave Irradiation on the Molecular Level: Emergence of Coherent Subterahertz Vibrations of Hydration Water in Reverse Micelles","authors":"Hiroshi Murakami","doi":"10.1021/acs.jpclett.5c00161","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00161","url":null,"abstract":"It is believed that the effect of microwave irradiation on samples has a thermal origin. Nevertheless, the nonthermal effect is often proposed and remains controversial because of incomplete experimental results such as the lack of local temperature around reactant molecules. We have conducted a new method of in situ terahertz (THz) time domain spectroscopy under microwave (MW) irradiation at 2.45 GHz for water in nanoscale reverse micelles, allowing one to determine the temperature of this water and its low-frequency vibrations simultaneously. Comparison with the results of temperature-dependent THz spectroscopy without MW irradiation has demonstrated that the water temperature in the reverse micelle is almost the same as the sample’s value measured by a thermographic camera under MW irradiation. In contrast, distinct sub-THz vibrational peaks of hydration water emerge nonthermally. Our findings provide a new aspect for understanding MW effects on the molecular level and may have biological implications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"85 2 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532770","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
Temperature-Dependent Stepwise Dissociation of Methanol on Co(0001)
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-03 DOI: 10.1021/acs.jpclett.5c00185
Junhao Li, Fangfang Liu, Yalong Jiang, Sijia Zhang, Ziling Zeng, Lanlan Yao, Xiao Chen, Yuan Tan, Xingkun Chen, Qing Guo, Chuanqi Huang, Jianqiang Zhong, Xueming Yang, Wenshao Yang
An atomic-level understanding of the elementary steps of catalytic reactions is crucial for a more molecularly driven catalyst design. Herein, we present a comprehensive study of temperature-dependent stepwise decomposition of methanol on a single-crystal Co(0001) surface using a series of surface science techniques and density functional theory calculation. Visualization of surface products was realized by scanning tunneling microscopy. The first step of methanol dissociation is cleavage of the OH bond to the methoxy group and H atom, showing clover-like and honeycomb structures, respectively. Further dissociation to CO through C–H cleavage was ascertained by infrared reflection absorption spectroscopy, and no intermediates, such as CH2O or CHO, were observed. The final product CO molecules showed versatile configurations with different periodicities on the surface under heating or tip-manipulation conditions.
{"title":"Temperature-Dependent Stepwise Dissociation of Methanol on Co(0001)","authors":"Junhao Li, Fangfang Liu, Yalong Jiang, Sijia Zhang, Ziling Zeng, Lanlan Yao, Xiao Chen, Yuan Tan, Xingkun Chen, Qing Guo, Chuanqi Huang, Jianqiang Zhong, Xueming Yang, Wenshao Yang","doi":"10.1021/acs.jpclett.5c00185","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00185","url":null,"abstract":"An atomic-level understanding of the elementary steps of catalytic reactions is crucial for a more molecularly driven catalyst design. Herein, we present a comprehensive study of temperature-dependent stepwise decomposition of methanol on a single-crystal Co(0001) surface using a series of surface science techniques and density functional theory calculation. Visualization of surface products was realized by scanning tunneling microscopy. The first step of methanol dissociation is cleavage of the OH bond to the methoxy group and H atom, showing clover-like and honeycomb structures, respectively. Further dissociation to CO through C–H cleavage was ascertained by infrared reflection absorption spectroscopy, and no intermediates, such as CH<sub>2</sub>O or CHO, were observed. The final product CO molecules showed versatile configurations with different periodicities on the surface under heating or tip-manipulation conditions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"55 11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532771","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
Coexistence of Direct and Indirect Crystallographic Pathways in Deoxidation of Molybdenum(VI) Oxide Nanowires
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-03 DOI: 10.1021/acs.jpclett.4c03725
Jiawei Huang, Min Gan, Chunxian Xing, Jiaqi Chen, Zhouyang Zhang, Lun Tan, Zhao Wang, Haoshuang Gu, Linfeng Fei
Molybdenum oxide (MoO3)-based materials have attracted considerable attention due to their significant applications in catalysis and optoelectronics. However, the introduction of oxygen vacancies into MoO3 materials under working conditions inevitably results in drastic changes in their properties and performance. Therefore, it is imperative to comprehend the deoxidation process of MoO3 in controlled environments. Herein, we reveal the deoxidation mechanisms of orthorhombic MoO3 using an advanced in situ transmission electron microscopy technique. We found that during heating-induced deoxidation, MoO3 material can follow two possible crystallographic pathways. The first is a direct topochemical transformation from orthorhombic MoO3 into monoclinic MoO2, whereas the other is an indirect transition involving a monoclinic MoO3 intermediate phase. The coexistence of these two pathways can be explained by the kinetic competition between elemental diffusion and phase transformation. Our findings provide fundamental insight into the deoxidation process of molybdenum oxides and offer potential guidance for their structural design.
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引用次数: 0
Engineering Work Function to Stabilize Metal Oxides in Reactive Hydrogen
IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-03-03 DOI: 10.1021/acs.jpclett.4c0340410.1021/acs.jpclett.4c03404
Abdul Rehman*, Robbert W. E. van de Kruijs, Wesley T. E. van den Beld, Jacobus M. Sturm and Marcelo Ackermann, 

Hydrogen, crucial for the green energy transition, poses a challenge due to its tendency to degrade surrounding wall materials. To harness hydrogen’s potential, it is essential to identify the parameter(s) of materials that modulates hydrogen–material interaction. In a recent publication, we have shown that the reduction (denitridation) of transition metal (TM) nitrides in hydrogen radicals (H*) stops when their work function drops below a threshold limit. In this work, we tailor the work function of a complex TM oxide by tuning the relative contents of its constituent TM atoms. We show that increasing the fraction of a low-work function TM decreases the work function of the complex oxide, thereby decreasing its reducibility (deoxidation) in H*. This leads to the stabilization of the higher oxidation states of a high-work function TM, which otherwise would be readily reduced in H*. We propose that the work function serves as a tunable parameter, modulating the interaction of hydrogen with TM compounds.

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引用次数: 0
期刊
The Journal of Physical Chemistry Letters
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