This study presents a practical approach for characterizing industrial water-splitting nickel foam electrodes under both cathodic and anodic conditions by employing synchrotron radiation near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). The in situ studies reveal quantitatively reduced and oxidized Ni species on the electrode surface by recording the Ni 2p3/2 signals after cycling the potential in cathodic and anodic regions, respectively. Operando studies demonstrate that a stable electrolyte film forms, allowing the probing of the solid/liquid interface under applied potentials. We attribute this stability to capillary forces within the porous structure of the foam, which enables the monitoring of surface deprotonation under anodic potentials and surface protonation under cathodic potentials. Given that the most common industrial alkaline water electrolyzer electrodes are based on nickel foams similar to the samples measured in this study, the demonstrated method offers a valuable approach for fundamental NAP-XPS examination directly on industrially employed electrodes.
{"title":"Operando Characterization of Porous Nickel Foam Water Splitting Electrodes Using Near-Ambient Pressure X-ray Photoelectron Spectroscopy","authors":"Ramadan Chalil Oglou, Morten Linding Frederiksen, Zhaozong Sun, Marcel Ceccato, Andrey Shavorskiy, Jeppe Vang Lauritsen","doi":"10.1021/acs.jpclett.4c03362","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03362","url":null,"abstract":"This study presents a practical approach for characterizing industrial water-splitting nickel foam electrodes under both cathodic and anodic conditions by employing synchrotron radiation near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). The in situ studies reveal quantitatively reduced and oxidized Ni species on the electrode surface by recording the Ni 2p<sub>3/2</sub> signals after cycling the potential in cathodic and anodic regions, respectively. Operando studies demonstrate that a stable electrolyte film forms, allowing the probing of the solid/liquid interface under applied potentials. We attribute this stability to capillary forces within the porous structure of the foam, which enables the monitoring of surface deprotonation under anodic potentials and surface protonation under cathodic potentials. Given that the most common industrial alkaline water electrolyzer electrodes are based on nickel foams similar to the samples measured in this study, the demonstrated method offers a valuable approach for fundamental NAP-XPS examination directly on industrially employed electrodes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"95 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766936","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1021/acs.jpclett.5c00697
Pan Xia, Jiahui Gui, Chengming Nie, Yupeng Yang, Jingyi Zhu, Mostafa. F. Abdelbar, Kaifeng Wu
InAs quantum dots (QDs) have emerged as a promising replacement for highly toxic lead- and mercury-based QDs for infrared optoelectronic devices. In order to understand the performance of InAs QD-devices and exploit their full potential, it is essential to elucidate the mechanisms of exciton migration or energy transfer in the films of InAs QDs, which, however, have remained lacking. Here we investigate exciton transfer dynamics in device-grade InAs QD films used in infrared photodetectors using femtosecond transient absorption spectroscopy. Interdot distances were precisely controlled by using InAs QDs of different sizes capped with ligands of varying lengths. Through minimizing interdot distances with halide ligands, we observed an energy transfer time constant as short as 1.7 ps. The distance dependence of the energy transfer rates was found to follow a Dexter-like mechanism with a damping coefficient of β = 0.31 ± 0.03 Å–1, which is a relatively small value compared to prior charge/energy transfer studies enabled by the strongly delocalized exciton wave functions of InAs QDs. These results provide hitherto lacking fundamental insights into the energy transfer/migration mechanisms inside device-grade InAs QD films, with direct relevance to optoelectronic devices ranging from photodetectors and solar cells to light-emitting diodes.
{"title":"Picosecond Dexter-Type Energy Transfer in Device-Grade InAs Quantum Dot Films","authors":"Pan Xia, Jiahui Gui, Chengming Nie, Yupeng Yang, Jingyi Zhu, Mostafa. F. Abdelbar, Kaifeng Wu","doi":"10.1021/acs.jpclett.5c00697","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00697","url":null,"abstract":"InAs quantum dots (QDs) have emerged as a promising replacement for highly toxic lead- and mercury-based QDs for infrared optoelectronic devices. In order to understand the performance of InAs QD-devices and exploit their full potential, it is essential to elucidate the mechanisms of exciton migration or energy transfer in the films of InAs QDs, which, however, have remained lacking. Here we investigate exciton transfer dynamics in device-grade InAs QD films used in infrared photodetectors using femtosecond transient absorption spectroscopy. Interdot distances were precisely controlled by using InAs QDs of different sizes capped with ligands of varying lengths. Through minimizing interdot distances with halide ligands, we observed an energy transfer time constant as short as 1.7 ps. The distance dependence of the energy transfer rates was found to follow a Dexter-like mechanism with a damping coefficient of β = 0.31 ± 0.03 Å<sup>–1</sup>, which is a relatively small value compared to prior charge/energy transfer studies enabled by the strongly delocalized exciton wave functions of InAs QDs. These results provide hitherto lacking fundamental insights into the energy transfer/migration mechanisms inside device-grade InAs QD films, with direct relevance to optoelectronic devices ranging from photodetectors and solar cells to light-emitting diodes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"183 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1021/acs.jpclett.5c00652
Giorgio Bonollo, Gauthier Trèves, Denis Komarov, Samman Mansoor, Elisabetta Moroni, Giorgio Colombo
Proteins and protein complexes form adaptable networks that regulate essential biochemical pathways and define cell phenotypes through dynamic mechanisms and interactions. Advances in structural biology and molecular simulations have revealed how protein systems respond to changes in their environments, such as ligand binding, stress conditions, or perturbations like mutations and post-translational modifications, influencing signal transduction and cellular phenotypes. Here, we discuss how computational approaches, ranging from molecular dynamics (MD) simulations to AI-driven methods, are instrumental in studying protein dynamics from isolated molecules to large assemblies. These techniques elucidate conformational landscapes, ligand-binding mechanisms, and protein–protein interactions and are starting to support the construction of multiscale realistic representations of highly complex systems, ranging up to whole cell models. With cryo-electron microscopy, cryo-electron tomography, and AlphaFold accelerating the structural characterization of protein networks, we suggest that integrating AI and Machine Learning with multiscale MD methods will enhance fundamental understating for systems of ever-increasing complexity, usher in exciting possibilities for predictive modeling of the behavior of cell compartments or even whole cells. These advances are indeed transforming biophysics and chemical biology, offering new opportunities to study biomolecular mechanisms at atomic resolution.
{"title":"Advancing Molecular Simulations: Merging Physical Models, Experiments, and AI to Tackle Multiscale Complexity","authors":"Giorgio Bonollo, Gauthier Trèves, Denis Komarov, Samman Mansoor, Elisabetta Moroni, Giorgio Colombo","doi":"10.1021/acs.jpclett.5c00652","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00652","url":null,"abstract":"Proteins and protein complexes form adaptable networks that regulate essential biochemical pathways and define cell phenotypes through dynamic mechanisms and interactions. Advances in structural biology and molecular simulations have revealed how protein systems respond to changes in their environments, such as ligand binding, stress conditions, or perturbations like mutations and post-translational modifications, influencing signal transduction and cellular phenotypes. Here, we discuss how computational approaches, ranging from molecular dynamics (MD) simulations to AI-driven methods, are instrumental in studying protein dynamics from isolated molecules to large assemblies. These techniques elucidate conformational landscapes, ligand-binding mechanisms, and protein–protein interactions and are starting to support the construction of multiscale realistic representations of highly complex systems, ranging up to whole cell models. With cryo-electron microscopy, cryo-electron tomography, and AlphaFold accelerating the structural characterization of protein networks, we suggest that integrating AI and Machine Learning with multiscale MD methods will enhance fundamental understating for systems of ever-increasing complexity, usher in exciting possibilities for predictive modeling of the behavior of cell compartments or even whole cells. These advances are indeed transforming biophysics and chemical biology, offering new opportunities to study biomolecular mechanisms at atomic resolution.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"34 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766937","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}
The scaling of advanced integrated circuits has posed significant challenges for traditional Cu interconnects, including increased resistivity and reduced electromigration lifetime. Materials with high cohesive energy and low ρ0 × λ values are emerging as promising alternatives. In this work, active learning coupling density functional theory (DFT) computation is employed to accelerate the discovery of binary intermetallic compounds for interconnect materials. Following five active learning iterations, 100 compounds are screened out. Among them, the proportion of promising materials reaches an impressive 76%, in sharp contrast to a paltry 4.9% under traditional random screening. Moreover, this research adopts an interpretable machine learning method to provide further physical insights. The Shapley additive explanations (SHAP) analysis revealed that binary intermetallic compounds featuring small cell volumes and similar Mendeleev numbers tend to possess low ρ0 × λ values. Several promising intermetallic candidates were also identified, including VMo, IrRh3, PtRh3, NbRu, and CrIr3, as potential alternatives to traditional Cu interconnects in future technology nodes. The findings in the study highlight the immense potential of machine learning techniques to accelerate the discovery of novel high-performance interconnect materials.
{"title":"Active Learning for the Discovery of Binary Intermetallic Compounds as Advanced Interconnects","authors":"Guoxiang Cui, Zikang Guo, Xiangyu Ren, Yuhang Jiang, Xinyu Jin, Yunwen Wu, Shenghong Ju","doi":"10.1021/acs.jpclett.5c00386","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00386","url":null,"abstract":"The scaling of advanced integrated circuits has posed significant challenges for traditional Cu interconnects, including increased resistivity and reduced electromigration lifetime. Materials with high cohesive energy and low ρ<sub>0</sub> × λ values are emerging as promising alternatives. In this work, active learning coupling density functional theory (DFT) computation is employed to accelerate the discovery of binary intermetallic compounds for interconnect materials. Following five active learning iterations, 100 compounds are screened out. Among them, the proportion of promising materials reaches an impressive 76%, in sharp contrast to a paltry 4.9% under traditional random screening. Moreover, this research adopts an interpretable machine learning method to provide further physical insights. The Shapley additive explanations (SHAP) analysis revealed that binary intermetallic compounds featuring small cell volumes and similar Mendeleev numbers tend to possess low ρ<sub>0</sub> × λ values. Several promising intermetallic candidates were also identified, including VMo, IrRh<sub>3</sub>, PtRh<sub>3</sub>, NbRu, and CrIr<sub>3</sub>, as potential alternatives to traditional Cu interconnects in future technology nodes. The findings in the study highlight the immense potential of machine learning techniques to accelerate the discovery of novel high-performance interconnect materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"22 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-02DOI: 10.1021/acs.jpclett.4c02930
Quanbing Pei, Xiaoxuan Zheng, Junjun Tan, Yi Luo, Shuji Ye
Unveiling how the interaction between self-assembled monolayers and plasmonic nanoparticles (PNPs) impacts molecular vibrational energy redistribution (VER) is crucial for optimizing plasmon-mediated chemical reactions (PMCRs). However, direct experimental evidence for molecule–PNP interactions opening new energy channels, such as up-pumping energy transfer and self-trapping of vibrational excitation, for VER has yet to be validated. Here, we demonstrate that electron–vibration coupling (EVC) induced by molecule–PNP interactions can open these new pathways for VER by utilizing femtosecond time-resolved sum-frequency generation vibrational spectroscopy. Using self-assembled 4-nitrothiophenol (4-NTP) monolayers on PNPs as a model, we observed that EVC opens a “forbidden” up-pumping energy transfer channel from 4-NTP nitro symmetric stretching (νNO2) to phenyl ring C═C stretching (νC═C) modes. The self-trapped state of excited νC═C modes is found, which originates from EVC-driven intermolecular coupling. These findings contribute to a better understanding of PMCR mechanisms and help guide the design of plasmonic catalysts with excellent performance.
{"title":"Electron–Vibration Couplings Open New Channels for Energy Redistribution of Self-Assembled Monolayers on Plasmonic Nanoparticles","authors":"Quanbing Pei, Xiaoxuan Zheng, Junjun Tan, Yi Luo, Shuji Ye","doi":"10.1021/acs.jpclett.4c02930","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02930","url":null,"abstract":"Unveiling how the interaction between self-assembled monolayers and plasmonic nanoparticles (PNPs) impacts molecular vibrational energy redistribution (VER) is crucial for optimizing plasmon-mediated chemical reactions (PMCRs). However, direct experimental evidence for molecule–PNP interactions opening new energy channels, such as up-pumping energy transfer and self-trapping of vibrational excitation, for VER has yet to be validated. Here, we demonstrate that electron–vibration coupling (EVC) induced by molecule–PNP interactions can open these new pathways for VER by utilizing femtosecond time-resolved sum-frequency generation vibrational spectroscopy. Using self-assembled 4-nitrothiophenol (4-NTP) monolayers on PNPs as a model, we observed that EVC opens a “forbidden” up-pumping energy transfer channel from 4-NTP nitro symmetric stretching (ν<sub>NO2</sub>) to phenyl ring C═C stretching (ν<sub>C═C</sub>) modes. The self-trapped state of excited ν<sub>C═C</sub> modes is found, which originates from EVC-driven intermolecular coupling. These findings contribute to a better understanding of PMCR mechanisms and help guide the design of plasmonic catalysts with excellent performance.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"73 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1021/acs.jpclett.5c00665
Jay Shukla, Xiaohui Qu, Zubin Darbari, Marija Iloska, J. Anibal Boscoboinik, Qin Wu
We demonstrate a data-driven approach to interpreting surface reactions by combining time-resolved gas pulsing infrared spectroscopy with chemical reaction neural networks (CRNNs). Using CO adsorption and desorption on Pd(111) at 460–490 K as a model system, we show how transient kinetic data can reveal detailed reaction mechanisms. Starting with a simple one-species model, we systematically evaluate increasingly complex mechanisms involving hollow and bridge site adsorption. Despite the similar goodness of fit to the same experimental absorbance data, our models predict distinct coverage dynamics for different adsorption sites. Through analysis of spectral peak stability and predicted dynamics, we identify a mechanism in which CO primarily adsorbs on bridge sites followed by rapid conversion to hollow sites as being the most physically consistent with experimental observations. This work provides a framework for extracting mechanistic insights from limited experimental data, demonstrating how machine learning can bridge the gap between transient kinetic measurements and a molecular-level understanding of surface reactions.
{"title":"Discovering CO Adsorption and Desorption Pathways from Chemical Reaction Neural Network Modeling of Transient Kinetics Spectroscopy","authors":"Jay Shukla, Xiaohui Qu, Zubin Darbari, Marija Iloska, J. Anibal Boscoboinik, Qin Wu","doi":"10.1021/acs.jpclett.5c00665","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00665","url":null,"abstract":"We demonstrate a data-driven approach to interpreting surface reactions by combining time-resolved gas pulsing infrared spectroscopy with chemical reaction neural networks (CRNNs). Using CO adsorption and desorption on Pd(111) at 460–490 K as a model system, we show how transient kinetic data can reveal detailed reaction mechanisms. Starting with a simple one-species model, we systematically evaluate increasingly complex mechanisms involving hollow and bridge site adsorption. Despite the similar goodness of fit to the same experimental absorbance data, our models predict distinct coverage dynamics for different adsorption sites. Through analysis of spectral peak stability and predicted dynamics, we identify a mechanism in which CO primarily adsorbs on bridge sites followed by rapid conversion to hollow sites as being the most physically consistent with experimental observations. This work provides a framework for extracting mechanistic insights from limited experimental data, demonstrating how machine learning can bridge the gap between transient kinetic measurements and a molecular-level understanding of surface reactions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"5 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-31DOI: 10.1021/acs.jpclett.5c00482
Heng Lu, Jianbo Li, Kunyan Nie, Ruilin Zhang, Yu’an Chen, Fusheng Pan
Magnesium hydride (MgH2) has been considered a promising hydrogen storage material, but its commercial application is severely limited by high operating temperature and slow de/hydrogenation kinetics. Herein, an efficient catalyst, CuSA/Ti3C2Tx, is successfully synthesized by introducing a Cu single-atom into Ti3C2Tx MXene nanosheets and applied to MgH2. The synthesized MgH2 + 5 wt %CuSA/Ti3C2Tx (CuSA/Ti3C2Tx/MgH2) composite exhibits low initial dehydrogenation temperature (T = 241.73 °C) and rapidly dehydrogenation kinetics (Ea = 76.38 kJ/mol H2). Impressively, the CuSA/Ti3C2Tx/MgH2 composite desorbs 3.3 wt % of hydrogen within 240 min at 180 °C after 20 cycles, as well as an initial dehydrogenation temperature of 164.29 °C. The superior catalytic effect of CuSA/Ti3C2Tx catalyst is ascribed to the numerous catalytic active area, in-situ-formed active metallic Ti, and multivalent Ti species, accelerating the electron transfer and weakening the strength of Mg–H bonds. In particular, the Cu single-atom improved the stability of Ti4+ in Ti3C2Tx, thereby enhancing its catalytic ability. This work provides a new perspective for ameliorating the catalytic ability of MXene.
{"title":"Single-Atom Cu Supported on Ti3C2Tx for Catalyzing Hydrogen Storage in MgH2","authors":"Heng Lu, Jianbo Li, Kunyan Nie, Ruilin Zhang, Yu’an Chen, Fusheng Pan","doi":"10.1021/acs.jpclett.5c00482","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00482","url":null,"abstract":"Magnesium hydride (MgH<sub>2</sub>) has been considered a promising hydrogen storage material, but its commercial application is severely limited by high operating temperature and slow de/hydrogenation kinetics. Herein, an efficient catalyst, Cu<sub>SA</sub>/Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub>, is successfully synthesized by introducing a Cu single-atom into Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> MXene nanosheets and applied to MgH<sub>2</sub>. The synthesized MgH<sub>2</sub> + 5 wt %Cu<sub>SA</sub>/Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> (Cu<sub>SA</sub>/Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub>/MgH<sub>2</sub>) composite exhibits low initial dehydrogenation temperature (<i>T</i> = 241.73 °C) and rapidly dehydrogenation kinetics (<i>E</i><sub>a</sub> = 76.38 kJ/mol H<sub>2</sub>). Impressively, the Cu<sub>SA</sub>/Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub>/MgH<sub>2</sub> composite desorbs 3.3 wt % of hydrogen within 240 min at 180 °C after 20 cycles, as well as an initial dehydrogenation temperature of 164.29 °C. The superior catalytic effect of Cu<sub>SA</sub>/Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub> catalyst is ascribed to the numerous catalytic active area, in-situ-formed active metallic Ti, and multivalent Ti species, accelerating the electron transfer and weakening the strength of Mg–H bonds. In particular, the Cu single-atom improved the stability of Ti<sup>4+</sup> in Ti<sub>3</sub>C<sub>2</sub>T<sub><i>x</i></sub>, thereby enhancing its catalytic ability. This work provides a new perspective for ameliorating the catalytic ability of MXene.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"58 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-31DOI: 10.1021/acs.jpclett.5c00492
Ying Chen, Xiangdong Li, Ke Liu, Qiqi Su, Hao Wang, Roland Mathieu, Sergey Ivanov, Matthias Weil, Hua Y. Geng, Zengming Zhang, Yonggang Wang, Peter Lazor, Lei Liu
Double perovskites represent a class of materials with promising fundamental properties and a broad spectrum of potential applications. However, the wide bandgap energy in double perovskites presents a hindrance to further enhancement of their photovoltaic efficiency. In the present study, a high-pressure technique is employed to tune the bandgap energy of double perovskite Co3TeO6 (CTO). A giant bandgap reduction of ∼37% from 2.93 to 1.85 eV has been observed after high-pressure treatment. Subsequent synchrotron-based X-ray diffraction and Raman spectroscopy results reveal that the significant bandgap reduction of CTO accompanies a sequence of structural phase transitions during compression and decompression. Furthermore, the high-pressure phase with a smaller bandgap energy of 1.85 eV turns out to be quenchable to ambient conditions, making the quenched CTO a promising light-harvesting material for photovoltaic applications. The present results demonstrate that high pressure can represent a green and efficient technique to tune the properties of multifunctional materials and serve as a guide for searching for stable and environmentally friendly light-harvesting materials.
{"title":"Giant Bandgap Reduction of Co3TeO6 via Pressure Engineering","authors":"Ying Chen, Xiangdong Li, Ke Liu, Qiqi Su, Hao Wang, Roland Mathieu, Sergey Ivanov, Matthias Weil, Hua Y. Geng, Zengming Zhang, Yonggang Wang, Peter Lazor, Lei Liu","doi":"10.1021/acs.jpclett.5c00492","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00492","url":null,"abstract":"Double perovskites represent a class of materials with promising fundamental properties and a broad spectrum of potential applications. However, the wide bandgap energy in double perovskites presents a hindrance to further enhancement of their photovoltaic efficiency. In the present study, a high-pressure technique is employed to tune the bandgap energy of double perovskite Co<sub>3</sub>TeO<sub>6</sub> (CTO). A giant bandgap reduction of ∼37% from 2.93 to 1.85 eV has been observed after high-pressure treatment. Subsequent synchrotron-based X-ray diffraction and Raman spectroscopy results reveal that the significant bandgap reduction of CTO accompanies a sequence of structural phase transitions during compression and decompression. Furthermore, the high-pressure phase with a smaller bandgap energy of 1.85 eV turns out to be quenchable to ambient conditions, making the quenched CTO a promising light-harvesting material for photovoltaic applications. The present results demonstrate that high pressure can represent a green and efficient technique to tune the properties of multifunctional materials and serve as a guide for searching for stable and environmentally friendly light-harvesting materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"183 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-31DOI: 10.1021/acs.jpclett.5c00545
Jonathan Vandenwijngaerden, Bapi Pradhan, Bob Van Hout, Eduard Fron, Yasuyuki Araki, Xianjun Zhang, Yutaka Shibata, Dario Santantonio, Roger Bresoli-Obach, Santi Nonell, Haifeng Yuan, Jialiang Xu, Mark Van der Auweraer, Maarten Roeffaers, Johan Hofkens, Hiroshi Fukumura, Elke Debroye
In this study, we report the first observation of a near-infrared (NIR) emission band from all-inorganic CsPbBr3 and CsPb(Br/Cl)3 perovskite microcrystals. By means of temperature- and power-dependent NIR and visible luminescence spectroscopy, we demonstrate that a fraction of the excited states in these materials relax through radiative transitions involving traps located deep within the band gap, leading to broadband NIR emission. The quantum yield of this deep trap emission is quantitatively determined for the first time and amounts to approximately 0.3% at room temperature. Furthermore, by examining the picosecond-to-nanosecond dynamics of the excited states, using time-resolved luminescence spectroscopy, we observe that the population of NIR initial states occurs on a 660 ps time scale, consistent with the capture of free carriers by deep trap sites. Hence, this work deepens our fundamental understanding of previously unexplored recombination channels in metal halide perovskite microcrystals.
{"title":"NIR Luminescence from Deep-Level Traps in CsPbBr3 Microcrystals","authors":"Jonathan Vandenwijngaerden, Bapi Pradhan, Bob Van Hout, Eduard Fron, Yasuyuki Araki, Xianjun Zhang, Yutaka Shibata, Dario Santantonio, Roger Bresoli-Obach, Santi Nonell, Haifeng Yuan, Jialiang Xu, Mark Van der Auweraer, Maarten Roeffaers, Johan Hofkens, Hiroshi Fukumura, Elke Debroye","doi":"10.1021/acs.jpclett.5c00545","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00545","url":null,"abstract":"In this study, we report the first observation of a near-infrared (NIR) emission band from all-inorganic CsPbBr<sub>3</sub> and CsPb(Br/Cl)<sub>3</sub> perovskite microcrystals. By means of temperature- and power-dependent NIR and visible luminescence spectroscopy, we demonstrate that a fraction of the excited states in these materials relax through radiative transitions involving traps located deep within the band gap, leading to broadband NIR emission. The quantum yield of this deep trap emission is quantitatively determined for the first time and amounts to approximately 0.3% at room temperature. Furthermore, by examining the picosecond-to-nanosecond dynamics of the excited states, using time-resolved luminescence spectroscopy, we observe that the population of NIR initial states occurs on a 660 ps time scale, consistent with the capture of free carriers by deep trap sites. Hence, this work deepens our fundamental understanding of previously unexplored recombination channels in metal halide perovskite microcrystals.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"4 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-31DOI: 10.1021/acs.jpclett.4c03374
Fuzhan Song, Xiang Ding, Yangyang Wan, Tong Zhang, Guogeng Yin, Jesse B. Brown, Yi Rao
Designing high-performance transition-metal electrocatalysts with controlled active heterointerfacial sites for catalyzing the electrochemical oxygen evolution reaction (OER) is very desirable but remains a great challenge. Here, a facile strategy for the synthesis of transition-metal nitride-based interfacial electrocatalysts boron-doped cobalt/cobalt nitride (B–Co/Co2N) is demonstrated with optimal heterointerfaces between Co and Co2N electrocatalysts by introducing boron as a dopant to the former. Benefiting from the unique electronegativity of B, the obtained B–Co/Co2N electrocatalysts show excellent OER performance with overpotential inputs of as low as 262 and 310 mV for 10 and 100 mA cm–2, which are 1.4 and 6.6 times higher than those of Co/Co2N with the same potential input, respectively. The experimental and theoretical results demonstrate the role of the B dopant in inducing charge redistribution of Co active sites in the Co/Co2N interfacial region, which results in a downshift of the Co 3d band center, the optimal oxidation state of active sites for *OOH formation, and lower energy barriers. Furthermore, the assembled electrolyzer can steadily produce an industrial-grade current density of 1000 mA cm–2 at a cell voltage input of only 1.81 V for at least 100 h with a Faradaic efficiency near 100%. This study provides a promising strategy for heteroatom-doped interfacial electrocatalysts with high performance for energy and environmental applications.
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