Mads Peter Sulbaek Andersen, Ellen Rosendal Kjaergaard, Connor Blair, Ole John Nielsen
Smog chamber experiments were used to investigate the kinetics and mechanisms of the Cl atom, OH radical and O3 initiated oxidation of (E)-1,2-difluoroethene (CHF=CHF) at (298 ± 2) K under atmospheric conditions. Relative and absolute rate methods were used to measure k(Cl + (E)-CHF=CHF) = (1.00 ± 0.10) × 10-10 , k(OH + (E)-CHF=CHF) = (8.42 ± 1.29) × 10-12 , and k(O3 + (E)-CHF=CHF) = (1.16 ± 0.07) × 10-18 cm3 molecule-1 s-1 in 700 Torr of N2 /air diluent. A slight pressure dependency for the kinetics of the Cl initiated oxidation was observed: 13% reduction at 50 Torr compared to atmospheric pressure. The observed products from the reaction of (E)-CHF=CHF with Cl were HC(O)F and the corresponding (Z)-CHF=CHF isomer (14% at 700 Torr, 62% at 50 Torr total pressure). In the OH radical initiated oxidation, the major product observed was HC(O)F in a yield of (205 ± 8)%. The O3 initiated oxidation leads to HC(O)F and HF in yields of (148 ± 4)% and (53 ± 2)%, respectively. The photochemical ozone creation potential, the radiative efficiency, and global warming potentials are estimated, and the results are discussed in the context of the atmospheric chemistry of (E)-CHF=CHF and other halogenated alkenes.
{"title":"Atmospheric chemistry of (E)-1,2-difluoroethene: Kinetics and Mechanisms of the reactions with Cl atoms, OH radicals and O3","authors":"Mads Peter Sulbaek Andersen, Ellen Rosendal Kjaergaard, Connor Blair, Ole John Nielsen","doi":"10.1039/d5cp04019a","DOIUrl":"https://doi.org/10.1039/d5cp04019a","url":null,"abstract":"Smog chamber experiments were used to investigate the kinetics and mechanisms of the Cl atom, OH radical and O<small><sub>3</sub></small> initiated oxidation of (<em>E</em>)-1,2-difluoroethene (CHF=CHF) at (298 ± 2) K under atmospheric conditions. Relative and absolute rate methods were used to measure k(Cl + (<em>E</em>)-CHF=CHF) = (1.00 ± 0.10) × 10<small><sup>-10</sup></small> , k(OH + (<em>E</em>)-CHF=CHF) = (8.42 ± 1.29) × 10<small><sup>-12</sup></small> , and <em>k</em>(O<small><sub>3</sub></small> + (<em>E</em>)-CHF=CHF) = (1.16 ± 0.07) × 10<small><sup>-18</sup></small> cm<small><sup>3</sup></small> molecule<small><sup>-1</sup></small> s<small><sup>-1</sup></small> in 700 Torr of N<small><sub>2</sub></small> /air diluent. A slight pressure dependency for the kinetics of the Cl initiated oxidation was observed: 13% reduction at 50 Torr compared to atmospheric pressure. The observed products from the reaction of (<em>E</em>)-CHF=CHF with Cl were HC(O)F and the corresponding (<em>Z</em>)-CHF=CHF isomer (14% at 700 Torr, 62% at 50 Torr total pressure). In the OH radical initiated oxidation, the major product observed was HC(O)F in a yield of (205 ± 8)%. The O<small><sub>3</sub></small> initiated oxidation leads to HC(O)F and HF in yields of (148 ± 4)% and (53 ± 2)%, respectively. The photochemical ozone creation potential, the radiative efficiency, and global warming potentials are estimated, and the results are discussed in the context of the atmospheric chemistry of (<em>E</em>)-CHF=CHF and other halogenated alkenes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"93 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145752913","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}
Encapsulation of dibenzo-18-crown-6 complexed with potassium ions (K+-DB18C6) inside single-walled carbon nanotubes (SWCNTs) enables electron doping while preserving the tubular structure. Thermoelectric measurements demonstrated that K+-DB18C6@SWCNTs switched from p-type (pristine SWCNTs) to n-type. Raman spectroscopy further confirmed electron doping through an upshift of the G-band and a decrease in radial breathing mode (RBM) intensity, while ultraviolet photoelectron spectroscopy (UPS) showed a decrease in work function from Φ = 4.41 eV to Φ = 4.21 eV. When iron(II) phthalocyanine (FePc) was supported on K+-DB18C6@SWCNTs (FePc/K+-DB18C6@SWCNT), the composite exhibited excellent oxygen reduction reaction (ORR) catalytic activity. Linear sweep voltammetry with a rotating ring-disk electrode (RRDE) revealed an onset potential (Eonset = 0.624 V vs. RHE) nearly identical to that of Pt/C electrodes. The enhanced ORR performance is attributed to perturbation of the FePc electronic state by the electron-doped SWCNT support, as evidenced by recovery of RBM intensity upon FePc loading. RRDE analysis further showed that the ORR followed a nearly complete four-electron pathway (n = 3.97). Durability tests by chronoamperometry at 0.4 V (vs. RHE) indicated that FePc/K+-DB18C6@SWCNT retained 31% of its initial current after 3 h, outperforming untreated SWCNT electrodes. This study demonstrates a novel strategy for ORR catalyst design, where molecular encapsulation within SWCNTs modulates the electronic states of supported metal complexes, offering a new route to high-performance and stable ORR electrodes.
将二苯并-18-冠-6与钾离子（K+-DB18C6）包裹在单壁碳纳米管（SWCNTs）内，可以在保持管状结构的同时进行电子掺杂。热电测量表明，K+-DB18C6@SWCNTs从p型（原始SWCNTs）切换到n型。拉曼光谱通过g波段的上升和径向呼吸模式（RBM）强度的降低进一步证实了电子掺杂，而紫外光电子能谱（UPS）显示功函数从Φ = 4.41 eV降低到Φ = 4.21 eV。当铁（II）酞菁（FePc）负载在K+-DB18C6@SWCNTs （FePc/K+-DB18C6@SWCNT）上时，复合材料表现出优异的氧还原反应（ORR）催化活性。旋转环盘电极（RRDE）的线性扫描伏安法显示其起始电位（Eonset = 0.624 V vs. RHE）几乎与Pt/C电极相同。ORR性能的增强是由于掺杂电子的swcnts载体对FePc电子态的扰动，在FePc加载后RBM强度的恢复证明了这一点。RRDE分析进一步表明，ORR遵循一个几乎完整的四电子通路（n = 3.97）。在0.4 V（相对于RHE）下进行的耐久性测试表明，FePc/K+-DB18C6@SWCNT在3小时后保留了31%的初始电流，优于未处理的swcnts电极。本研究展示了一种新的ORR催化剂设计策略，其中SWCNTs内的分子包封可以调节负载金属配合物的电子状态，为高性能和稳定的ORR电极提供了新的途径。
{"title":"Enhancement of oxygen reduction activity of iron phthalocyanine electrocatalyst supported on carbon nanotubes through molecular encapsulation.","authors":"Tatsuya Akiyama,Yosuke Ishii,Shinji Kawasaki","doi":"10.1039/d5cp04139b","DOIUrl":"https://doi.org/10.1039/d5cp04139b","url":null,"abstract":"Encapsulation of dibenzo-18-crown-6 complexed with potassium ions (K+-DB18C6) inside single-walled carbon nanotubes (SWCNTs) enables electron doping while preserving the tubular structure. Thermoelectric measurements demonstrated that K+-DB18C6@SWCNTs switched from p-type (pristine SWCNTs) to n-type. Raman spectroscopy further confirmed electron doping through an upshift of the G-band and a decrease in radial breathing mode (RBM) intensity, while ultraviolet photoelectron spectroscopy (UPS) showed a decrease in work function from Φ = 4.41 eV to Φ = 4.21 eV. When iron(II) phthalocyanine (FePc) was supported on K+-DB18C6@SWCNTs (FePc/K+-DB18C6@SWCNT), the composite exhibited excellent oxygen reduction reaction (ORR) catalytic activity. Linear sweep voltammetry with a rotating ring-disk electrode (RRDE) revealed an onset potential (Eonset = 0.624 V vs. RHE) nearly identical to that of Pt/C electrodes. The enhanced ORR performance is attributed to perturbation of the FePc electronic state by the electron-doped SWCNT support, as evidenced by recovery of RBM intensity upon FePc loading. RRDE analysis further showed that the ORR followed a nearly complete four-electron pathway (n = 3.97). Durability tests by chronoamperometry at 0.4 V (vs. RHE) indicated that FePc/K+-DB18C6@SWCNT retained 31% of its initial current after 3 h, outperforming untreated SWCNT electrodes. This study demonstrates a novel strategy for ORR catalyst design, where molecular encapsulation within SWCNTs modulates the electronic states of supported metal complexes, offering a new route to high-performance and stable ORR electrodes.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"5 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704470","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 GMTKN55 data set is a collection of standard benchmarks used in molecular quantum chemistry that spans small-and large-molecule thermochemistry, reaction barriers, and non-covalent interactions. Herein, we identify a flaw in the weighted mean absolute deviation (WTMAD) definitions commonly used to quantify performance of various electronic-structure methods for the GMTKN55 set, which under-weight some of its component benchmarks by orders of magnitude. A new WTMAD-4 metric is proposed, based on typical errors observed for well-behaved density-functional approximations (DFAs), ensuring fair treatment across all benchmarks. The performance of 135 dispersion-corrected DFAs is assessed by combining literature data with new results for 20 minimally empirical methods, primarily involving the exchange-hole dipole moment and many-body dispersion corrections, available in the FHI-aims code. Lastly, we highlight a literature example where a DFA parametrised by minimising WTMAD-2 underperforms for benchmarks marginalised by that metric.
{"title":"WTMAD-4: A Fair Weighting Scheme for GMTKN55","authors":"Kyle R. Bryenton, Erin R. Johnson","doi":"10.1039/d5cp03741g","DOIUrl":"https://doi.org/10.1039/d5cp03741g","url":null,"abstract":"The GMTKN55 data set is a collection of standard benchmarks used in molecular quantum chemistry that spans small-and large-molecule thermochemistry, reaction barriers, and non-covalent interactions. Herein, we identify a flaw in the weighted mean absolute deviation (WTMAD) definitions commonly used to quantify performance of various electronic-structure methods for the GMTKN55 set, which under-weight some of its component benchmarks by orders of magnitude. A new WTMAD-4 metric is proposed, based on typical errors observed for well-behaved density-functional approximations (DFAs), ensuring fair treatment across all benchmarks. The performance of 135 dispersion-corrected DFAs is assessed by combining literature data with new results for 20 minimally empirical methods, primarily involving the exchange-hole dipole moment and many-body dispersion corrections, available in the FHI-aims code. Lastly, we highlight a literature example where a DFA parametrised by minimising WTMAD-2 underperforms for benchmarks marginalised by that metric.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"6 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704777","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}
Polyurethane (PU) and its numerous fine-tuned derivatives are widely employed as CO 2 scavengers thanks to (1) physisorption and (2) functionalization of the PU backbone with other CO 2 sorbents. In the present work, it has been unraveled why PU cannot exhibit CO 2 chemisorption, despite possessing the nitrogen docking sites and exhibiting strong electrostatic sorbent-sorbate interactions. Furthermore, a few types of spatial separation of the active sorption sites have been proposed to unleash the chemisorption functionality of PU. By comparing various structural modifications of PU by using the in-silico methodology, we have identified that CO 2 chemisorption by PU takes place in the case of implementing methyl and ethyl fragments between the oxygen and nitrogen atoms of PU. Herewith, the introduction of the ethyl moiety even makes CO 2 chemisorption energetically favorable relative to physisorption. The reported specific progress on materials design represents an obvious practical value for chemical engineers developing inexpensive CO 2 scavengers.
{"title":"Investigation of a Novel Urethane-based CO 2 Chemisorbent: Structure Modifications and Activation Barriers","authors":"Vitaly V. Chaban","doi":"10.1039/d5cp04112k","DOIUrl":"https://doi.org/10.1039/d5cp04112k","url":null,"abstract":"Polyurethane (PU) and its numerous fine-tuned derivatives are widely employed as CO 2 scavengers thanks to (1) physisorption and (2) functionalization of the PU backbone with other CO 2 sorbents. In the present work, it has been unraveled why PU cannot exhibit CO 2 chemisorption, despite possessing the nitrogen docking sites and exhibiting strong electrostatic sorbent-sorbate interactions. Furthermore, a few types of spatial separation of the active sorption sites have been proposed to unleash the chemisorption functionality of PU. By comparing various structural modifications of PU by using the in-silico methodology, we have identified that CO 2 chemisorption by PU takes place in the case of implementing methyl and ethyl fragments between the oxygen and nitrogen atoms of PU. Herewith, the introduction of the ethyl moiety even makes CO 2 chemisorption energetically favorable relative to physisorption. The reported specific progress on materials design represents an obvious practical value for chemical engineers developing inexpensive CO 2 scavengers.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728698","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}
Solid surfaces can relatively easy be modified and the surface properties can be tailored through functionalisation with self-assembled monolayers (SAMs). Degradation or damage of these layers can affect the surface properties introduced through the functionalisation with self-assembled monolayers, and hence the functionality of the respective surface in an application.In this study, we investigated the damage induced by X-ray exposure-to the structure of carboxylicterminated SAMs. The integrity of both the carboxylic and thiol groups, with thiol groups being essential for anchoring the monolayers to the gold substrate, was compromised through X-ray exposure. Analysis of ultraviolet photoelectron spectroscopy (UPS) and metastable impact electron spectroscopy (MIES) data shows that such damage leads to changes in the work function and affecting the electronic distribution within the outermost layer. The change is caused by the altering of the electronic structure at the interface, leading to a change of the dipole formed at this interface.Both changes can occur independent of each other. It can be expected that exposure to UV light has a similar influence on the structure of the SAMs as exposure to X-ray radiation.
{"title":"X-ray Exposure Effects on Carboxylic-Terminated Self-Assembled Monolayers and Change of the Interface Electronic Structure","authors":"Ahlam R Alharbi, Gunther G Andersson, Ingo Koeper","doi":"10.1039/d5cp03717d","DOIUrl":"https://doi.org/10.1039/d5cp03717d","url":null,"abstract":"Solid surfaces can relatively easy be modified and the surface properties can be tailored through functionalisation with self-assembled monolayers (SAMs). Degradation or damage of these layers can affect the surface properties introduced through the functionalisation with self-assembled monolayers, and hence the functionality of the respective surface in an application.In this study, we investigated the damage induced by X-ray exposure-to the structure of carboxylicterminated SAMs. The integrity of both the carboxylic and thiol groups, with thiol groups being essential for anchoring the monolayers to the gold substrate, was compromised through X-ray exposure. Analysis of ultraviolet photoelectron spectroscopy (UPS) and metastable impact electron spectroscopy (MIES) data shows that such damage leads to changes in the work function and affecting the electronic distribution within the outermost layer. The change is caused by the altering of the electronic structure at the interface, leading to a change of the dipole formed at this interface.Both changes can occur independent of each other. It can be expected that exposure to UV light has a similar influence on the structure of the SAMs as exposure to X-ray radiation.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"26 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704799","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}
Correction for ‘High-temperature and solid-state NMR investigation of the structural evolution and special phase transition in LiF–NaF–BeF2 mixed salts’ by Jianchao Sun et al., Phys. Chem. Chem. Phys., 2025, 27, 8903–8909.
{"title":"Correction: High-temperature and solid-state NMR investigation of the structural evolution and special phase transition in LiF–NaF–BeF2 mixed salts","authors":"Jianchao Sun, Hailong Huang, Ling Han, Xiaobin Fu, Hongtao Liu, Yuan Qian","doi":"10.1039/d5cp90210j","DOIUrl":"https://doi.org/10.1039/d5cp90210j","url":null,"abstract":"Correction for ‘High-temperature and solid-state NMR investigation of the structural evolution and special phase transition in LiF–NaF–BeF<small><sub>2</sub></small> mixed salts’ by Jianchao Sun <em>et al.</em>, <em>Phys. Chem. Chem. Phys.</em>, 2025, <strong>27</strong>, 8903–8909.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"30 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696985","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 work, we report the synthesis and comprehensive characterization of pristine and Fe-doped SnSe2 single crystals, revealing how light Fe doping enhances photoconductivity and induces magnetism in this layered 2D material. The Fe substitution leads to a reduction in the band-gap and activation energy, as noted from its electrical transport measurements. The phonon characteristics and crystal symmetry remain unaltered, as confirmed by temperature-dependent Raman spectroscopy measurements. Magnetic measurements demonstrate that even low Fe concentrations induce a ferromagnetic interaction in otherwise diamagnetic pristine and this interaction increases with increasing Fe-concentration. Photoconductivity measurements demonstrate a pronounced superlinear photocurrent response in both pristine and Fe-doped SnSe2-based photodetectors. A model based on three recombination centers is proposed to explain this superlinear behavior. Interestingly, 1% Fe-doped SnSe2 exhibits the highest external quantum efficiency (∼ 1.4×104%) and detectivity (∼ 1012Jones), along with a reduced response time. The coexistence of robust ferromagnetism and superior photodetector performance in Fe-doped SnSe2 highlights its potential as a promising candidate for next-generation spintronic, optoelectronic, and energy-related applications.
{"title":"Coexistence of Ferromagnetism and Enhanced Photo-response in Fe-Doped SnSe2 Single Crystals","authors":"Aarti Lakhara, P. A. Bhobe","doi":"10.1039/d5cp03461b","DOIUrl":"https://doi.org/10.1039/d5cp03461b","url":null,"abstract":"In this work, we report the synthesis and comprehensive characterization of pristine and Fe-doped SnSe<small><sub>2</sub></small> single crystals, revealing how light Fe doping enhances photoconductivity and induces magnetism in this layered 2D material. The Fe substitution leads to a reduction in the band-gap and activation energy, as noted from its electrical transport measurements. The phonon characteristics and crystal symmetry remain unaltered, as confirmed by temperature-dependent Raman spectroscopy measurements. Magnetic measurements demonstrate that even low Fe concentrations induce a ferromagnetic interaction in otherwise diamagnetic pristine and this interaction increases with increasing Fe-concentration. Photoconductivity measurements demonstrate a pronounced superlinear photocurrent response in both pristine and Fe-doped SnSe<small><sub>2</sub></small>-based photodetectors. A model based on three recombination centers is proposed to explain this superlinear behavior. Interestingly, 1% Fe-doped SnSe<small><sub>2</sub></small> exhibits the highest external quantum efficiency (∼ 1.4×10<small><sup>4</sup></small>%) and detectivity (∼ 10<small><sup>12</sup></small>Jones), along with a reduced response time. The coexistence of robust ferromagnetism and superior photodetector performance in Fe-doped SnSe<small><sub>2</sub></small> highlights its potential as a promising candidate for next-generation spintronic, optoelectronic, and energy-related applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"30 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696947","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}
Addressing urgent global energy demands, efficient multifunctional electrocatalysts are critical for next-generation clean energy technologies including fuel cells and metal-air batteries. Through systematic first-principles calculations, this work comprehensively evaluates 2D kagome MB₃ (M = Be, Ca, Sr) monolayers as promising electrocatalytic substrates. Transition metal single-atom decoration achieves exceptional bifunctional performance in Ni@CaB₃ with remarkably low oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) overpotentials of 0.37 V and 0.41 V, respectively. However, these gains are compromised by thermally induced metastability at 300 K, where heavy transition metal atoms migrate into kagome interlayers, distorting the active surface. We develop an innovative cesium anchoring strategy that suppresses atomic migration while preserving catalytic sites. Ni@CaB₃ maintains its OER activity (0.38 V) despite a moderate ORR overpotential increase to 0.60 V. Electronic analysis further reveals that Cs⁺ indirectly modulates the hydrogen evolution (HER) activity via boron-mediated charge transfer. This charge redistribution induces predictable shifts in the d-band centers of the transition metals, thereby rationally elevating the performance of Fe@CaB₃ above Mn@CaB₃. Beyond establishing Ni@CaB₃ as a prime bifunctional catalyst, this work resolves decoration-induced metastability in otherwise stable kagome lattices and delivers a generalizable stabilization paradigm applicable to engineered 2D electrocatalysts for sustainable energy conversion.
高效多功能电催化剂是燃料电池和金属-空气电池等下一代清洁能源技术的关键。通过系统的第一性原理计算，这项工作全面评价了2D kagome MB₃（M = Be, Ca, Sr）单层膜作为有前途的电催化底物。过渡金属单原子修饰在Ni@CaB₃中实现了优异的双官能团性能，其析氧反应（OER）和氧还原反应（ORR）过电位分别为0.37 V和0.41 V。然而，这些增益受到300 K时热诱导亚稳的影响，重过渡金属原子迁移到kagome中间层，扭曲了活性表面。我们开发了一种创新的铯锚定策略，在保留催化位点的同时抑制原子迁移。Ni@CaB₃保持其OER活性（0.38 V），尽管ORR过电位适度增加到0.60 V。电子分析进一步表明，Cs +通过硼介导的电荷转移间接调节析氢（HER）活性。这种电荷再分配引起了过渡金属d带中心的可预测的位移，从而合理地将Fe@CaB₃的性能提升到Mn@CaB₃之上。除了建立Ni@CaB₃作为主要的双功能催化剂之外，这项工作还解决了在其他稳定的kagome晶格中装饰诱导的亚稳态问题，并提供了一种适用于工程二维电催化剂的可持续性能量转换的可推广的稳定范例。
{"title":"Cesium-Anchored MB₃ (M = Be, Ca, Sr) Kagome Monolayers: Stabilizing Active Sites for Bifunctional Oxygen Electrocatalysis","authors":"Yaowen Long, Hong Zhang","doi":"10.1039/d5cp03509k","DOIUrl":"https://doi.org/10.1039/d5cp03509k","url":null,"abstract":"Addressing urgent global energy demands, efficient multifunctional electrocatalysts are critical for next-generation clean energy technologies including fuel cells and metal-air batteries. Through systematic first-principles calculations, this work comprehensively evaluates 2D kagome MB₃ (M = Be, Ca, Sr) monolayers as promising electrocatalytic substrates. Transition metal single-atom decoration achieves exceptional bifunctional performance in Ni@CaB₃ with remarkably low oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) overpotentials of 0.37 V and 0.41 V, respectively. However, these gains are compromised by thermally induced metastability at 300 K, where heavy transition metal atoms migrate into kagome interlayers, distorting the active surface. We develop an innovative cesium anchoring strategy that suppresses atomic migration while preserving catalytic sites. Ni@CaB₃ maintains its OER activity (0.38 V) despite a moderate ORR overpotential increase to 0.60 V. Electronic analysis further reveals that Cs⁺ indirectly modulates the hydrogen evolution (HER) activity via boron-mediated charge transfer. This charge redistribution induces predictable shifts in the d-band centers of the transition metals, thereby rationally elevating the performance of Fe@CaB₃ above Mn@CaB₃. Beyond establishing Ni@CaB₃ as a prime bifunctional catalyst, this work resolves decoration-induced metastability in otherwise stable kagome lattices and delivers a generalizable stabilization paradigm applicable to engineered 2D electrocatalysts for sustainable energy conversion.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"29 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696945","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}
Zhu Chang, Rajat Walia, Dandan Zhang, Xian-Kai Chen, Jiaqi Li
Multi-resonant thermally activated delayed fluorescence (MR-TADF) molecules have emerged as promising candidates for high-resolution organic light-emitting diode (OLED) displays. However, their performance is often limited by intrinsically large singlet-triplet energy gaps (∆EST), leading to an unsatisfactory reverse intersystem crossing rate (kRISC). Herein, we systematically investigate how to modulate excited-state characteristics by strategically integrating diversified electron-donating units with an MR skeleton, enabling precise control over short-range charge transfer (SRCT) and long-range charge transfer (LRCT) components. The excited-state characters of S1, including SRCT, SRCT+LRCT, and LRCT, are achieved by fine-tuning the donor and MR interactions. Compared with unsubstituted analogues, the increase of LRCT component significantly reduces ∆EST, thereby elevating kRISC values. However, the LRCT-dominated S1 states show broad and structureless emission spectra due to substantial relaxation energy. For molecules with mixed SRCT and LRCT characters, triplet up-conversion occurs efficiently owing to the small ΔEST mediated by the mixed characters. Furthermore, the SRCT character with relatively small relaxation energy relevant to the S1→S0 process could help achieve narrowband emission. This work establishes a molecular design framework for high-efficiency and narrowband MR-TADF materials, highlighting the critical role of donor units engineering in exciton utilization and color purity.
{"title":"Modulating excited state via diversified electron-donating units in MR-TADF emitters: a theoretical exploration of structure-property relationships","authors":"Zhu Chang, Rajat Walia, Dandan Zhang, Xian-Kai Chen, Jiaqi Li","doi":"10.1039/d5cp03248b","DOIUrl":"https://doi.org/10.1039/d5cp03248b","url":null,"abstract":"Multi-resonant thermally activated delayed fluorescence (MR-TADF) molecules have emerged as promising candidates for high-resolution organic light-emitting diode (OLED) displays. However, their performance is often limited by intrinsically large singlet-triplet energy gaps (∆EST), leading to an unsatisfactory reverse intersystem crossing rate (kRISC). Herein, we systematically investigate how to modulate excited-state characteristics by strategically integrating diversified electron-donating units with an MR skeleton, enabling precise control over short-range charge transfer (SRCT) and long-range charge transfer (LRCT) components. The excited-state characters of S1, including SRCT, SRCT+LRCT, and LRCT, are achieved by fine-tuning the donor and MR interactions. Compared with unsubstituted analogues, the increase of LRCT component significantly reduces ∆EST, thereby elevating kRISC values. However, the LRCT-dominated S1 states show broad and structureless emission spectra due to substantial relaxation energy. For molecules with mixed SRCT and LRCT characters, triplet up-conversion occurs efficiently owing to the small ΔEST mediated by the mixed characters. Furthermore, the SRCT character with relatively small relaxation energy relevant to the S1→S0 process could help achieve narrowband emission. This work establishes a molecular design framework for high-efficiency and narrowband MR-TADF materials, highlighting the critical role of donor units engineering in exciton utilization and color purity.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"217 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696946","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}
Protein-protein interaction (PPI) between the receptor-binding domain (RBD) of the SARS-CoV-2 spike protein and human angiotensin-converting enzyme 2 (hACE2) plays a critical role in viral infections. Therefore, comprehensively understanding the effects of amino acid mutations in the RBD, which are associated with viral evolution, on this PPI is important. Recently, we developed a PPI analysis method called "visualization of interfacial electrostatic complementarity (VIINEC)." VIINEC provides an intuitive understanding of the effect of amino acid mutations on PPIs by visualizing the electrostatic potential (ESP) at the interface. In this study, we used VIINEC to study the RBD-hACE2 complexes of 15 SARS-CoV-2 variants. The results demonstrated clear alterations in the ESPs of the RBDs during viral evolution. Interestingly, despite the absence of mutations in hACE2, its ESP changed significantly in response to RBD mutations, maintaining high electrostatic complementarity across the variants. In addition, these adaptive ESP changes in hACE2 were attributed to switch-like conformational changes in four charged residues.
{"title":"Visualization of Interfacial Electrostatic Complementarity Reveals Evolutionary Changes in SARS-CoV-2 RBD–hACE2 Interactions","authors":"Yosuke Muroya, Hiroki Ozono, Takeshi Ishikawa","doi":"10.1039/d5cp03728j","DOIUrl":"https://doi.org/10.1039/d5cp03728j","url":null,"abstract":"Protein-protein interaction (PPI) between the receptor-binding domain (RBD) of the SARS-CoV-2 spike protein and human angiotensin-converting enzyme 2 (hACE2) plays a critical role in viral infections. Therefore, comprehensively understanding the effects of amino acid mutations in the RBD, which are associated with viral evolution, on this PPI is important. Recently, we developed a PPI analysis method called \"visualization of interfacial electrostatic complementarity (VIINEC).\" VIINEC provides an intuitive understanding of the effect of amino acid mutations on PPIs by visualizing the electrostatic potential (ESP) at the interface. In this study, we used VIINEC to study the RBD-hACE2 complexes of 15 SARS-CoV-2 variants. The results demonstrated clear alterations in the ESPs of the RBDs during viral evolution. Interestingly, despite the absence of mutations in hACE2, its ESP changed significantly in response to RBD mutations, maintaining high electrostatic complementarity across the variants. In addition, these adaptive ESP changes in hACE2 were attributed to switch-like conformational changes in four charged residues.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":"127 1","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145696944","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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