Pub Date : 2026-02-06DOI: 10.1021/acs.jpcc.5c07983
Hong-Lang Du, Huijie Liu, Yang Meng, Jing-Liang Yang, Xiaosi Qi, Ye Yang, Hua Zhang, Jian-Feng Li
Plasmonic metal–semiconductor nanostructure photocatalytic water splitting has attracted extensive attention owing to its bright future in using visible light. However, the role of semiconductor defects in modulating the carrier dynamics and charge transfer pathways within these nanostructures remains unclear. Herein, Au@CdS nanoparticles were employed as a model catalyst for the photocatalytic hydrogen evolution reaction (HER), and the effect of sulfur (S) vacancy type on plasmon-enhanced photocatalysis was investigated. Spectral and theoretical analyses revealed that surface S vacancies in untreated samples serve as adsorption sites for H2O adsorption, while interfacial S vacancies facilitate carrier separation and the transfer of photogenerated electrons from CdS and plasmon-induced hot electrons generated via Au interband transition to surface reactive sites, enhancing Au@CdS photocatalytic activity under short-wavelength light. In contrast, treated samples with fewer interfacial vacancies and improved crystallinity exhibit reduced recombination, prolonged carrier lifetimes, and more efficient hot-electron utilization via Au intraband transitions, resulting in superior performance under long-wavelength light. Finally, by integration of low-S-vacancy Au@CdS (Au@CdS(L)) with S-rich-vacancy CdS (CdS(R)) into a Au@CdS(R-L-R) sandwich nanostructure, the visible-light photocatalytic HER activity was considerably improved. These findings not only advance the understanding of defect-mediated plasmonic photocatalysis but also offer a general strategy for the design of high-performance plasmonic photocatalysts.
{"title":"Unveiling Sulfur Vacancy-Regulated Carrier Dynamics in Plasmonic Photocatalytic Hydrogen Evolution Reaction via Transient Absorption and Raman Spectroscopy","authors":"Hong-Lang Du, Huijie Liu, Yang Meng, Jing-Liang Yang, Xiaosi Qi, Ye Yang, Hua Zhang, Jian-Feng Li","doi":"10.1021/acs.jpcc.5c07983","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07983","url":null,"abstract":"Plasmonic metal–semiconductor nanostructure photocatalytic water splitting has attracted extensive attention owing to its bright future in using visible light. However, the role of semiconductor defects in modulating the carrier dynamics and charge transfer pathways within these nanostructures remains unclear. Herein, Au@CdS nanoparticles were employed as a model catalyst for the photocatalytic hydrogen evolution reaction (HER), and the effect of sulfur (S) vacancy type on plasmon-enhanced photocatalysis was investigated. Spectral and theoretical analyses revealed that surface S vacancies in untreated samples serve as adsorption sites for H<sub>2</sub>O adsorption, while interfacial S vacancies facilitate carrier separation and the transfer of photogenerated electrons from CdS and plasmon-induced hot electrons generated via Au interband transition to surface reactive sites, enhancing Au@CdS photocatalytic activity under short-wavelength light. In contrast, treated samples with fewer interfacial vacancies and improved crystallinity exhibit reduced recombination, prolonged carrier lifetimes, and more efficient hot-electron utilization via Au intraband transitions, resulting in superior performance under long-wavelength light. Finally, by integration of low-S-vacancy Au@CdS (Au@CdS(L)) with S-rich-vacancy CdS (CdS(R)) into a Au@CdS(R-L-R) sandwich nanostructure, the visible-light photocatalytic HER activity was considerably improved. These findings not only advance the understanding of defect-mediated plasmonic photocatalysis but also offer a general strategy for the design of high-performance plasmonic photocatalysts.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"38 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1021/acs.jpcc.5c08072
Zhixiong Yao, An Hou, Jiawei Lin, Zhongnan Guo, Jing Zhao, Quanlin Liu
Lead-free organic–inorganic metal halides (OIMHs) with robust zero-dimensional (0D) frameworks are highly attractive for practical optoelectronic applications. Here, we propose a precursor-engineering strategy using the organic molecule C15H15N to stabilize Sn-based metal halide thin films. Four 0D OIMHs were synthesized via a solution method, namely, (C15H16N)4SnCl6, (C15H16N)2SnBr6, (C15H16N)6BiBr9·2H2O, and (C15H16N)3(C2H8N)BiBr7·H2O, all adopting 0D structures. (C15H16N)4SnCl6 exhibits excitation-dependent multichannel photoluminescence: under 370 nm excitation it shows blue–white emission, whereas 306 nm excitation yields two bands at 410 and 750 nm, indicating multiple emissive centers. Time-resolved photoluminescence and density functional theory calculations reveal distinct emissive channels from the organic cation and Sn2+ centers, evidencing excitation-controlled redistribution among singlet and triplet manifolds within the rigid 0D framework. (C15H16N)4SnCl6 shows excellent stability and optical properties, and when combined with polymers to form composite films, its excitation-dependent luminescence offers a highly promising route for information encryption.
{"title":"Excitation-Controlled Singlet–Triplet Channel Redistribution in a Stable 0D Sn(II) Hybrid Halide","authors":"Zhixiong Yao, An Hou, Jiawei Lin, Zhongnan Guo, Jing Zhao, Quanlin Liu","doi":"10.1021/acs.jpcc.5c08072","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08072","url":null,"abstract":"Lead-free organic–inorganic metal halides (OIMHs) with robust zero-dimensional (0D) frameworks are highly attractive for practical optoelectronic applications. Here, we propose a precursor-engineering strategy using the organic molecule C<sub>15</sub>H<sub>15</sub>N to stabilize Sn-based metal halide thin films. Four 0D OIMHs were synthesized via a solution method, namely, (C<sub>15</sub>H<sub>16</sub>N)<sub>4</sub>SnCl<sub>6</sub>, (C<sub>15</sub>H<sub>16</sub>N)<sub>2</sub>SnBr<sub>6</sub>, (C<sub>15</sub>H<sub>16</sub>N)<sub>6</sub>BiBr<sub>9</sub>·2H<sub>2</sub>O, and (C<sub>15</sub>H<sub>16</sub>N)<sub>3</sub>(C<sub>2</sub>H<sub>8</sub>N)BiBr<sub>7</sub>·H<sub>2</sub>O, all adopting 0D structures. (C<sub>15</sub>H<sub>16</sub>N)<sub>4</sub>SnCl<sub>6</sub> exhibits excitation-dependent multichannel photoluminescence: under 370 nm excitation it shows blue–white emission, whereas 306 nm excitation yields two bands at 410 and 750 nm, indicating multiple emissive centers. Time-resolved photoluminescence and density functional theory calculations reveal distinct emissive channels from the organic cation and Sn<sup>2+</sup> centers, evidencing excitation-controlled redistribution among singlet and triplet manifolds within the rigid 0D framework. (C<sub>15</sub>H<sub>16</sub>N)<sub>4</sub>SnCl<sub>6</sub> shows excellent stability and optical properties, and when combined with polymers to form composite films, its excitation-dependent luminescence offers a highly promising route for information encryption.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"38 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122391","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1021/acs.jpcc.5c08434
H. Idriss, A. Ziani, Y. K. Mishra
Time resolved picosecond measurements of the UV and visible emissions from two ZnO tetrapod sample variants, synthesized with the flame transport synthesis method under two different conditions, were investigated upon UV light excitation. Spontaneous emissions of both regions were found, in line with previous measurements, to be long-lived with two time constants for the UV emission decay. Upon excitation with 340 nm, 100 fs pulses at fluences up to 3.3 × 10–4 J cm–2 (≈1.5 × 1015 photons cm–2 per pulse, corresponding to an estimated carrier density of ≈1 × 1019 cm–3), both ultraviolet (≈ 380 nm) and visible (≈ 490–510 nm) emissions were observed and studied. The UV emission exhibits stimulated characteristics, including spectral narrowing and a superlinear increase with pump fluence, with temporal full widths at half-maximum (FWHM) approaching the instrument response (≈0.8 ps). Wavelength-resolved TRPL reveals opposite early time spectral shifts: the UV emission red-shifts with increasing delay (consistent with exciton–electron scattering and electron–hole plasma formation with band gap renormalization), while the visible emission blue-shifts (assigned to progressive filling of defect-related trap states). Overall, these changes were seen to be nearly identical for both ZnO tetrapods (with minor differences), indicating that both synthesis variants delivered materials with similar optical response, ensuring high reliability of the flame method. These results demonstrate the opposite ultrafast dynamics of excitonic and defect-assisted processes in ZnO tetrapods and highlight their potential for applications requiring tunable emission in both the ultraviolet and visible ranges. Interpretations of the principles behind these events are presented in detail.
{"title":"Time-Resolved Picosecond Luminescence Spectroscopy of ZnO Tetrapods: Opposite Ultrafast Energy Shifts of UV Stimulated and Visible Defect Emission","authors":"H. Idriss, A. Ziani, Y. K. Mishra","doi":"10.1021/acs.jpcc.5c08434","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08434","url":null,"abstract":"Time resolved picosecond measurements of the UV and visible emissions from two ZnO tetrapod sample variants, synthesized with the flame transport synthesis method under two different conditions, were investigated upon UV light excitation. Spontaneous emissions of both regions were found, in line with previous measurements, to be long-lived with two time constants for the UV emission decay. Upon excitation with 340 nm, 100 fs pulses at fluences up to 3.3 × 10<sup>–4</sup> J cm<sup>–2</sup> (≈1.5 × 10<sup>15</sup> photons cm<sup>–2</sup> per pulse, corresponding to an estimated carrier density of ≈1 × 10<sup>19</sup> cm<sup>–3</sup>), both ultraviolet (≈ 380 nm) and visible (≈ 490–510 nm) emissions were observed and studied. The UV emission exhibits stimulated characteristics, including spectral narrowing and a superlinear increase with pump fluence, with temporal full widths at half-maximum (FWHM) approaching the instrument response (≈0.8 ps). Wavelength-resolved TRPL reveals opposite early time spectral shifts: the UV emission red-shifts with increasing delay (consistent with exciton–electron scattering and electron–hole plasma formation with band gap renormalization), while the visible emission blue-shifts (assigned to progressive filling of defect-related trap states). Overall, these changes were seen to be nearly identical for both ZnO tetrapods (with minor differences), indicating that both synthesis variants delivered materials with similar optical response, ensuring high reliability of the flame method. These results demonstrate the opposite ultrafast dynamics of excitonic and defect-assisted processes in ZnO tetrapods and highlight their potential for applications requiring tunable emission in both the ultraviolet and visible ranges. Interpretations of the principles behind these events are presented in detail.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"24 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1021/acs.jpcc.5c08463
Yi Xu, Mingyang Lv, Shaoyue Shuai, Xianggui Kong, Wenying Shi
Time-dependent phosphorescence color (TDPC) materials, characterized by persistent luminescence, high quantum yield, and superior optical performance, have attracted increasing attention for information encryption applications. However, achieving high performance room-temperature phosphorescence (RTP) remains challenging, as oxygen readily quenches triplet excitons and nonradiative decay pathways arising from molecular vibrations and rotations further suppress phosphorescence. In this study, we designed and integrated three functional components: luminescent carbon dots (CDs), layered double hydroxides (LDHs), and the polymer matrix poly(vinyl alcohol) (PVA). Owing to the synergistic interplay of multiple interactions, the CDs-LDH composites exhibit pronounced TDPC behavior. The confinement within LDHs and the electrostatic interactions between LDHs and CDs effectively restrict the motion of CDs and suppress aggregation-induced quenching, thereby laying the groundwork for RTP properties. Furthermore, interfacial electrostatic repulsion and hydrogen bonding within the CDs-LDH@PVA system collaboratively generate a rigid architecture that suppresses nonradiative decay pathways of triplet excitons, thereby enhancing TDPC. Benefiting from these synergistic effects, the CDs-LDH@PVA composite demonstrates an ultralong RTP lifetime of 87.81 ms, representing a significant performance breakthrough and providing a novel strategy for the design of high-efficiency organic–inorganic TDPC materials.
{"title":"Breaking the Interfacial Interaction Bottleneck: PVA-Engineered CDs-LDH Hybrids with Enhanced Time-Dependent Phosphorescence for Advanced Information Anti-Counterfeiting","authors":"Yi Xu, Mingyang Lv, Shaoyue Shuai, Xianggui Kong, Wenying Shi","doi":"10.1021/acs.jpcc.5c08463","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08463","url":null,"abstract":"Time-dependent phosphorescence color (TDPC) materials, characterized by persistent luminescence, high quantum yield, and superior optical performance, have attracted increasing attention for information encryption applications. However, achieving high performance room-temperature phosphorescence (RTP) remains challenging, as oxygen readily quenches triplet excitons and nonradiative decay pathways arising from molecular vibrations and rotations further suppress phosphorescence. In this study, we designed and integrated three functional components: luminescent carbon dots (CDs), layered double hydroxides (LDHs), and the polymer matrix poly(vinyl alcohol) (PVA). Owing to the synergistic interplay of multiple interactions, the CDs-LDH composites exhibit pronounced TDPC behavior. The confinement within LDHs and the electrostatic interactions between LDHs and CDs effectively restrict the motion of CDs and suppress aggregation-induced quenching, thereby laying the groundwork for RTP properties. Furthermore, interfacial electrostatic repulsion and hydrogen bonding within the CDs-LDH@PVA system collaboratively generate a rigid architecture that suppresses nonradiative decay pathways of triplet excitons, thereby enhancing TDPC. Benefiting from these synergistic effects, the CDs-LDH@PVA composite demonstrates an ultralong RTP lifetime of 87.81 ms, representing a significant performance breakthrough and providing a novel strategy for the design of high-efficiency organic–inorganic TDPC materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"24 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122434","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1021/acs.jpcc.5c08124
Ilya V. Yudanov, Svetlana S. Laletina, Konstantin M. Neyman
Adsorption of CO probe molecules on metal catalysts is widely used to characterize the surface reactivity and morphology of these nanomaterials by assigning measured C–O vibrational frequencies to particular surface sites. Density-functional calculations of the corresponding CO adsorption complexes provide key complementary data for such characterization. However, even for the adequate structural models, the calculated frequencies do not quantitatively match the experimental values due to approximations in conventional generalized-gradient exchange–correlation functionals. We proposed a frequency-dependent scaling of the density-functional C–O frequencies for adsorption on different sites of nanostructured Pd catalysts, enabling quantitative agreement with the reference experimental values. Then, we computationally studied coverage-dependent bridge CO adsorption on edge sites of Pd nanoparticles, which revealed the energetic feasibility of the full CO occupation of these sites. Due to the static and dynamic CO–CO interactions, the calculated C–O stretching frequency grows by as much as 100 cm–1 from the singleton CO adsorbed value with the number of coadsorbates at the neighboring bridge-edge sites. The saturation frequency approaches 1990 cm–1, quantitatively matching the value experimentally observed for moderately large Pd particles. Using our frequency scaling, such particles are estimated to be at least 3 nm large.
{"title":"CO Adsorption on Pd Nanoparticles: Assignment of Experimental C–O Vibrational Frequencies by DFT Calculations","authors":"Ilya V. Yudanov, Svetlana S. Laletina, Konstantin M. Neyman","doi":"10.1021/acs.jpcc.5c08124","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08124","url":null,"abstract":"Adsorption of CO probe molecules on metal catalysts is widely used to characterize the surface reactivity and morphology of these nanomaterials by assigning measured C–O vibrational frequencies to particular surface sites. Density-functional calculations of the corresponding CO adsorption complexes provide key complementary data for such characterization. However, even for the adequate structural models, the calculated frequencies do not quantitatively match the experimental values due to approximations in conventional generalized-gradient exchange–correlation functionals. We proposed a frequency-dependent scaling of the density-functional C–O frequencies for adsorption on different sites of nanostructured Pd catalysts, enabling quantitative agreement with the reference experimental values. Then, we computationally studied coverage-dependent bridge CO adsorption on edge sites of Pd nanoparticles, which revealed the energetic feasibility of the full CO occupation of these sites. Due to the static and dynamic CO–CO interactions, the calculated C–O stretching frequency grows by as much as 100 cm<sup>–1</sup> from the singleton CO adsorbed value with the number of coadsorbates at the neighboring bridge-edge sites. The saturation frequency approaches 1990 cm<sup>–1</sup>, quantitatively matching the value experimentally observed for moderately large Pd particles. Using our frequency scaling, such particles are estimated to be at least 3 nm large.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1021/acs.jpcc.5c08623
Eris Villalona, Rodrigo E. Domínguez, Edwin J. Gonzalez Lopez, Walter D. Guerra, Daniel A. Heredia, Anton Y. Khmelnitskiy, Daniel G. Oblinsky, Yohana Palacios, Thomas A. Moore, Gregory D. Scholes, Robert R. Knowles, Ana L. Moore
In photoredox reactions, charge recombination (CR) limits quantum yields, hindering the efficient conversion of light energy into catalytic activity. To address this, we drew inspiration from redox relays in photosystem II (PSII) and developed a new series of iridium(III) complexes featuring covalently attached benzimidazole-phenol-pyridine (BIP-Py) groups to facilitate intramolecular multiproton-coupled electron transfer (MPCET). Herein, we evaluate the effects of MPCET through an extended and well-defined hydrogen-bond network to improve photocatalytic activity and mitigate rapid charge recombination. Infrared spectroelectrochemistry reveals pyridine protonation upon phenol oxidation, while visible spectroelectrochemistry and transient absorption spectroscopy confirm the electro- and photochemical formation of charge-separated states (CSS) involving oxidized BIP, resulting from intramolecular proton-coupled electron transfer (PCET). The application of the BIP-Py platform in a photocatalytic N-hydroxyphthalimide ester reduction reaction resulted in a ∼106-fold reduction in CR rate and a quantum yield enhancement of up to 157%. Our findings suggest that incorporating MPCET-based redox relays into photocatalyst frameworks is an effective strategy to enhance the efficiency of photocatalytic systems.
{"title":"Leveraging Multiproton-Coupled Electron Transfer to Improve Ir(III) Photocatalyst Efficiency","authors":"Eris Villalona, Rodrigo E. Domínguez, Edwin J. Gonzalez Lopez, Walter D. Guerra, Daniel A. Heredia, Anton Y. Khmelnitskiy, Daniel G. Oblinsky, Yohana Palacios, Thomas A. Moore, Gregory D. Scholes, Robert R. Knowles, Ana L. Moore","doi":"10.1021/acs.jpcc.5c08623","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08623","url":null,"abstract":"In photoredox reactions, charge recombination (CR) limits quantum yields, hindering the efficient conversion of light energy into catalytic activity. To address this, we drew inspiration from redox relays in photosystem II (PSII) and developed a new series of iridium(III) complexes featuring covalently attached benzimidazole-phenol-pyridine (BIP-Py) groups to facilitate intramolecular multiproton-coupled electron transfer (MPCET). Herein, we evaluate the effects of MPCET through an extended and well-defined hydrogen-bond network to improve photocatalytic activity and mitigate rapid charge recombination. Infrared spectroelectrochemistry reveals pyridine protonation upon phenol oxidation, while visible spectroelectrochemistry and transient absorption spectroscopy confirm the electro- and photochemical formation of charge-separated states (CSS) involving oxidized BIP, resulting from intramolecular proton-coupled electron transfer (PCET). The application of the BIP-Py platform in a photocatalytic <i>N</i>-hydroxyphthalimide ester reduction reaction resulted in a ∼106-fold reduction in CR rate and a quantum yield enhancement of up to 157%. Our findings suggest that incorporating MPCET-based redox relays into photocatalyst frameworks is an effective strategy to enhance the efficiency of photocatalytic systems.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"17 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1021/acs.jpcc.5c07658
Zhengyang Gao, Ze Liu, Chu Wang, Ziwei Miao, Tongao Yao, Jianghao Cai, Yixiao Sun, Yuanzheng Qu, Weijie Yang
Catalytic oxidation represents a predominant strategy for NO abatement. While SO2 has been recognized as a critical promoter of NO oxidation, the fundamental principles governing catalytic performance and robust descriptors for material selection remain inadequately explored. Herein, we investigate the catalytic oxidation of NO with HSO3 as the oxidant over transition metal single-atom catalysts (TM-N4–C, TM = V ∼ Zn) through density functional theory (DFT) calculations. For HSO3 generation, the energy barriers showed minimal variation among catalysts, providing an insufficient basis for screening. Thus, we focused on the critical HSO3-mediated NO oxidation step (HSO3 + NO → SO2 + HNO2). Using the Brønsted–Evans–Polanyi relationship and microkinetic modeling, we established HSO3 adsorption energy as a descriptor and constructed a catalytic activity volcano plot. Notably, through screening 3d-5d transition metal single-atom catalysts identified Co–N4–C as the most active catalyst, which exhibits an optimal balance between a moderate 0.42 eV energy barrier and weak 0.43 eV Co-SO2 interaction. Subsequently, fixed-bed experiments performed on the theoretically screened optimal catalyst (Co–N4–C) confirmed the significant promotional effect of SO2, demonstrating that appropriate SO2 concentrations effectively enhance NO oxidation via the HSO3-mediated pathway. This work elucidates the fundamental promotion mechanism of SO2 and establishes a descriptor-based framework for the rational design of high-performance NO oxidation catalysts.
{"title":"Optimizing SO2–Promoted NO Oxidation over Single-Atom Catalysts via Activity Volcano Plot","authors":"Zhengyang Gao, Ze Liu, Chu Wang, Ziwei Miao, Tongao Yao, Jianghao Cai, Yixiao Sun, Yuanzheng Qu, Weijie Yang","doi":"10.1021/acs.jpcc.5c07658","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07658","url":null,"abstract":"Catalytic oxidation represents a predominant strategy for NO abatement. While SO<sub>2</sub> has been recognized as a critical promoter of NO oxidation, the fundamental principles governing catalytic performance and robust descriptors for material selection remain inadequately explored. Herein, we investigate the catalytic oxidation of NO with HSO<sub>3</sub> as the oxidant over transition metal single-atom catalysts (TM-N<sub>4</sub>–C, TM = V ∼ Zn) through density functional theory (DFT) calculations. For HSO<sub>3</sub> generation, the energy barriers showed minimal variation among catalysts, providing an insufficient basis for screening. Thus, we focused on the critical HSO<sub>3</sub>-mediated NO oxidation step (HSO<sub>3</sub> + NO → SO<sub>2</sub> + HNO<sub>2</sub>). Using the Brønsted–Evans–Polanyi relationship and microkinetic modeling, we established HSO<sub>3</sub> adsorption energy as a descriptor and constructed a catalytic activity volcano plot. Notably, through screening 3d-5d transition metal single-atom catalysts identified Co–N<sub>4</sub>–C as the most active catalyst, which exhibits an optimal balance between a moderate 0.42 eV energy barrier and weak 0.43 eV Co-SO<sub>2</sub> interaction. Subsequently, fixed-bed experiments performed on the theoretically screened optimal catalyst (Co–N<sub>4</sub>–C) confirmed the significant promotional effect of SO<sub>2</sub>, demonstrating that appropriate SO<sub>2</sub> concentrations effectively enhance NO oxidation via the HSO<sub>3</sub>-mediated pathway. This work elucidates the fundamental promotion mechanism of SO<sub>2</sub> and establishes a descriptor-based framework for the rational design of high-performance NO oxidation catalysts.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"89 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135317","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1021/acs.jpcc.5c07848
Henry Thake, Stephen J. Jenkins
We present first-principles calculations for hydrogen peroxide adsorbed on the monohydrogenated {001} surfaces of silicon and germanium. These calculations reveal a preference for binding through one or two dihydrogen bonds─uncommon variants of traditional hydrogen bonds that have hitherto been almost absent from the surface science literature. Their presence here is confirmed through the identification of electronic and vibrational bonding signatures. Dihydrogen bonds on the silicon surface are found to be shorter and straighter than those on the germanium surface but not any stronger. Binding through a pair of dihydrogen bonds is more stable than through one, but by less than a factor of 2.
{"title":"Prediction of Double Dihydrogen Bonds at Two Semiconductor Surfaces","authors":"Henry Thake, Stephen J. Jenkins","doi":"10.1021/acs.jpcc.5c07848","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07848","url":null,"abstract":"We present first-principles calculations for hydrogen peroxide adsorbed on the monohydrogenated {001} surfaces of silicon and germanium. These calculations reveal a preference for binding through one or two dihydrogen bonds─uncommon variants of traditional hydrogen bonds that have hitherto been almost absent from the surface science literature. Their presence here is confirmed through the identification of electronic and vibrational bonding signatures. Dihydrogen bonds on the silicon surface are found to be shorter and straighter than those on the germanium surface but not any stronger. Binding through a pair of dihydrogen bonds is more stable than through one, but by less than a factor of 2.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122428","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}
This study explores the structure–property relationships controlling the aggregation-induced emission (AIE) behavior of parent isoindigo (1) and its p-phenylene (2) and m-phenylene (3) spaced derivatives. While all three chromophores exhibit excitation-dependent emission in dilute dimethyl sulfoxide (DMSO) solutions, only 2 and 3 display strong solid-state luminescence, accompanied by large bathochromic shifts, characteristic of AIE. The AIE phenomenon is further corroborated by steady-state and time-resolved emission studies in DMSO–benzene mixtures and theoretical calculations. Powder X-ray diffraction analysis reveals π–π intermolecular through-space interactions in 2 and 3, facilitated by phenylene-π-spacers and likely a key factor for the observed AIE. Cyclic voltammetry in dichloromethane (DCM) (oxidation) and dimethylformamide (DMF) (reduction) underscores the structure-dependent redox behavior, with significant variation in reduction potentials. Thermal analysis indicates reduced thermal stability in 2 and 3 compared to 1, possibly due to the incorporation of spacers. Furthermore, time-dependent density functional theory (TD-DFT) computations (CAM-B3LYP/6-31G) for S1 and T1 states for 1–3 show that the primary energetic criterion is fulfilled for singlet fission, which holds the promise to generate highly efficient solar cells.
{"title":"Effects of Phenylene-π-Spacers on the Photophysics of Isoindigo: Aggregation-Induced Emission","authors":"Bidyut Das, Banashmita Barman, Habiyara Begum, Ananya Dutta, Dhruba Jyoti Kalita, Abdul Wahab","doi":"10.1021/acs.jpcc.5c05375","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05375","url":null,"abstract":"This study explores the structure–property relationships controlling the aggregation-induced emission (AIE) behavior of parent isoindigo (<b>1</b>) and its <i>p</i>-phenylene (<b>2</b>) and <i>m</i>-phenylene (<b>3</b>) spaced derivatives. While all three chromophores exhibit excitation-dependent emission in dilute dimethyl sulfoxide (DMSO) solutions, only <b>2</b> and <b>3</b> display strong solid-state luminescence, accompanied by large bathochromic shifts, characteristic of AIE. The AIE phenomenon is further corroborated by steady-state and time-resolved emission studies in DMSO–benzene mixtures and theoretical calculations. Powder X-ray diffraction analysis reveals π–π intermolecular through-space interactions in <b>2</b> and <b>3</b>, facilitated by phenylene-π-spacers and likely a key factor for the observed AIE. Cyclic voltammetry in dichloromethane (DCM) (oxidation) and dimethylformamide (DMF) (reduction) underscores the structure-dependent redox behavior, with significant variation in reduction potentials. Thermal analysis indicates reduced thermal stability in <b>2</b> and <b>3</b> compared to <b>1</b>, possibly due to the incorporation of spacers. Furthermore, time-dependent density functional theory (TD-DFT) computations (CAM-B3LYP/6-31G) for S<sub>1</sub> and T<sub>1</sub> states for <b>1</b>–<b>3</b> show that the primary energetic criterion is fulfilled for singlet fission, which holds the promise to generate highly efficient solar cells.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"58 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135315","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 interplay between photoswitching and second-order nonlinear optical responses in azobenzene-DASA dyads linked by alkyl spacers of variable length is investigated by using a custom in situ setup. This original experiment combines wavelength-selective LED irradiation to trigger orthogonal photoswitching. The irradiation is operated in counter-propagation with the near-infrared laser, while the second-harmonic scattered signal is collected at right angle. Systematic comparison with the isolated subunits and their physical mixtures reveals how intersubunit interactions modulate both the kinetics of photoswitching and the magnitude of the nonlinear molecular polarizability. Time-dependent density functional theory calculations provide a molecular-level rationale for the observed photophysical and nonlinear optical behavior.
{"title":"Orthogonal Photoswitching and Second-Harmonic Generation in Azobenzene-DASA Dyads: Progress toward Fully Wavelength-Controlled Multistate Nonlinear Optical Switching","authors":"Chloé Courdurié,Verònica Postils,Simon Dubuis,Angela Dellai,Coline Ducos,Luc Vellutini,Vincent Rodriguez,Emilie Genin,Frédéric Castet","doi":"10.1021/acs.jpcc.5c07901","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07901","url":null,"abstract":"The interplay between photoswitching and second-order nonlinear optical responses in azobenzene-DASA dyads linked by alkyl spacers of variable length is investigated by using a custom in situ setup. This original experiment combines wavelength-selective LED irradiation to trigger orthogonal photoswitching. The irradiation is operated in counter-propagation with the near-infrared laser, while the second-harmonic scattered signal is collected at right angle. Systematic comparison with the isolated subunits and their physical mixtures reveals how intersubunit interactions modulate both the kinetics of photoswitching and the magnitude of the nonlinear molecular polarizability. Time-dependent density functional theory calculations provide a molecular-level rationale for the observed photophysical and nonlinear optical behavior.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"91 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111231","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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