The Journal of Physical Chemistry C最新文献

{"title":"Novel Fabrication and Characterization of a Bespoke Ultralow Loading Platinum Nanocluster on Carbon Black Catalyst","authors":"Richard O.D. Clark, Eman Alharbi, Gazi N. Aliev, Wolfgang Theis, Emerson C. Kohlrausch, Graham Rance, Jesum Alves Fernandes, Neil V. Rees","doi":"10.1021/acs.jpcc.4c08590","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08590","url":null,"abstract":"Magnetron sputtering offers a single-step, flexible, and environmentally friendly fabrication route to catalyst production, avoiding the requirement for complex syntheses or toxic chemicals normally required for more traditional wet chemical techniques. Using this facile method, a nanocluster platinum-on-carbon black catalyst is fabricated, rigorously characterized physically and electrochemically, and compared to a well-understood commercial catalyst (TKK). Scanning transmission electron microscopy (STEM) imaging reveals a mean cluster size of 1.1 ± 0.4 nm, half the commercial equivalent, with an associated electrochemically active surface area (ECSA) of 122.2 ± 9.6 m² g^–1, 40% higher than the commercial comparison. Catalytic performance is measured using the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR); results indicate a turnover frequency (TOF) 33 times higher than the commercial analogue in the HER and distinct kinetic differences between samples in the ORR. Rotating ring disc electrode voltammetry (RRDE) is utilized to study the mechanism further, and a discussion of activity vs size of particle is presented.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"16 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745169","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}

{"title":"Sulfur-Alloyed CuI for Highly Conducting and Stable p-Type Transparent Conductor via Scalable Iodination of Cu2S","authors":"Xiong Jing Chen, Gui Shan Liu, En Yao Fan, Qing Xing Duan, Zhan Hua Li, Bei Deng, Yuan Shen Qi, Kin Man Yu, Chao Ping Liu","doi":"10.1021/acs.jpcc.5c00604","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00604","url":null,"abstract":"High-performance p-type transparent conductors are crucial for next-generation optoelectronics but currently lag behind their n-type counterparts. Copper iodide (CuI), despite promising hole mobility, suffers from limited conductivity and stability. We address these limitations by reporting highly conducting and stable Cu–I–S thin films, fabricated via scalable solid iodination of sputtered Cu₂S. Comprehensive characterization reveals that these S-alloyed CuI films primarily consist of polycrystalline zincblende S-incorporated CuI as the dominant phase, along with a minor amorphous Cu_<i>x</i>S phase, exhibiting outstanding electrical properties: a remarkable hole concentration of ∼3 × 10²¹ cm^–3, a hole mobility of ∼1 cm² V^–1 s^–1, and a low resistivity of ∼2 × 10^–3 Ω·cm, surpassing most p-type transparent conductors. These films demonstrate 50–70% visible transparency (with an optical bandgap of ∼3.1 eV) and robust environmental stability. This enhanced conductivity and stability arise from S-alloying-induced copper vacancies within the S-incorporated CuI matrix, and notably within the Cu_<i>x</i>S phase, which also significantly contributes to the improved stability. Post-thermal annealing of longer-iodinated Cu–I–S films increases copper sulfide content due to iodine out-diffusion at elevated temperatures, promoting copper and sulfur segregation. Our results also suggest a low concentration of sulfur substitution at iodine sites (S_I) in the zincblende CuI phase under equilibrium growth conditions, consistent with the high formation energy of S_I predicted by recent density functional theory calculations. These findings provide valuable insights into sulfur’s role in modifying CuI properties to achieve superior electrical and optical performance along with excellent durability, making this scalable approach promising for advanced transparent electronic devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"29 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737224","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}

{"title":"Visible-Light-Driven Desulfurization Reaction Using Partially Oxidized TiN Nanoparticles as Photocatalysts","authors":"Matas Simukaitis, Shea Stewart, Yugang Sun","doi":"10.1021/acs.jpcc.5c00745","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00745","url":null,"abstract":"Desulfurization represents an important process in chemical synthesis that produces new molecules and accesses useful carbon radicals. Photocatalytically driving the reactions under broadband visible light illumination is still challenging due to the high cost of noble metal complex photocatalysts and controlled inert atmospheres widely used in the reported methods. This work uses partially oxidized TiN nanoparticles comprising earth-abundant elements as photocatalysts to drive the desulfurization of methyl thioglycolate in the ambient atmosphere with a visible LED lamp. The yield of the desulfurization product, methyl acetate, is up to 73% after reaction for 18 h. The generation of accessible carbon radicals is confirmed by forming C–C coupling products with styrene. The results shed light on the promise of modified TiN nanoparticles, which possess strong broadband optical absorption originating from localized surface plasmon resonances (LSPRs), to facilitate chemical synthesis using light.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"21 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737225","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}

{"title":"Affinity of MoP (001) and MoP (010) Surfaces toward Nucleobases: A DFT Outlook","authors":"Sonam, Mukesh K. Choudhary, Neetu Goel, Ravindra Pandey","doi":"10.1021/acs.jpcc.5c00929","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00929","url":null,"abstract":"The work presents density functional study of the adsorption of nucleobases, adenine (A), guanine (G), cytosine (C), thymine (T) and uracil (U) on the MoP (001) and (010) surfaces. The results indicate that nucleobases (i.e., G, A, C, T, and U) chemisorb onto the metallic MoP (001) and (010) surfaces with high binding energies. The oxygen-mediated interactions lead to cytosine being strongly chemisorbed on both surfaces. The variation in the structural and electronic properties after the nucleobase adsorption has been assessed in terms of charge transfer, charge density difference, energy band structures, quantum conductance, current–voltage curves, and total density of states plots. While the surfaces retain their metallic character, there is a decrease in quantum conductance as the number of energy bands crossing the Fermi level decreases following nucleobase adsorption. Both pristine and chemisorbed surfaces display ohmic-like conduction in the current–voltage curves; the MoP (010) surface exhibits considerably higher sensitivity for adenine. The findings divulge the promising potential of the MoP (001) and (010) surfaces as biochemical adsorbents for DNA/RNA nucleobases.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"32 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736339","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}

{"title":"SnO2-Doped CuO Nanosheets for Enhanced CO Selectivity in Electrochemical CO2 Reduction","authors":"Rui Lin, Xiaomeng He","doi":"10.1021/acs.jpcc.5c00404","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00404","url":null,"abstract":"The electrocatalytic reduction of carbon dioxide (CO₂) to carbon monoxide (CO) on CuO-based catalysts garnered significant attention due to their promising commercial potential. However, further catalyst design is required to enhance the catalytic selectivity of the CuO catalyst for CO. This work presents a simple method to fabricate oxygen vacancy defects in CuO nanosheets for enhanced CO selectivity. Bimetallic CuO–SnO₂ catalysts with varying oxygen vacancy concentrations are obtained via a coprecipitation method. The concentration of oxygen vacancies is controlled by the molar ratio of copper to tin. At a copper–tin molar ratio of 30:1, the catalyst exhibits the highest concentration of oxygen vacancies and shows the best catalytic performance. At −0.5 V (versus RHE), the Faraday efficiency (FE) of CO reaches 87% and maintains stability for about 1 day. In situ electrochemical Fourier transform infrared (FTIR) spectroscopy directly demonstrated that oxygen vacancies facilitate the formation of the key intermediate *COOH and suppress the dimerization of *CO, thereby promoting CO production. The methodology for preparing the catalyst in this study is relatively simple and suggests a promising strategy for efficiently reducing CO₂ to CO.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"15 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734475","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}

{"title":"In Situ Synthesis of Zn/Silicalite-1 via Subcrystals: Constructing a Framework with Abundant Weak Acid Sites and High Stability","authors":"Xinan Xue, Jinquan Tao, Yijing Jia, Tianyu Bai, Wenbin Huang, Shixuan Guo, Yunmei Zhang, Yasong Zhou, Qiang Wei","doi":"10.1021/acs.jpcc.4c08252","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08252","url":null,"abstract":"This study focuses on developing effective methods for incorporating Zn species into the Silicalite-1 zeolite framework, leveraging the open structure of MFI zeolite subcrystals, to enhance its acidic properties for broader catalytic applications. This study developed a Zn-modified Silicalite-1 zeolite (ZnS-1-Sc) with enhanced acidic properties via the subcrystals in situ method. The ZnS-1-Sc showed a 3.9-fold increase in weak acid sites compared to unmodified Silicalite-1, confirmed by NH₃-TPD and Py-IR. It also maintains a complete framework structure to exhibit excellent stability and hydrothermal stability, which was determined by UV–vis, XPS, FT-IR, ²⁹Si MAS SSNMR and the hydrothermal stability test. In synthesizing pyridine bases, ZnS-1-Sc outperformed traditional HZSM-5, maintaining over 15% yield after 20 h versus less than 10% yield in 9 h. This study not only provides a new strategy for the metal modification of Silicalite-1 zeolite but also provides an important reference for the metal modification of other zeolite materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"183 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736380","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}

{"title":"Synthesis of 1T′-MoS2 Nanoribbons via Thermal Evaporation for the Hydrogen Evolution Reaction","authors":"Xue-Wei Lu, Xiaoliang Zhang, Ruxuan Chen, Shuwei Wang, Zile Wang, Huajun Tian, Xiaoqing Zhu","doi":"10.1021/acs.jpcc.5c01134","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01134","url":null,"abstract":"Two-dimensional metallic 1T′ phase molybdenum disulfide (1T′-MoS₂) nanoribbon is considered to be one of the promising electrocatalysts for the hydrogen evolution reaction (HER) on account of its exposed more active edge sites, activated basal, and preferable electrical conductivity. However, the direct growth of 1T′-MoS₂ nanoribbons still remains challenging because of their higher formation energy and the lack of effective methods for morphology control. Here, a facile thermal evaporation method is reported to prepare 1T′-MoS₂ nanoribbons using dipotassium tetrathiomolybdate (K₂MoS₄) as the precursor. Benefiting from the assistance of potassium (K) and the controllable growth conditions inside our homemade thermal evaporation system, we achieve the large-scale synthesis of 1T′-MoS₂ nanoribbons with widths of a few tens of nanometers to a few micrometers and controllable thickness of a few tens of nanometers. The optimized high-purity 1T′-MoS₂ samples exhibit excellent catalytic activity toward HER. This work not only proposes a novel strategy for the one-step fabrication of 1T′-MoS₂ nanoribbons but also demonstrates their macroscopic catalytic activity toward HER.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"36 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736382","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}

{"title":"Origin of the Indirect–Direct Band Gap Transition in GaP and Its Alloys","authors":"Yatian Ning, Man Wang, Xubo Jia, Honggang Ye, Jinying Yu, Yelong Wu","doi":"10.1021/acs.jpcc.4c08736","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08736","url":null,"abstract":"Indirect GaP-based photoelectric devices often exhibit low photoelectric conversion efficiencies. Numerous research efforts have been undertaken to facilitate indirect–direct transitions; however, a comprehensive understanding of the nature of these transitions remains elusive. In this study, we demonstrate that the occupied d orbitals, strain, and electronegativity are the three critical factors influencing the indirect–direct transition in GaP. Elevating the occupied d orbitals can raise the conduction band <i>X</i> and <i>L</i> valleys through s–d and p–d coupling while leaving the Γ valley unchanged, thereby facilitating the transition. The <i>X</i> valley possesses positive deformation potentials, whereas the Γ and <i>L</i> valleys exhibit negative ones. Consequently, a mere 0.6% tensile strain can convert the GaP band gap from indirect to direct. Additionally, larger electronegativity anions can lower the conduction band Γ valley via s–s coupling, further triggering the transition. Further investigation into the mechanisms at play in GaP alloys reveals that strain is the most sensitive factor and is crucial under most conditions. Based on these underlying mechanisms, we propose new alloys such as (GaP)_1–<i>x</i>(ZnO)_<i>x</i> and (GaP)_1–<i>x</i>(ZnS)_<i>x</i>. This work provides a framework for analyzing semiconductor indirect–direct transitions and offers insights for designing photoelectric devices based on indirect band gap semiconductors.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"70 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734474","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}

{"title":"Synergy for Enhancing Strength and Toughness of Diamond through Polytypic Heterointerface","authors":"Tengfei Xu, Zhaorui Liu, Dominik Legut, Ruifeng Zhang","doi":"10.1021/acs.jpcc.5c00702","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00702","url":null,"abstract":"Hierarchical diamond nanocomposites, incorporating diverse coherently interfaced diamond polytypes, exhibit remarkable fracture toughness while maintaining exceptional hardness. However, the underlying mechanisms governing the strengthening and toughening of these polytypic heterointerfaces (PHIs) remain elusive. In this study, we employed first-principles approaches to derive the ideal strength and Peierls stress, conducting a comprehensive investigation into the influence of various PHIs on the plasticity of nanostructured diamond. A ubiquitous strengthening effect was observed across all PHI types under uniform shear deformation, as the introduction of PHIs invariably aligned a portion of the crystal in the hard shear direction, yielding strength comparable to that of the nanotwinned diamond. Surprisingly, graphitization and bond collapse were suppressed through a sequential transformation of stacking sequences, including an experimentally observed non-3C to 3C polytype transition. This phenomenon was attributed to the systematic bond realignment driven by continuous metallization confined to specific atomic layers. The heterointerface-mediated bonding reorganization effectively dissipated energy through phase transitions, thereby achieving supertoughness. Under localized deformation, all PHIs were found to enhance the barrier against parallel slip of 1/2 ⟨110⟩ shuffle-set full dislocations and 1/6 ⟨112⟩ glide-set partial dislocations, leading to a pronounced strengthening effect. These findings not only deepen our fundamental understanding of the synergistic strengthening and toughening of diamond through PHIs but also offer valuable insights for the design of other superhard materials and engineering ceramics via coherent heterointerfaces.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"36 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734476","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}

{"title":"Shell Composition-Mediated Band Alignment and Defect Engineering in Indium Phosphide-Based Core/Shell Quantum Dots","authors":"Qinggang Hou, Yixiao Huang, Jiahua Kong, Ruiling Zhang, Aleksandr A. Sergeev, Zhannan Peng, Zhenhua Sun, Jianguo Tang, Andrey L. Rogach, Zhonglin Du","doi":"10.1021/acs.jpcc.5c01061","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01061","url":null,"abstract":"Realization of a suitable energy band structure of core–shell-structured indium phosphide (InP)-based quantum dots (QDs) is crucial for their anticipated use in various optoelectronic devices. In this study, we demonstrate how to achieve the optimal band alignment and defect engineering of InP core/Zn_1–<i>x</i>Cd_<i>x</i>Se shell QDs by systematically varying the shell composition. Using advanced spectroscopic techniques, we show how the alloyed Zn_1–<i>x</i>Cd_<i>x</i>Se shell reduces surface defects while simultaneously tuning the charge carrier wave functions from localization to delocalization mode due to the band alignment shift from type-I to quasi-type-II. These InP-based core/shell QDs also exhibit outstanding stability under high-energy ultraviolet irradiation and thermal treatment, as well as long-term storage stability, which is essential for device applications. Furthermore, studies using floating gate transistors based on InP-based core/shell QDs demonstrate the synergistic influence of the energy band structure and defects on charge injection and the spontaneous recovery of the trapped charges.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"18 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723681","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}