The Journal of Physical Chemistry C最新文献

{"title":"50 and 100 Years Ago in The Journal of Physical Chemistry – 2025 Edition","authors":"Joan-Emma Shea, T. Daniel Crawford, Barbara Kirchner, Cary Pint, Gregory V. Hartland","doi":"10.1021/acs.jpcc.5c02643","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02643","url":null,"abstract":"In this series of editorials we look back at the work published in the Journal of Physical Chemistry 50 and 100 years ago. In 1925, <i>The Journal of Physical Chemistry</i> published 153 articles, a 40% increase from the previous year and continuing the trend of journal growth in the 1920s. A large number of the papers dealt with the properties of colloids and emulsions, which was an important topic at the time and a major focus of the Journal’s editor-in-chief. The most prolific authors were N. R. Dhar from the University of Allahabad, India, and W. A. Patrick from Johns Hopkins University with eight papers each. Patrick pioneered a method to quickly and cheaply produce silica gel, which has a variety of uses, an important example being as the active agent in gas masks in World War I. His papers and correspondence have been archived by Johns Hopkins University. All of Patrick’s papers published <i>The Journal of Physical Chemistry</i> in 1925 were studies of absorption of different species onto silica gel, except for a study of boiling points and conductivity of soap in alcohol solutions. (1) The soap study showed, not too surprisingly, that sodium oleate is dissociated in alcohol solutions at the boiling point. Dhar published on a wide range of topics including the viscosity of colloid solutions, (2) studies of corrosion of metals by nitric acid, (3) how the color of colloidal solutions changes with ion adsorption, (4) and photosynthesis in tropical light compared to artificial UV light. (5) Dhar was an extremely prolific scientist, and was an early leader of physical chemistry in India. The most cited papers in 1925 were studies of the performance of different types of adhesives by McBain and Hopkins (6) and how thin films affect water evaporation by E. K. Rideal (who later achieved fame for his work on surface catalysis). (7) A diagram of the apparatus used by McBain and Hopkins to measure the strength of adhesives is shown in Figure 1. (6) This paper was cited 14 times in 2024! Also in 1925 Kharasch and Sher presented a 33-page “preliminary communication” on determining the heat of combustion by counting the number of valence electrons─see Figure 1. (8) In their view of bonding, atoms have a series of orbits and two atoms can hold a pair of electrons at the points where the orbits intersect. Which orbit is used depends on the affinity of the atom for electrons. Although this is not the modern view, the differences between the calculated and measured heats of combustion were generally <1%, which is outstanding. Also in 1925 Barker published a similar set of calculations based on Lewis structures; (9) however, the predicted combustion energies were less accurate. The Journal also published two papers on the stabilization of gold colloids (“Zsigmondy’s gold sols”) by surface active agents (10,11) and four papers on the properties of phosgene (dielectric constant, conductivity and solution density) by Germann and co-workers. (12−15) The work ","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"404 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143921150","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":"Optically Active Dopants in II–VI and Metal Halide Perovskite Nanocrystals","authors":"Manoj Sharma, Jacek J. Jasieniak","doi":"10.1021/acs.jpcc.5c01016","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01016","url":null,"abstract":"Doping provides an important pathway toward tailoring the optoelectronic properties of nanocrystals. In this Perspective, we critically evaluate optically active dopants that produce Stokes-shifted emission pathways in traditional II–VI and emerging metal halide perovskite colloidal nanocrystals. The structural difference between these materials induces substantive variations in how such dopants, which include Cu¹⁺, Ag¹⁺, Mn²⁺, and Yb³⁺ ions, incorporate into the lattices. When further coupled to the size and shape of the nanocrystals, modified excited state dynamics are exhibited. The modified optoelectronic properties of such doped nanocrystals have found use in nanocrystal-based light-emitting devices, luminescent solar concentrators, and photocatalysis, as examples. Continuing progress in terms of dimensionality and shape control, optimized dopant distributions, and refined energy transfer processes are considered as key future directions to fulfill the promise of doped nanocrystals across such application areas.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"31 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143921159","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":"50 and 100 Years Ago in The Journal of Physical Chemistry – 2025 Edition","authors":"Joan-Emma Shea, T. Daniel Crawford, Barbara Kirchner, Cary Pint and Gregory V. Hartland*, ","doi":"10.1021/acs.jpcc.5c0264310.1021/acs.jpcc.5c02643","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02643https://doi.org/10.1021/acs.jpcc.5c02643","url":null,"abstract":"","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 18","pages":"8483–8485 8483–8485"},"PeriodicalIF":3.3,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143917093","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":"Enhancement of Luminescence in Anatase TiO2 Photocatalysts by Ethanol under Hole-Scavenging Conditions","authors":"Yuuki Tomitsuka, Takeru Saito, Ryuzi Katoh","doi":"10.1021/acs.jpcc.5c01492","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01492","url":null,"abstract":"We studied the enhancement of the photoluminescence intensity of anatase TiO₂ photocatalysts by adding ethanol vapor. Time-resolved measurements of luminescence and transient absorption indicated that the luminescence was due to excitons, and there was no luminescence associated with the recombination of trapped charges. We found that the ethanol-induced enhancement of the luminescence was dominated by an increase of the efficiency of generation of excitons. We concluded that this increased efficiency was due to the recombination of electrons that accumulated in particles due to hole-scavenging by ethanol with photogenerated holes before the holes were trapped at the surface of particles.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"228 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143921144","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":"Vitamin B12-Functionalized NiMn2O4 Spinel: A Promising Bioinspired Electrocatalyst for Dechlorination in the Aqueous Phase","authors":"Jun Duan, Yaqi Yang, Shiying Fan, Xinyong Li, Shaomin Liu","doi":"10.1021/acs.jpcc.5c01002","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01002","url":null,"abstract":"Electrochemical selective dechlorination of dichloromethane (DCM) to methane and chloromethane is a promising and sustainable strategy to remove halogenated contaminants and generate clean energy. In this work, we present an approach wherein vitamin B₁₂ (VB₁₂) is immobilized on the surface of NiMn₂O₄ hollow tubular nanofibers (NM-HTNFs) for electrocatalytic DCM reduction dechlorination in the aqueous phase system. This bioinspired catalytic system, which integrates a natural molecule, demonstrates remarkable yields of organic products. Remarkably, a total organic product yield of 127.845 mmol g^–1 h^–1 (methane, 49.017 mmol g^–1 h^–1; chloromethane, 69.740 mmol g^–1 h^–1; ethylene, 9.097 mmol g^–1 h^–1) at −1.60 V (vs Ag/AgCl) was achieved, and an impressive methane Faradaic efficiency up to 26.78% was achieved. Experimental findings were supported by in situ adsorption FTIR spectroscopy that shed light on a synergistic effect of NM-HTNFs and VB₁₂, facilitating the adsorption ability of DCM and the charge transfer rate, further enhancing the carbon–chlorine (C–Cl) bond scission. It dramatically improved the reductive performance of DCM dechlorination. This work is expected to provide a bioinspired way where naturally abundant VB₁₂ has been taken full advantage of for the efficient transformation of DCM to high-value-added products.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"31 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915990","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":"Gas- versus Liquid-Phase Silylation as a Way to Inhibit Thin-Film Atomic Layer Deposition (ALD) on Silicon Oxide Substrates","authors":"Mohammed Sadman Alam, Md. Abdul Motin, Francisco Zaera","doi":"10.1021/acs.jpcc.5c02266","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c02266","url":null,"abstract":"The effectiveness of silylation treatments of silicon oxide surfaces using <i>N</i>-(trimethylsilyl)dimethylamine (TMSDMA) for the passivation of atomic layer depositions (ALDs) was evaluated by using X-ray photoelectron spectroscopy (XPS). It was determined that such silylation does indeed block the silanol (Si–OH) nucleation centers where the ALD precursors react and therefore inhibits film growth, but only temporarily; after a few ALD cycles, deposition becomes evident. By testing this chemistry on two types of SiO₂ surfaces, prepared by plasma-enhanced chemical vapor deposition (PE-CVD) and by chemical (RCA) treatment of Si(100) wafers, it was concluded that the nature of the initial substrate does not play a crucial role in the silylation or ALD blocking processes. The material being deposited, on the other hand, does make a difference: TiO₂ film growth can be blocked for almost 10 ALD cycles, whereas HfO₂ starts building up on the surface after less than 5 ALD cycles. Moreover, the steady-state deposition rate reached for TiO₂ on the silylated surfaces is lower than that seen for the untreated substrate, whereas with HfO₂ not only is that not the case, but the new films may in fact grow as 3D nanostructures. One of the key findings of this work is that the silylation can be carried out using either gas- or liquid-phase treatments. It was found that the extent of silylation and the inhibition of the subsequent ALD were comparable in both cases, but the gas-phase method was determined to be cleaner and to deposit less carbon contaminants. This silylation-based ALD inhibition is expected to be selective with respect to the nature of the substrate and therefore useful for the design of area-selective ALD (AS-ALD) processes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"48 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143916005","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":"Surface Metal Salt Modulating and Inner-Shell Doping of Green Indium Phosphide Quantum Dots toward High Efficiency and Narrow Emission","authors":"Danyang Liu, Shuya Huang, Yongbao Lu, Jiaxin Kang, Zhaobin Zhang, Guofa Li, Shibiao Wei, Lishuang Wang, Bingsuo Zou","doi":"10.1021/acs.jpcc.5c00845","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00845","url":null,"abstract":"Low-toxicity indium phosphide (InP) QDs are considered to be an ideal alternative to heavy metal QDs and have emerged as a promising candidate for next-generation optoelectronic applications. However, the optical performance of InP QDs still lags behind that of Cd-based QDs, partly due to the surface traps caused by the lattice mismatch between InP and ZnS. Here, Al, Ga, and In salts are used to modify the surface of the green InP core before the growth of the inner shell of ZnSeS. These metal ions are thought to play an effective role in removing P dangling bonds on the surface of the InP core. By using AlCl₃ as a modifier, the line width is reduced from 36.7 to 35.6 nm. Then, a small amount of Mn ions is doped in the second step of ZnSeS inner-shell growth to form the inner-shell structure of Zn(Mn)SeS alloys. Mn doping may change the crystal structure of ZnSeS, and reduce interfacial defects and stresses. After surface metal salt modulating and inner-shell doping, Al-, Ga-, and In-InP QDs all reach better efficiency and line width than the untreated ones. And the best performance is obtained by Ga-InP/Zn(Mn)SeS/ZnS QDs with a fwhm of 35 nm and a PLQY of 94%.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"12 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143921145","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":"Application of the Quantum Confinement Effect in the Determination of Activation Energy: Growth of CsPbBr3 Nanocrystals Under Stirring Conditions","authors":"You-Lin Huang, Wei Li, Nipun Chandrasiri, Fuqian Yang","doi":"10.1021/acs.jpcc.5c01221","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01221","url":null,"abstract":"Determining the activation energy is of great importance in understanding the growth kinetics of crystalline materials. In this work, we investigate the feasibility of using the temperature dependence of the Stokes shift and bandgap from the Tauc plot of the absorbance spectrum to determine the activation energy for the growth of cesium lead bromide (CsPbBr₃) nanocrystals (NCs) under stirring conditions. The principle is based on the quantum confinement effect, i.e., the size dependence of the bandgap of semiconductor NCs. The nominal activation energies determined by using the temperature dependences of the bandgap from the Tauc plot and the Stokes shift exhibit the same increasing trend with the increase of stirring speed as the corresponding ones determined by the temperature dependences of the crystal size of CsPbBr₃ NCs and the photoluminescence (PL) peak wavelength. The nominal activation energies determined by using the temperature dependences of the PL peak wavelength, the crystal size, and the bandgap from the Tauc plot are in good accordance with each other. However, the nominal activation energies determined by using the Stokes shift are slightly larger than the corresponding energies determined by the other approaches. There might exist other factors contributing to the Stokes shift in addition to the size effect. These results highlight that the Stokes shift and absorbance analyses have the potential for analyzing the growth behavior of semiconductor NCs under dynamic synthesis conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"698 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915991","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":"Host–Guest Interactions in the C59N•⊂[10]CPP Supramolecular Radical","authors":"Yuri Tanuma, Bastien Anézo, Tilen Knaflič, Jannis Volkmann, Hermann A. Wegner, Ioanna K. Sideri, Nikos Tagmatarchis, Christopher P. Ewels, Denis Arčon","doi":"10.1021/acs.jpcc.4c07474","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07474","url":null,"abstract":"A remarkable stability of a supramolecular radical comprising an azafullerene (C₅₉N^•) radical sterically protected by a [10]cycloparaphenylene ([10]CPP) nanoring, C₅₉N^•⊂[10]CPP, has recently been observed by various experimental probes. In order to investigate the host–guest interaction in these supramolecular complexes, we carried out electron paramagnetic resonance (EPR) measurements, theoretically supported by density functional theory (DFT) calculations. The continuous wave (CW) EPR spectrum shows the presence of two active spin components: C₅₉N^•⊂[10]CPP monomers that can in certain cases polymerize into oligomeric radicals. Two- and three-pulse electron spin echo envelope modulation (ESEEM) measurements allow for determination of experimental hyperfine coupling constants for ¹³C and ¹H atoms and also show the strong coupling to the ¹⁴N atom adjacent to the radical C of the azafullerene. These experimental hyperfine coupling constants reasonably agree with those calculated for the DFT optimized supramolecular structures. The results are consistent with a small spin delocalization from the guest (C₅₉N^•) to the host ([10]CPP), thereby explaining weak but non-negligible interaction between them. Our study demonstrates that ESEEM experiments in alliance with DFT computations can offer valuable insights into the radical host–guest structures.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"103 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915987","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":"Prediction of New Crystal of Titanium Oxides and Property Calculations Using Structure Prediction Software and First-Principles Theory","authors":"Jinrong Huo, Pengfei Liu, Yuxin Tang, Kai Zhang, Chaozheng He","doi":"10.1021/acs.jpcc.5c00915","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00915","url":null,"abstract":"The crystal structure prediction software CBD-GM, based on the Bayesian optimization algorithm combined with deep learning, was used to predict the crystal structure of titanium oxide. One known bulk structure and three new structures were predicted. The first-principles of density functional theory (DFT) have been used to calculate and analyze the properties associated with three new material structures. The results show that these structures have outstanding thermodynamic and kinetic stability. The elastic constants, bulk modulus, and Young’s modulus indicate that the structure materials have excellent mechanical properties. Calculation of the energy band structure using hybrid density flooding shows that the prediction structures are all broadband semiconductors and also have a high dielectric constant and high optical response in the UV region, which has great scope for development in semiconductor devices and deep exotic optoelectronics, providing a completely new research direction for the development and experimental synthesis of new structures.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"61 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915988","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}