The Journal of Physical Chemistry C最新文献

{"title":"Mixed Organic Cation in Chiral Two-Dimensional Organic–Inorganic Hybrid Metal Halides─An Ab Initio Study of Nonlinear Optical (NLO) Properties","authors":"Xiyue Cheng, S. Muthukrishnan, Hanxiang Mi, Shuiquan Deng, Goncagül Serdaroğlu, R. Vidya, Alessandro Stroppa","doi":"10.1021/acs.jpcc.4c02520","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c02520","url":null,"abstract":"The mixing of organic cations represents yet another direction to explore in the field of chiral <i>organic</i>-<i>inorganic hybrid metal halides</i> (OIHMH). Here, we perform structural optimizations, electronic structures, and nonlinear optical (NLO) studies using density functional theory of two recently synthesized chiral OIHMHs, [R-MePEA][C3A]PbBr₄ and [R-MePEA][C4A]PbBr₄, with mixed chiral arylammonium and achiral alkylammonium cations. We find that the noncovalent weak interactions (e.g., Br···NH interactions) play an important role in the description of these OIHMHs. Our study further indicates that the two noncentrosymmetric compounds exhibit relatively wide bandgaps (∼3.5 eV), strong second harmonic generation (SHG) responses (∼0.5–1.5 × KDP), and moderate birefringence (∼0.088 at 1064 nm), indicating possible applications for NLO materials. Atom response theory analysis reveals that the SHG responses are determined mainly by the occupied Br <i>3p</i> nonbonding orbitals as well as by the unoccupied Pb <i>5p</i> orbitals, which shows the important contribution of the inorganic PbBr₄ layer to the nonlinear optical properties.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462082","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":"Understanding the Influence of Electrode Potential on Differently Charged Hydrogen Sources in a Hydrogen Evolution Reaction under Neutral Environments","authors":"Xiusong Huang, Junjie Xu, Jian Gao, Yongkang Cui, Xuefei Xu, Shujuan Wang","doi":"10.1021/acs.jpcc.4c01056","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c01056","url":null,"abstract":"Electrochemical water splitting is a promising strategy for reducing hydrogen production costs. However, the conventional phosphate buffer (PBS) electrolyte incurs a huge energy penalty in high overpotential ranges. This study investigates the hydrogen evolution reaction (HER) performance using two buffer electrolytes with different charge properties: H₂ PO₄^–/HPO₄^2– (PBS p<i>K</i>_a = 6.90) and IMZH⁺/IMZ (IMZS p<i>K</i>_a = 7.03). On Pt microelectrodes, results reveal that the plateau current density of PBS correlates closely with the electrode potential, a trend not observed with IMZS. In addition, when using commercial Pt/C nanocatalysts loaded on carbon paper, the plateau current density phenomenon disappears in the IMZS electrolyte, which is attributed to the preconcentration effect of the positively charged hydrogen source. In situ Raman characterization indicates that the configuration of H₂ PO₄^– at the electrochemical interface changes as the electrode potential becomes progressively negative. In comparison, the adsorption configuration of IMZH⁺ remains considerably stable across the tested potential range. The grand canonical density functional theory method with both implicit and explicit solvation models was further used to investigate the influence of electrode potential on the dissociation of a differently charged hydrogen source. Results indicate that when the electrode potential becomes progressively negative, H₂ PO₄^– is repelled from the electrode surface owing to electrostatic forces, increasing Gibbs free energy of dissociation accordingly. This phenomenon contributes to the inevitable energy penalty observed in the PBS electrolyte for the HER. In comparison, the Gibbs free energy of dissociation of IMZH⁺ decreases monotonically with the progressive negative cathode potential. To explain this discrepancy, this study briefly examined the influence of electrode potential in two aspects: theoretical thermodynamics energy and the state of the hydrogen source near the electrode surface.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462113","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":"Raman and Synchrotron X-ray Diffraction Studies of Cd2(C2H6N6)4(NO3)·4H2O under High Pressures","authors":"Jie Ding, Zhongze Pu, Junru Jiang, Peifen Zhu, Hongyang Zhu","doi":"10.1021/acs.jpcc.4c03060","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c03060","url":null,"abstract":"Cd₂(C₂H₆N₆)₄(NO₃)₄·H₂O (<b>CdHATr</b>), a triazole-based energetic compound, was selected for high-pressure research. Employing in situ Raman scattering and synchrotron angle-dispersive X-ray diffraction (ADXRD) technologies, this study investigated <b>CdHATr</b> up to ∼16.3 GPa at room temperature. The vibrational modes of <b>CdHATr</b> at ambient pressure were comprehensively resolved based on the experimental results. Detailed spectral analyses revealed that <b>CdHATr</b> underwent three pressure-induced phase transitions at 0.5, 2.2, and 5.2 GPa. ADXRD experiments confirmed the presence of these phase transitions, as observed in Raman spectral analyses. By analyzing the changes of the vibrational spectra and the lattice parameters under pressure, it is suggested that the first phase transition arises from the deformation of the 3-hydrazino-4-amino-1,2,4-triazole (HATr) ligand, the second phase transition results from the rearrangement of hydrogen bonds, and the third phase transition is caused by the conformational change of the triazole ring. ADXRD results show that <b>CdHATr</b> may experience an abnormal expansion at 0.5 GPa, which is probably caused by the deformation of the HATr ligand. This work contributes to the understanding of the structures of triazole-based energetic compounds under pressure, which will help in the synthesis of new compounds in the future.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462141","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":"Insight into the Importance of Charge Transfer Dynamics in CsPbBr3 Perovskite Nanocrystals for Photovoltaic Applications","authors":"Priyanka Dubey, Leepsa Mishra, Aradhana Panigrahi, Soumi Dutta, Ranjan Kumar Behera, Sankalan Mondal, Manas Kumar Sarangi","doi":"10.1021/acs.jpcc.4c03301","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c03301","url":null,"abstract":"Charge transfer (CT) kinetics at the interfaces of lead-halide-based perovskite nanocrystals (PNCs) are pivotal in dictating the efficacies of energy conversion. Our investigation delves into the intricacies of CT between cesium lead bromide (CsPbBr₃)-based PNCs and fullerene (C₆₀) employing a suite of spectroscopic and theoretical investigations. Notably, we discern a facile interfacial photoinduced electron transfer (ET) from CsPbBr₃ PNCs to C₆₀, in good agreement with their respective aligned energy levels. Complementary current sensing atomic force microscopy measurements unveil a substantial enhancement in conductivity across the electrode–PNC–electrode nanojunction in the presence of C₆₀. To establish the implications of such ET in photovoltaic devices, we have simulated the performance of two devices: one without C₆₀ and one with C₆₀. We unfold an impressive increment in the power conversion efficiency from 12.5% to 15.8% in FTO/CsPbBr₃/PEDOT:PSS/Au configurations upon integrating a band-aligned C₆₀ layer. These outcomes accentuate the relevance of regulated interlayer CT in optimizing photovoltaic device performance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462072","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":"Quasi-Elastic Neutron Scattering of Citrate-Capped Iron Oxide Nanoparticles: Distinguishing between Ligand, Water, and Magnetic Dynamics","authors":"Maksim S. Plekhanov, Sabrina L. J. Thomä, Andreas Magerl, Markus Appel, Mirijam Zobel","doi":"10.1021/acs.jpcc.4c00479","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c00479","url":null,"abstract":"Experimental access to the diffusional properties of organic ligand molecules on nanoparticle (NP) surfaces is scarce, although surface functionalization is widespread in synthesis and for the control of functional particle properties. This work focuses on the dynamics of citrate ligands and water molecules on the surface of 6 nm iron oxide NPs (IONPs) equilibrated at a relative humidity of 8% by quasi-elastic neutron scattering. Given the complex quasi-elastic scattering signal including the magnetic nature of the IONPs, we build on fixed window scans to separate multiple dynamic processes, namely, phonons, magnetic relaxations, and hydrogen dynamics. In addition, deuterated samples allowed us to separate the ligand and water dynamics. With a simultaneous fit approach, multiple fixed window scans and energy-resolved spectra are described to determine the activation energies and relaxation times. It is found that surface-bound citrate ligands rotate continuously with <i>E</i>_a = 240 meV and τ_<i>0</i> = 0.21 ps, while surface water diffuses translationally with <i>E</i>_a = 190 meV and τ_<i>0</i> = 0.12 ps, significantly slower than bulk water. The separation of the coexisting dynamic processes in this study proves the high potential of quasi-elastic neutron scattering to reach a detailed understanding of interfacial processes in nanostructured materials.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462086","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":"Dopant-Inherent Mechanisms of Atmospheric Stability in Chemically N-Doped Semiconducting Carbon Nanotubes Revealed by Tracking Optical Absorption","authors":"Kazuhiro Yoshida, Yuki Kuwahara, Takeshi Saito, Yoshiyuki Nonoguchi","doi":"10.1021/acs.jpcc.4c03020","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c03020","url":null,"abstract":"The stability of n-type single-walled carbon nanotubes (CNTs) in air is crucial for the development of CNT-based electronics and energy-harvesting generators. Various attempts using chemical dopants have led to significant improvements in the air tolerance of n-type CNTs; however, our understanding of their stability depending on the CNTs’ structural features and dopant species, particularly that of the air sensitivity of semiconducting CNTs, remains incomplete. In this study, we investigated the atmospheric stability of chemically n-doped CNTs using time-course infrared absorption spectroscopy. This technique is advantageous for selectively monitoring the stability of semiconducting CNTs by tracking changes in the excitonic absorption and plasmonic response. Furthermore, its adaptability was confirmed by examining the stability dependences on the average tube diameters. Based on this evaluation method, distinct stabilization mechanisms for doping CNTs using supramolecular salt-based dopants (e.g., crown ether complexes) and superelectron donors (SEDs; e.g., 4-(2,3-dihydro-1,3-dimethyl-1<i>H</i>-benzimidazol-2-yl)-<i>N</i>,<i>N</i>-dimethylbenzenamine) were examined. These findings can pave the way for the promising design of practical, flexible electronic devices and energy generators involving n-doped semiconducting CNTs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462111","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":"Unraveling the Adsorption Mechanism of Rhodamine B onto Conjugated Polymeric Nanoparticles Using Isothermal Calorimetry and Monte Carlo Simulations","authors":"Rodrigo A. Ponzio, Emmanuel Odella, Elise Prost, Raquel Gutiérrez-Climente, Rodrigo E. Palacios, Luminita Duma, Carlos A. Chesta","doi":"10.1021/acs.jpcc.4c01624","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c01624","url":null,"abstract":"We present herein a comprehensive study on the thermodynamics of rhodamine B (RhB) adsorption onto poly(9,9-dioctylfluorene-<i>alt</i>-benzothiadiazole) (F8BT) nanoparticles (NPs) dispersed in water using the isothermal calorimetric titration (ITC) technique. ITC experiments were carried out over a wide temperature range (5–65 °C), and the resulting thermograms were subjected to a detailed thermodynamic analysis using different adsorption models. For this purpose, we developed a versatile computational code based on the Monte Carlo method. We found that the thermograms obtained at the different temperatures cannot be interpreted using the Langmuir, bi-Langmuir, or Brunauer, Emmet, Teller (BET) models. However, excellent thermogram fits were attained by applying the Langmuir model coupled with the formation of a RhB dimer on the surface of F8BT NPs. Using this model, the best fit to the experimental data at 25 °C yielded the following parameters for direct RhB adsorption on the F8BT NPs surface: equilibrium constant (<i>K</i>_<i>l</i>) of ∼2 × 10⁷ M^–1, enthalpy change (Δ<i>H</i>_<i>l</i>) of ∼1 kJ mol^–1, and entropy change (Δ<i>S</i>_<i>l</i>) of ∼140 J K^–1 mol^–1. These results indicate that dye adsorption is predominantly an entropy-controlled process. The fit also provided parameters associated with the formation of a second dye adsorption layer, <i>i.e</i>., the formation of the RhB dimer on the F8BT NPs surface, revealing values of ∼1.7 × 10⁵ M^–1, ca. −20 kJ mol^–1, and ∼30 J K^–1 mol^–1 for <i>K_m</i>, Δ<i>H_m</i>, and Δ<i>S_m</i>, respectively. The latter two parameters are similar to those previously reported for RhB dimer formation in water (Δ<i>H</i>_d = −12 kJ mol^–1 and Δ<i>S</i>_d = 22 J K^–1 mol^–1) supporting the chosen Langmuir-dimer model. The analysis of the thermograms also suggests that the NPs surface available for RhB adsorption is small, as compared to the total surface, and that it decreases with decreasing temperature. The latter observation is intriguing, especially since the F8BT NPs hydrodynamic diameter shows only a small decrease with decreasing temperature. To explain these results, we propose that the surface of the NPs harbors highly hydrated polar groups that reduce the accessibility of the dye for adsorption.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462039","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":"Electrical Properties and Current-Illumination Characteristics of the SiC/GaN Lateral Heterostructure","authors":"Enling Li, Ke Qin, Zhen Cui, Yang Shen, Deming Ma, Pei Yuan, Hanxiao Wang","doi":"10.1021/acs.jpcc.4c01809","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c01809","url":null,"abstract":"The construction of lateral heterostructures (LHSs) has the potential to adjust the electrical properties and current-illumination characteristics through interfacial interactions, providing new possibilities for the development of electron and photoelectric devices. In this research, the electronic and electrical properties as well as the current-illumination characteristics of the SiC/GaN LHSs have been investigated using first principles. The band structure analysis indicates that the band gap of the SiC/GaN LHSs can be regulated by the number of layers, and the type-II heterostructure and built-in electric field are formed. The SiC/GaN LHS have high electron carrier mobility along the <i>Y</i>-axis and higher current compared to the intrinsic g-GaN and g-SiC under the same forward bias voltage (<i>V</i>_b). Furthermore, the SiC/GaN LHS is a nanoscale p–n junction with a reverse current much smaller than the forward current. Photocurrent exhibits a strong response near-ultraviolet, and the maximum photocurrent is 79.03 <i>a</i>₀²/photon. The results show that SiC/GaN LHSs can be used as a potential material for electron and photoelectric devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462051","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":"Probing the Formation and Evolution of Pd Nanoparticles on the Surface of γ-Al2O3 Using a Pd(II) Coordination Polymer as a Precursor: An In Situ X-ray Scattering and Spectroscopy Study","authors":"Siddhant Singh, Robert W. J. Scott","doi":"10.1021/acs.jpcc.4c03277","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c03277","url":null,"abstract":"Due to the small size and very low metal loadings in heterogeneously supported nanoparticle catalysts, it is a characterization challenge to trace and control the formation and structural evolution of nanoparticles during their synthesis. In this report, we have probed the formation of alumina-supported Pd nanoparticles by thermal treatment of a 1:3 composite of a Pd(II) coordination polymer (Pd(II)-CP) and a γ-Al₂O₃ powder using in situ X-ray total scattering and X-ray absorption spectroscopy. By comparing the pyrolysis process of Pd(II)-CP in the absence and presence of γ-Al₂O₃, we found that the sintering of Pd nanoparticles by the coalescence of nucleation sites can be significantly reduced on γ-Al₂O₃ surfaces. The introduction of γ-Al₂O₃ provides far better control over the size, distribution, and speciation of the synthesized Pd nanoparticles. The results showed that the sintering of Pd nanoparticles does not occur on the surface of γ-Al₂O₃ until the Pd(II)-CP structure is fully collapsed at 400 °C, most likely because the organic framework of Pd(II)-CP provides spatially distinct sites for Pd nucleation. Moreover, the interface of the γ-Al₂O₃ surface and Pd(II)-CP protected the Pd nanoparticle nucleation sites from air oxidation up to 500 °C. Thereafter, a slow conversion of the Pd fcc phase to the PdO phase started taking place, which was facilitated by the formation of an amorphous PdO_<i>x</i> phase as an intermediate.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462062","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":"Noncovalent Functionalization of Black Phosphorus: Free Energy Simulations vs Adsorption Experiments","authors":"Hanieh Ghodrati, Piotr Zabierowski, Bing Wu, Iva Plutnarová, Zdeněk Sofer, Christoph Allolio","doi":"10.1021/acs.jpcc.4c02403","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c02403","url":null,"abstract":"We investigate the adsorption behavior of various molecules on black phosphorus (BP), employing molecular dynamics (MD)-based free energy calculations in combination with experimental measurements. We find a semiquantitative agreement between experiment and theory. Our approach works best at the low concentration limit, as this allows us to neglect adsorbate–adsorbate interactions, both in solution and on the surface. We also conducted simulations at high concentrations to qualitatively estimate these effects and propose a suitable isotherm model for adsorbates. Our results highlight the impact of molecular structure, shape, polarity, and the alignment of adsorbates relative to the BP surface along with the solvent environment on adsorption. Our approach uses generally available methods and can be extended to arbitrary organic molecules and solvents, potentially allowing for a high throughput screening of candidate molecules for noncovalent functionalization of BP.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":null,"pages":null},"PeriodicalIF":4.126,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141462122","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}