Journal of Chemical Physics最新文献

Toward data-driven predictive modeling of electrocatalyst stability and surface reconstruction. 电催化剂稳定性和表面重建的数据驱动预测建模。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0271797

Jiayu Peng

{"title":"Toward data-driven predictive modeling of electrocatalyst stability and surface reconstruction.","authors":"Jiayu Peng","doi":"10.1063/5.0271797","DOIUrl":"10.1063/5.0271797","url":null,"abstract":"Catalyst dissolution and surface restructuring are ubiquitous in electrocatalysis, often leading to formidable activity-stability trade-offs and obscure electrochemically induced surface species that severely hinder the understanding and optimization of electrocatalysts under diverse harsh operating conditions. As even state-of-the-art characterization techniques lack the resolution and efficiency for the unambiguous elucidation of decomposition kinetics and reconstruction dynamics at electrocatalytic interfaces, many atomistic modeling approaches-following the recent advances in physics-driven machine learning-have been widely used to facilitate the atom-by-atom understanding and rational engineering of electrocatalyst stability and dynamics. This Perspective systematically assesses classical and data-driven approaches in theoretical surface science and computational catalysis, recognizing their achievements and highlighting their limitations in throughput, efficiency, accuracy, bias, transferability, and scalability toward enabling realistic and predictive modeling of electrocatalyst degradation and reconstruction. By examining different methods spanning first-principle simulations, surface sampling, neural network interatomic potentials, and generative deep learning models, it is underscored how such data-driven computational techniques help elucidate the precise nature of various key interfacial atomistic processes to address existing technical challenges in surface modeling and provide a new paradigm to optimize dissolution kinetics and restructuring dynamics for electrocatalyst design.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unraveling the mechanisms of charge-separation in a dibenzo[b,d]thiophene sulfone polymer photocatalyst using time-resolved electronic absorption spectroscopy. 利用时间分辨电子吸收光谱法揭示二苯并[b，d]噻吩砜聚合物光催化剂中的电荷分离机制。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0274944

Richard J Lyons, Ewan McQueen, Rhys J Bourhill, Owen Thwaites, Andrew I Cooper, Reiner Sebastian Sprick, Alexander J Cowan, Adrian M Gardner

{"title":"Unraveling the mechanisms of charge-separation in a dibenzo[b,d]thiophene sulfone polymer photocatalyst using time-resolved electronic absorption spectroscopy.","authors":"Richard J Lyons, Ewan McQueen, Rhys J Bourhill, Owen Thwaites, Andrew I Cooper, Reiner Sebastian Sprick, Alexander J Cowan, Adrian M Gardner","doi":"10.1063/5.0274944","DOIUrl":"10.1063/5.0274944","url":null,"abstract":"Organic polymer photocatalysts have gained much interest in recent years, largely because of their photocatalytic activity toward sacrificial hydrogen production from water. Time-resolved electronic absorption spectroscopy is commonly employed to understand the photophysical processes occurring following photon absorption, which in turn is used to rationalize photocatalytic activities. The homopolymer of dibenzo[b,d]thiophene sulfone (P10) is a well-studied and high performing photocatalyst for sacrificial hydrogen evolution from water. While sacrificial reagents are well documented as a prerequisite for this reaction, their roles in the picosecond-nanosecond photodynamics have yet to be determined using transient electronic signatures. By employing lifetime density analysis of time-resolved electronic absorption spectra of P10 in a variety of solvent mixtures, we show that the electron polaron (the required charge for hydrogen evolution) is produced on the 0.5-100 and 50-800 ps timescales via excitonic quenching by triethylamine and methanol, respectively, two common sacrificial electron donors. We conclude that there is significant pre-association of triethylamine with the P10 polymer, resulting in efficient excitonic quenching. This mechanism competes effectively with radiative excitonic relaxation, which occurs on similar timescales, reducing exciton losses and improving polaron yields.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Spin-orbit ab initio and density functional theory study of vinyl iodide: Molecular properties and photodissociation dynamics. 自旋轨道从头算和密度泛函理论研究碘化乙烯的分子性质和光解动力学。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0272176

Joonghan Kim, Jeongmin Park, Ingyeong Kim, Wonil Seo, Yurim Jin, Junho Lee, Tae Kyu Kim

{"title":"Spin-orbit ab initio and density functional theory study of vinyl iodide: Molecular properties and photodissociation dynamics.","authors":"Joonghan Kim, Jeongmin Park, Ingyeong Kim, Wonil Seo, Yurim Jin, Junho Lee, Tae Kyu Kim","doi":"10.1063/5.0272176","DOIUrl":"10.1063/5.0272176","url":null,"abstract":"We present a comprehensive theoretical investigation of vinyl iodide (VI), examining its molecular properties and photodissociation dynamics using high-level ab initio and density functional theory methods explicitly incorporating spin-orbit coupling (SOC). To align with experimental results, accurately determining the bond dissociation energy requires an explicit consideration of SOC. For ab initio calculations, correcting for basis set superposition error proves essential for obtaining quantitatively accurate values consistent with the experimental value. We calculate vertical excitation energies and systematically characterize the potential energy curves (PECs) along the C-I dissociation coordinate. This study establishes explicit excited state assignments for VI for the first time, highlighting the significant role of triplet states, particularly the 4A' and 4A″ states in photodissociation dynamics. These states are found to contribute the broad UV absorption band around 250 nm mainly through σ* ← n″ and σ* ← n' excitations rather than the previously proposed π* ← n″ excitation. Our calculated PECs provide theoretical validation and detailed explanations for the experimentally observed wavelength-dependent quantum yields and anisotropy parameters of I(2P3/2) and I*(2P1/2) species.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electron spin, kinetic energy, and stereodynamics control of the reaction between 9-methyl-8-oxoguanine radical cation and nitric oxide. 9-甲基-8-氧鸟嘌呤自由基阳离子与一氧化氮反应的电子自旋、动能和立体动力学控制。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0283629

Jonathan Benny, Jianbo Liu

{"title":"Electron spin, kinetic energy, and stereodynamics control of the reaction between 9-methyl-8-oxoguanine radical cation and nitric oxide.","authors":"Jonathan Benny, Jianbo Liu","doi":"10.1063/5.0283629","DOIUrl":"10.1063/5.0283629","url":null,"abstract":"8-oxoguanine (OG) is a prevalent DNA lesion and exhibits a significantly lower oxidation potential than natural nucleic acid components, making the formation of OG•+ radical cation the most efficient hole trap in the one-electron oxidation of DNA. Nitric oxide (•NO) is a precursor to reactive nitrogen species and plays multiple roles in biological activities, including DNA base nitrosation and enhancement of DNA radiosensitivity in radiotherapy. Herein, we report the reaction of •NO with 9-methyl-8-oxoguanine radical cation (9MOG•+), a model compound for OG•+ nucleoside. 9MOG•+ was generated via redox dissociation of [CuII(9MOG)3]•2+ and its reaction with •NO was investigated using electrospray ionization guided-ion beam mass spectrometry as a function of kinetic energy. Multiple coupled reaction potential energy surfaces were computed using spin-projected ωB97XD, DLPNO-CCSD(T), and CASPT2 methods, with theoretical results benchmarked against experimentally determined reaction thermodynamics. The synergistic experiment and computation revealed distinct reaction mechanisms and dynamics across the open-shell singlet, close-shell singlet, and triplet states formed in radical-radical collisions. Comparison with the reaction of •NO with guanine radical cation (G•+) [Benny and Liu, J. Chem. Phys. 159, 085102 (2023) and Benny et al., J. Chem. Phys. 161, 125101 (2024)] addressed the resemblances and distinctions between •NO reaction dynamics with OG•+ vs G•+. On the one hand, both systems present spin-orbit charge transfer, forming vibrationally excited NO+(ν+ = 1) product ions. On the other hand, OG•+ demonstrates lower nitrosation efficiency than G•+ due to few pathways, less favorable thermodynamics, and constrained stereodynamics. Only the closed-shell singlet [5-NO-9MOG]+ product was detected. This study provides new insights into •NO-mediated DNA damage.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731167","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Quantum dynamics of dissipative two-level systems and intradimer excitation energy transfer in the presence of static disorder. 耗散二能级系统的量子动力学与静态失序存在下的内部激发能传递。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0278194

Eleanor L Vandel, Nancy Makri

{"title":"Quantum dynamics of dissipative two-level systems and intradimer excitation energy transfer in the presence of static disorder.","authors":"Eleanor L Vandel, Nancy Makri","doi":"10.1063/5.0278194","DOIUrl":"10.1063/5.0278194","url":null,"abstract":"We use the numerically exact, fully quantum mechanical small matrix path integral (SMatPI) methodology to investigate the time evolution of the reduced density matrix (RDM) following photoexcitation of model molecular dimers in the presence or absence of static disorder. The dimer is modeled in terms of a two-level system that represents the excited electronic states of the monomers, which are coupled to a dissipative bath of vibrational modes with an Ohmic spectral density under diverse conditions that correspond to homo- or heterodimers, weak or moderately strong exciton-vibration coupling, high- or low-frequency vibrations, and high or low temperature. Through the equivalence class path integral algorithm, the averaging with respect to static disorder is performed with computational effort comparable to that of a single SMatPI calculation. We find that static disorder alters the dynamics and equilibrium properties of the RDM in significant and often subtle ways, which can mimic effects associated with stronger or weaker dissipation. The impact of disorder is most pronounced at low temperatures, where it tends to suppress coherence and often induces upward shifts in the population of the higher-lying state, while the effects on the off-diagonal RDM element and the eigenstate populations depend nonmonotonically on the asymmetry parameter. At high temperatures, the population shift is weaker and reversed for some parameters.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Kinetics of seeded protein aggregation: Theory and application. 种子蛋白聚集动力学：理论与应用。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0273677

Alexander J Dear, Georg Meisl, Jing Hu, Tuomas P J Knowles, Sara Linse

{"title":"Kinetics of seeded protein aggregation: Theory and application.","authors":"Alexander J Dear, Georg Meisl, Jing Hu, Tuomas P J Knowles, Sara Linse","doi":"10.1063/5.0273677","DOIUrl":"10.1063/5.0273677","url":null,"abstract":"\"Seeding\" is the addition of preformed fibrils to a solution of monomeric protein to accelerate its aggregation into new fibrils. It is a versatile and widely used tool for scientists studying protein aggregation kinetics, as it enables the isolation and separate study of discrete reaction steps contributing to protein aggregation, specifically elongation and secondary nucleation. However, the seeding levels required to achieve dominating effects on each of these steps separately have been established largely by trial-and-error due in part to the lack of availability of integrated rate laws valid for moderate to high seeding levels and generally applicable to all common underlying reaction mechanisms. Here, we improve on a recently developed mathematical method based on Lie symmetries for solving differential equations and with it derive such an integrated rate law. We subsequently develop simple expressions for the amounts of seed required to isolate each step. We rationalize the empirical observation that fibril seeds must often be broken up into small pieces to successfully isolate elongation. We also derive expressions for average fibril lengths at different times in the aggregation reaction and explore different methods to break up fibrils. This paper will provide an invaluable reference for future experimental and theoretical studies in which seeding techniques are employed and should enable more sophisticated analyses than have been performed to date.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The role of the pre-exponential factor on temperature programmed desorption spectra: A computational study of frozen species on interstellar icy grain mantles. 指前因子对温度程序解吸光谱的作用：星际冰粒地幔上冻结物质的计算研究。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0266978

S Pantaleone, L Tinacci, V Bariosco, A Rimola, C Ceccarelli, P Ugliengo

{"title":"The role of the pre-exponential factor on temperature programmed desorption spectra: A computational study of frozen species on interstellar icy grain mantles.","authors":"S Pantaleone, L Tinacci, V Bariosco, A Rimola, C Ceccarelli, P Ugliengo","doi":"10.1063/5.0266978","DOIUrl":"https://doi.org/10.1063/5.0266978","url":null,"abstract":"Temperature programmed desorption (TPD) is a well-known technique to study gas-surface processes, and it is characterized by two main quantities: the adsorbate binding energy and the pre-exponential factor. While the former has been well addressed in recent years by both experimental and computational methods, the latter remains somewhat ill-defined, and different schemes have been proposed in the literature for its evaluation. In the astrochemistry context, binding energies and pre-exponential factors are key parameters that enter microkinetic models for studying the evolution over time of the chemical species in the universe. In this paper, we studied, by computer simulations, the effect of different pre-exponential factor models using water, ammonia, and methanol adsorbed on amorphous and crystalline ices as test cases: specifically, the one most widely used by the astrochemical community (Herbst-Hasegawa), the models provided by Tait and Campbell, and an extension of the Tait formulation including the calculation of the vibrational partition function. We suggest the methods proposed by Tait and Campbell that provide TPD temperature peaks within 30 K of each other while avoiding demanding quantum mechanical calculations, as they are based on tabulated data. Finally, when the explicit inclusion of the vibrational partition function is needed, we propose a cost-effective strategy to include all the thermal contributions in the partition functions without the need for performing a full vibrational calculation of the whole system.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144742216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Imaging the photodissociation dynamics of vibrationless and vibrationally excited CH3S radicals. 无振动和振动激发的CH3S自由基光解动力学成像。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0283366

Pedro Recio, Alexandre Zanchet, David V Chicharro, Sonia Marggi Poullain, Luis Rubio-Lago, Gustavo A Pino, Luis Bañares

{"title":"Imaging the photodissociation dynamics of vibrationless and vibrationally excited CH3S radicals.","authors":"Pedro Recio, Alexandre Zanchet, David V Chicharro, Sonia Marggi Poullain, Luis Rubio-Lago, Gustavo A Pino, Luis Bañares","doi":"10.1063/5.0283366","DOIUrl":"10.1063/5.0283366","url":null,"abstract":"The photodissociation dynamics of CH3S radicals was studied at different excitation energies within the first absorption band. The CH3S radicals were produced with a broad vibrational energy distribution from the photodissociation of CH3SH at 210 nm, which allowed us to study the effect of the vibrational excitation on the photodissociation dynamics. The photofragments, CH3(ν), S(3PJ), and S(1D) were detected by resonance enhanced multiphoton ionization schemes in slice-imaging experiments, and the corresponding translational energy and angular distributions were obtained for each fragment. Vibrationless CH3S radicals are excited to the Ã2A1 state that predissociates via three possible dissociative states (ã4A2, B̃2A2, and 4E), leading to the formation of CH3(ν = 0), CH3(ν2) with inverted population and S(3PJ) with J = 0, 1, and 2. Instead, vibrationally excited CH3S radicals are excited in the Franck-Condon region of the B̃2A2 dissociative state, where they dissociate directly to produce fast and anisotropic S(3P0) fragments, according to the adiabatic correlation established by the new calculated potential energy curves reported in this work. The B̃2A2 state is crossed by the dissociative 4E state, and this crossing leads to the formation of slower and less anisotropic S(3P1) and S(3P2) fragments that apparently correlate with CH3 populated with one quantum in the C-H stretch (ν1), suggesting that this vibrational mode is involved in the non-adiabatic dynamics associated to the B̃2A2/4E crossing. Finally, S(1D) fragments show a Boltzmann-like kinetic energy distribution with an isotropic angular distribution, associated with slow fragments produced by statistical dissociation from the locally excited Ã2A1 state of CH3S.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Nonadiabatic ring-polymer instanton rate theory: A generalized dividing-surface approach. 非绝热环-聚合物瞬态速率理论：一种广义划分曲面方法。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0279454

Rhiannon A Zarotiadis, Joseph E Lawrence, Jeremy O Richardson

{"title":"Nonadiabatic ring-polymer instanton rate theory: A generalized dividing-surface approach.","authors":"Rhiannon A Zarotiadis, Joseph E Lawrence, Jeremy O Richardson","doi":"10.1063/5.0279454","DOIUrl":"10.1063/5.0279454","url":null,"abstract":"Constructing an accurate approximation to nonadiabatic rate theory that is valid for arbitrary values of the electronic coupling has been a long-standing challenge in theoretical chemistry. Ring-polymer instanton theories offer a very promising approach to solve this problem, since they can be rigorously derived using semiclassical approximations and can capture nuclear quantum effects such as tunneling and zero-point energy at a cost similar to that of a classical calculation. A successful instanton rate theory already exists within the Born-Oppenheimer approximation, for which the optimal tunneling pathway is located on a single adiabatic surface. A related instanton theory has also been developed for nonadiabatic reactions using two weakly coupled diabatic surfaces within the framework of Fermi's golden rule. However, many chemical reactions do not satisfy the conditions of either limit. By employing a tunable dividing surface that measures the flux both along nuclear coordinates and between electronic states, we develop a generalized nonadiabatic instanton rate theory that bridges between these two limits. The resulting theory approximates the quantum-mechanically exact rates well for the systems studied and, in addition, offers a novel mechanistic perspective on nonadiabatic reactions.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731171","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hierarchically cactus-like nickel sulfide-lanthanum carbonate hydroxide composite for urea-assisted water splitting. 仙人掌状硫化镍-氢氧化碳酸盐复合材料用于尿素辅助水分解。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0279752

Mingliang Yang, Hua Jin, Jianfeng Song, Shiqian She, Jia Chen, Kun Xiong

{"title":"Hierarchically cactus-like nickel sulfide-lanthanum carbonate hydroxide composite for urea-assisted water splitting.","authors":"Mingliang Yang, Hua Jin, Jianfeng Song, Shiqian She, Jia Chen, Kun Xiong","doi":"10.1063/5.0279752","DOIUrl":"10.1063/5.0279752","url":null,"abstract":"Hydrogen production from water electrolysis is mainly affected by the high overpotential and slow reaction kinetics of the anodic oxygen evolution reaction (OER). Replacing slow oxygen evolution reaction (OER) with thermodynamically favorable urea oxidation reaction (UOR) is one of the feasible strategies for achieving energy-saving hydrogen production. In this work, a cactus-like nickel sulfide-lanthanum carbonate hydroxide (NiSx-LaCH) composite was synthesized on the surface of Ni foam by a hydrothermal method and sulfurization process for the first time. This cactus-like structure can significantly improve the specific surface area of the catalyst and the electrolyte accessibility. The coupling of NiSx and LaCH brought about the electron structure redistribution and enhanced the stability and conductivity. The generated synergistic effect of NiSx-LaCH/NF improved the adsorption of urea/water molecules and the intrinsic catalytic activity. It exhibited outstanding electrocatalytic performance for UOR and hydrogen evolution reaction, which can drive the current density of 100 mA cm-2 at low potentials of 1.36 V and -0.26 V, respectively. Assembling NiSx-LaCH/NF into urea electrolysis system can reduce the cell voltage by 0.22 V compared to water electrolysis. This indicates that using UOR instead of OER could achieve energy-saving hydrogen production and has promising prospects in treating urea-rich wastewater.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0