Interactions between carboxylated (PS-COOH), aminated (PS-NH₂), and plain (PS-Bare) polystyrene nanoplastics (PSNPs) and trypsin (TRY) were investigated using multispectral techniques and molecular docking. PSNPs enhanced enzymatic activity as PS-COOH (23%) > PS-Bare (16%) > PS-NH₂ (13%). Molecular docking revealed their entry into the TRY active site, inducing conformational and functional changes. Multispectral analysis confirmed PSNPs aggravated TRY backbone peak reduction and redshift, with PS-COOH reducing the α-helix content of TRY from 4.7% to 2.5%. This structural loosening induced active pocket opening and hyperactivation. In conclusion, the conformational changes of proteins induced by functionalized PSNPs closely correlate with their physiological functions.
{"title":"Investigation on the interaction between trypsin and nanoplastics: Effects of surface functionalization","authors":"Wenshu Yin, Yaoyao Wang, Shuaixing Mei, Penglong Zhou, Zongshan Zhao, Jing Lan","doi":"10.1016/j.cplett.2025.142538","DOIUrl":"10.1016/j.cplett.2025.142538","url":null,"abstract":"<div><div>Interactions between carboxylated (PS-COOH), aminated (PS-NH₂), and plain (PS-Bare) polystyrene nanoplastics (PSNPs) and trypsin (TRY) were investigated using multispectral techniques and molecular docking. PSNPs enhanced enzymatic activity as PS-COOH (23%) > PS-Bare (16%) > PS-NH₂ (13%). Molecular docking revealed their entry into the TRY active site, inducing conformational and functional changes. Multispectral analysis confirmed PSNPs aggravated TRY backbone peak reduction and redshift, with PS-COOH reducing the α-helix content of TRY from 4.7% to 2.5%. This structural loosening induced active pocket opening and hyperactivation. In conclusion, the conformational changes of proteins induced by functionalized PSNPs closely correlate with their physiological functions.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142538"},"PeriodicalIF":3.1,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-14DOI: 10.1016/j.cplett.2025.142540
Huimei Mo , Zhanhong Chen , Xiaoying Liao , Shiting Liang , Jin Xu , Haolang Zeng , Shuqian Shen , Junhui Yi
Morphology engineering and heteroatom doping are established strategies for developing high-performance photocatalysts. In this study, phosphorus-doped three-dimensional porous g-C₃N₄ nanosheets were synthesized by calcining melamine–cyanuric acid supramolecular precursors, followed by gas-phase phosphidation using NaH₂PO₂ at 300 °C. The optimized material exhibited exceptional photocatalytic activity, achieving over 99 % Rhodamine B degradation within 40 min under visible light, significantly outperforming undoped 3D and bulk g-C₃N4. It also showed the highest photocurrent density and prolonged carrier lifetime, indicating enhanced charge separation. The catalyst maintained >90 % efficiency after four cycles, demonstrating remarkable stability. Mechanistic studies revealed that holes and superoxide radicals serve as the primary active species, with hydroxyl radicals also participating. The enhanced performance is attributed to the synergistic effect of P-doping—which modifies the electronic structure—and the 3D porous framework, which facilitates mass transfer and exposes active sites. This work provides a scalable route to efficient photocatalysts for environmental remediation.
形态工程和杂原子掺杂是开发高性能光催化剂的常用方法。采用三聚氰胺-三聚氰酸超分子前驱体煅烧制备了磷掺杂的三维多孔g-C₃N₄纳米片，然后在300℃下用na2 PO 2气相磷化。优化的材料表现出优异的光催化活性，在可见光下40分钟内实现超过99%的罗丹明B降解，显著优于未掺杂的3D和大块g-C₃N4。它还显示出最高的光电流密度和延长的载流子寿命，表明电荷分离增强。经过4次循环后，催化剂的效率保持在90%以上，表现出显著的稳定性。机制研究表明，空穴和超氧自由基是主要的活性物质，羟基自由基也参与其中。增强的性能归因于p掺杂的协同效应（改变了电子结构）和3D多孔框架（促进了传质和暴露了活性位点）。这项工作为高效光催化剂的环境修复提供了一条可扩展的途径。
{"title":"Supramolecular precursor-derived P-doped 3D porous g-C₃N₄ nanosheets with highly efficient rhodamine B degradation","authors":"Huimei Mo , Zhanhong Chen , Xiaoying Liao , Shiting Liang , Jin Xu , Haolang Zeng , Shuqian Shen , Junhui Yi","doi":"10.1016/j.cplett.2025.142540","DOIUrl":"10.1016/j.cplett.2025.142540","url":null,"abstract":"<div><div>Morphology engineering and heteroatom doping are established strategies for developing high-performance photocatalysts. In this study, phosphorus-doped three-dimensional porous g-C₃N₄ nanosheets were synthesized by calcining melamine–cyanuric acid supramolecular precursors, followed by gas-phase phosphidation using NaH₂PO₂ at 300 °C. The optimized material exhibited exceptional photocatalytic activity, achieving over 99 % Rhodamine B degradation within 40 min under visible light, significantly outperforming undoped 3D and bulk g-C₃N<sub>4</sub>. It also showed the highest photocurrent density and prolonged carrier lifetime, indicating enhanced charge separation. The catalyst maintained >90 % efficiency after four cycles, demonstrating remarkable stability. Mechanistic studies revealed that holes and superoxide radicals serve as the primary active species, with hydroxyl radicals also participating. The enhanced performance is attributed to the synergistic effect of P-doping—which modifies the electronic structure—and the 3D porous framework, which facilitates mass transfer and exposes active sites. This work provides a scalable route to efficient photocatalysts for environmental remediation.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142540"},"PeriodicalIF":3.1,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-13DOI: 10.1016/j.cplett.2025.142535
Ana B. Salazar-Arriaga, Hector Dominguez
Using molecular dynamics simulations, surfactant efficiency in capturing CO in water is investigated. Three different micelles were prepared in a water:sodium dodecyl sulfate, biosurfactants, and a mixture of both. Simulations are performed at different gas concentrations and temperatures, and it is observed that the biosurfactant micelles and the mixture exhibit better CO retention. Adsorption plots are created, and energies are calculated by fitting Langmuir isotherms. It is determined that these are spontaneous processes. The results show that the packing of the micelles is a factor in determining retention; micelles with low packing factors are better at retaining CO.
{"title":"Using synthetic and biological surfactant molecules for carbon dioxide capture in water: A molecular dynamics approach","authors":"Ana B. Salazar-Arriaga, Hector Dominguez","doi":"10.1016/j.cplett.2025.142535","DOIUrl":"10.1016/j.cplett.2025.142535","url":null,"abstract":"<div><div>Using molecular dynamics simulations, surfactant efficiency in capturing CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> in water is investigated. Three different micelles were prepared in a water:sodium dodecyl sulfate, biosurfactants, and a mixture of both. Simulations are performed at different gas concentrations and temperatures, and it is observed that the biosurfactant micelles and the mixture exhibit better CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> retention. Adsorption plots are created, and energies are calculated by fitting Langmuir isotherms. It is determined that these are spontaneous processes. The results show that the packing of the micelles is a factor in determining retention; micelles with low packing factors are better at retaining CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142535"},"PeriodicalIF":3.1,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-13DOI: 10.1016/j.cplett.2025.142532
Yu-Heng Peng , Ming-Yu Li , Chun-Yaung Lu , Chia-Chun Chou
We present a moving-boundary truncated-grid approach for integrating the time-dependent Schrödinger equation in collinear triatomic reactive scattering (H + H, F + H). The grid is pruned by density and gradient criteria, boundary values are extrapolated in the logarithmic amplitude, and propagation proceeds on a compact, time-varying set. Relative to full-grid baselines, this method delivers smooth, small relative- errors, preserves transmission probabilities and significant interference features, and uses far fewer grid points, achieving up to 1.56-fold shorter wall time. The comparisons with the FG benchmarks in the state-specific energy-resolved probabilities further accentuate the excellent performance of our TG method for practical applications. Computational results demonstrate that this method provides accurate and economical wave packet propagation for reactive scattering.
我们提出了一种移动边界截断网格方法来积分共线三原子反应散射（H + H2, F + H2）中随时间变化的Schrödinger方程。网格由密度和梯度准则修剪，边界值在对数振幅中外推，并在紧凑的时变集合上传播。与全网格基线相比，该方法提供了平滑、较小的相对l2误差，保留了传输概率和显著的干扰特征，并且使用了更少的网格点，将壁时间缩短了1.56倍。在特定状态的能量分解概率上与FG基准的比较进一步强调了我们的TG方法在实际应用中的优异性能。计算结果表明，该方法对反应散射具有准确、经济的波包传播效果。
{"title":"Moving boundary truncated grid method for collinear triatomic reaction dynamics","authors":"Yu-Heng Peng , Ming-Yu Li , Chun-Yaung Lu , Chia-Chun Chou","doi":"10.1016/j.cplett.2025.142532","DOIUrl":"10.1016/j.cplett.2025.142532","url":null,"abstract":"<div><div>We present a moving-boundary truncated-grid approach for integrating the time-dependent Schrödinger equation in collinear triatomic reactive scattering (H + H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>, F + H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>). The grid is pruned by density and gradient criteria, boundary values are extrapolated in the logarithmic amplitude, and propagation proceeds on a compact, time-varying set. Relative to full-grid baselines, this method delivers smooth, small relative-<span><math><msub><mrow><mi>L</mi></mrow><mrow><mn>2</mn></mrow></msub></math></span> errors, preserves transmission probabilities and significant interference features, and uses far fewer grid points, achieving up to 1.56-fold shorter wall time. The comparisons with the FG benchmarks in the state-specific energy-resolved probabilities further accentuate the excellent performance of our TG method for practical applications. Computational results demonstrate that this method provides accurate and economical wave packet propagation for reactive scattering.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142532"},"PeriodicalIF":3.1,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577625","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-13DOI: 10.1016/j.cplett.2025.142536
Kangyue Qiao, Songyao Du, Yue Wang, Tongxin Xiao, Guodong Hao, Chao Sui, Yihan Yan
To address the severe Cr(VI) contamination in industrial wastewater, an NH2-MIL-101(Fe)/g-C3N4 type-II heterojunction photocatalyst was synthesized via a solvothermal one-pot method. Structural characterization using XRD, SEM, XPS, and BET confirmed successful composite formation with high specific surface area and favorable interfacial contact. Photocatalytic experiments revealed that under conditions of pH = 2, a catalyst dosage of 20 mg, and an initial concentration of 10 mg/L, NM-101(Fe)/0.2CN achieved a 99.5 % reduction efficiency within 80 min. Its reaction rate constant was 3.6 times higher than that of NM-101(Fe) used alone. This study provides new insights for developing highly efficient MOF/polymer composite photocatalysts.
{"title":"Investigation of the photocatalytic reduction of Cr(VI) by NH2-MIL-101(Fe)/g-C3N4 composite materials","authors":"Kangyue Qiao, Songyao Du, Yue Wang, Tongxin Xiao, Guodong Hao, Chao Sui, Yihan Yan","doi":"10.1016/j.cplett.2025.142536","DOIUrl":"10.1016/j.cplett.2025.142536","url":null,"abstract":"<div><div>To address the severe Cr(VI) contamination in industrial wastewater, an NH<sub>2</sub>-MIL-101(Fe)/g-C<sub>3</sub>N<sub>4</sub> type-II heterojunction photocatalyst was synthesized via a solvothermal one-pot method. Structural characterization using XRD, SEM, XPS, and BET confirmed successful composite formation with high specific surface area and favorable interfacial contact. Photocatalytic experiments revealed that under conditions of pH = 2, a catalyst dosage of 20 mg, and an initial concentration of 10 mg/L, NM-101(Fe)/0.2CN achieved a 99.5 % reduction efficiency within 80 min. Its reaction rate constant was 3.6 times higher than that of NM-101(Fe) used alone. This study provides new insights for developing highly efficient MOF/polymer composite photocatalysts.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142536"},"PeriodicalIF":3.1,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577621","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}
In this work, DFT and ab initio molecular dynamics are used to offer a thorough first-principles study of the structural, electronic, thermal, and optical properties of the lead-free double perovskite CsPdBr. Excellent mechanical, thermal, dynamic, and energy stability are displayed by the compound. Cs-Br and Pd-Br exhibit mixed ionic–covalent bonding, according to Bader charge analysis. A direct band gap of 0.8 eV (GGA) and 1.95 eV (HSE06) is found using electronic calculations. While optical studies show excellent visible and ultraviolet responses, thermal analysis points to high lattice thermal conductivity, validating the potential of CsPdBr for next-generation optoelectronic and nanotechnological applications.
在这项工作中，使用DFT和从头算分子动力学对无铅双钙钛矿Cs2PdBr6的结构、电子、热学和光学性质进行了彻底的第一性原理研究。该化合物具有优异的机械、热、动力和能量稳定性。根据Bader电荷分析，Cs-Br和Pd-Br表现出混合离子共价键。通过电子计算发现直接带隙为0.8 eV （GGA）和1.95 eV （HSE06）。虽然光学研究显示出优异的可见光和紫外响应，但热分析指出了高晶格导热性，验证了Cs2PdBr6在下一代光电和纳米技术应用中的潜力。
{"title":"High thermal conductivity of the double perovskite semiconductor Cs2PdBr6: An examination of stability, phononic, thermal, and optical properties employing DFT and AIMD simulations under HSE06","authors":"Bashdar Rahman Pirot , Yousif Hussein Azeez , Nzar Rauf Abdullah , Chi-Shung Tang , Vidar Gudmundsson","doi":"10.1016/j.cplett.2025.142534","DOIUrl":"10.1016/j.cplett.2025.142534","url":null,"abstract":"<div><div>In this work, DFT and ab initio molecular dynamics are used to offer a thorough first-principles study of the structural, electronic, thermal, and optical properties of the lead-free double perovskite Cs<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>PdBr<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span>. Excellent mechanical, thermal, dynamic, and energy stability are displayed by the compound. Cs-Br and Pd-Br exhibit mixed ionic–covalent bonding, according to Bader charge analysis. A direct band gap of 0.8 eV (GGA) and 1.95 eV (HSE06) is found using electronic calculations. While optical studies show excellent visible and ultraviolet responses, thermal analysis points to high lattice thermal conductivity, validating the potential of Cs<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>PdBr<span><math><msub><mrow></mrow><mrow><mn>6</mn></mrow></msub></math></span> for next-generation optoelectronic and nanotechnological applications.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142534"},"PeriodicalIF":3.1,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145527248","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-12DOI: 10.1016/j.cplett.2025.142510
Ernesto Garcia , Marta Menendez , F. Javier Aoiz
State-selected cross sections for full and partial dissociation have been calculated for collisions between a hydrogen molecule in its ground rovibrational state and a rovibrationally excited hydrogen molecule. The calculations were performed using quasiclassical trajectories on an ab initio-based potential energy surface. All vibrational states and, several rotational states for each, of the excited molecule (a total of 105 rovibrational states) were considered. Collision energies of up to 900 kcal mol−1 were explored, enabling the determination of rate coefficients of up to 50,000 K. Additionally, the rovibrational distribution of the surviving molecule in partial dissociation events was analyzed.
{"title":"Full and partial dissociation in H2(0,0) + H2 (v, j) collisions","authors":"Ernesto Garcia , Marta Menendez , F. Javier Aoiz","doi":"10.1016/j.cplett.2025.142510","DOIUrl":"10.1016/j.cplett.2025.142510","url":null,"abstract":"<div><div>State-selected cross sections for full and partial dissociation have been calculated for collisions between a hydrogen molecule in its ground rovibrational state and a rovibrationally excited hydrogen molecule. The calculations were performed using quasiclassical trajectories on an <em>ab initio</em>-based potential energy surface. All vibrational states and, several rotational states for each, of the excited molecule (a total of 105 rovibrational states) were considered. Collision energies of up to 900 kcal mol<sup>−1</sup> were explored, enabling the determination of rate coefficients of up to 50,000 K. Additionally, the rovibrational distribution of the surviving molecule in partial dissociation events was analyzed.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142510"},"PeriodicalIF":3.1,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577614","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-10DOI: 10.1016/j.cplett.2025.142530
Ningmeng Shi , Jiaxin Wu , Yuhong Huo , Yixing Shi , Xuexian Yang , Heping Zhao
Based on the bond-order-length-strength (BOLS) theory and the core-shell model, a functional correlation is established to describe the size-dependent melting properties of Group IVA semiconductors. It is found that: (i) The melting temperature of Group IVA decreases with reduced size, lower coordination number and lower cohesive energy, and higher surface-to-volume ratio. (ii) The melting entropy and enthalpy of Group IVA follow a consistent hierarchy: nanofilms > nanowires > nanoparticles. This present formulation is accurate and convenient, which not only shows deeper insight into the physical origins of a melting thermodynamic properties, but also provides guidance for the device's design.
{"title":"Influences of size and dimensionality on melting thermodynamics of group IVA semiconductors","authors":"Ningmeng Shi , Jiaxin Wu , Yuhong Huo , Yixing Shi , Xuexian Yang , Heping Zhao","doi":"10.1016/j.cplett.2025.142530","DOIUrl":"10.1016/j.cplett.2025.142530","url":null,"abstract":"<div><div>Based on the bond-order-length-strength (BOLS) theory and the core-shell model, a functional correlation is established to describe the size-dependent melting properties of Group IVA semiconductors. It is found that: (i) The melting temperature of Group IVA decreases with reduced size, lower coordination number and lower cohesive energy, and higher surface-to-volume ratio. (ii) The melting entropy and enthalpy of Group IVA follow a consistent hierarchy: nanofilms > nanowires > nanoparticles. This present formulation is accurate and convenient, which not only shows deeper insight into the physical origins of a melting thermodynamic properties, but also provides guidance for the device's design.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142530"},"PeriodicalIF":3.1,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-10DOI: 10.1016/j.cplett.2025.142529
Jun-ichi Fujisawa
Methylene blue (MB) is a redox-active dye for various fundamental research and applications. MB is well-known to form face-to-face dimers in various environments, which show the blue-shift of the absorption band. So far, MB dimers have been studied assuming the 180°-twisted structure. However, the assumed structure has not been verified yet. Here, we computationally reveal that the 180°-twisted configuration is the most stable and explains the reported blue-shift quantitatively. This result supports the believed dimer structure. In addition, we also show that the almost-non-twisted dimer structure may be present as a minor component at room temperature.
{"title":"The structure and optical properties of methylene blue dimers","authors":"Jun-ichi Fujisawa","doi":"10.1016/j.cplett.2025.142529","DOIUrl":"10.1016/j.cplett.2025.142529","url":null,"abstract":"<div><div>Methylene blue (MB) is a redox-active dye for various fundamental research and applications. MB is well-known to form face-to-face dimers in various environments, which show the blue-shift of the absorption band. So far, MB dimers have been studied assuming the 180°-twisted structure. However, the assumed structure has not been verified yet. Here, we computationally reveal that the 180°-twisted configuration is the most stable and explains the reported blue-shift quantitatively. This result supports the believed dimer structure. In addition, we also show that the almost-non-twisted dimer structure may be present as a minor component at room temperature.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142529"},"PeriodicalIF":3.1,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145577617","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-10DOI: 10.1016/j.cplett.2025.142533
Hui Li , Jing Zhang , Bin Wang , Han Dai , Chunyan Xu , Junfeng Zhao
Ammonia (NH3) is an essential chemical feedstock for agriculture and industry, yet its conventional Haber–Bosch synthesis is energy-intensive and carbon-emitting. Recently, the electrochemical nitric oxide reduction reaction (NORR) has attracted considerable attention as a sustainable approach that simultaneously removes toxic NO and generates NH3 under ambient conditions. In this work, density functional theory (DFT) calculations were employed to systematically investigate the catalytic performance of two-dimensional conjugated metal–organic framework (2D c-MOF) TM3(HAT)2 monolayers (TM = Cr, Fe, Co, Ni) for NORR. The results reveal that all TM3(HAT)2 systems exhibit favorable thermodynamic and electrochemical stability, along with metallic conductivity that promotes efficient charge transport. Adsorption energy analysis and charge density difference mapping show that NO molecules preferentially bind via N-end adsorption at the TM centers, where a donation/back-donation mechanism weakens the NO bond and facilitates activation. Free-energy profiles further demonstrate that these catalysts effectively suppress the competing hydrogen evolution reaction (HER) and enable selective NO-to-NH3 conversion. Among them, Ni3(HAT)2 exhibit the lowest limiting potentials and N-distal optimal reaction pathways. This study highlights the promise of 2D MOFs as atomically precise single-atom electrocatalysts and provides theoretical guidance for developing efficient and sustainable NH3 synthesis strategies.
{"title":"Two-dimensional conjugated MOF TM3(HAT)2 (TM = Cr, Fe, Co and Ni) monolayers as efficient catalysts for electrochemical NO to NH3conversion","authors":"Hui Li , Jing Zhang , Bin Wang , Han Dai , Chunyan Xu , Junfeng Zhao","doi":"10.1016/j.cplett.2025.142533","DOIUrl":"10.1016/j.cplett.2025.142533","url":null,"abstract":"<div><div>Ammonia (NH<sub>3</sub>) is an essential chemical feedstock for agriculture and industry, yet its conventional Haber–Bosch synthesis is energy-intensive and carbon-emitting. Recently, the electrochemical nitric oxide reduction reaction (NORR) has attracted considerable attention as a sustainable approach that simultaneously removes toxic NO and generates NH<sub>3</sub> under ambient conditions. In this work, density functional theory (DFT) calculations were employed to systematically investigate the catalytic performance of two-dimensional conjugated metal–organic framework (2D c-MOF) TM<sub>3</sub>(HAT)<sub>2</sub> monolayers (TM = Cr, Fe, Co, Ni) for NORR. The results reveal that all TM<sub>3</sub>(HAT)<sub>2</sub> systems exhibit favorable thermodynamic and electrochemical stability, along with metallic conductivity that promotes efficient charge transport. Adsorption energy analysis and charge density difference mapping show that NO molecules preferentially bind via N-end adsorption at the TM centers, where a donation/back-donation mechanism weakens the N<img>O bond and facilitates activation. Free-energy profiles further demonstrate that these catalysts effectively suppress the competing hydrogen evolution reaction (HER) and enable selective NO-to-NH<sub>3</sub> conversion. Among them, Ni<sub>3</sub>(HAT)<sub>2</sub> exhibit the lowest limiting potentials and N-distal optimal reaction pathways. This study highlights the promise of 2D MOFs as atomically precise single-atom electrocatalysts and provides theoretical guidance for developing efficient and sustainable NH<sub>3</sub> synthesis strategies.</div></div>","PeriodicalId":273,"journal":{"name":"Chemical Physics Letters","volume":"883 ","pages":"Article 142533"},"PeriodicalIF":3.1,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145527250","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号