Pub Date : 2025-11-06DOI: 10.1016/j.comptc.2025.115564
Koushik Makhal , Bhabani S. Mallik
We examined the mechanistic insights into hydrogenation and dehydrogenation reactions, encompassing various conceivable pathways of two-electron and two-proton addition reactions catalyzed by redox Fe dithiolene complexes using computational methods. The investigation considers both ligand-mediated and ligand-metal-mediated reaction paths. The plausible pathway for adding two protons and two electrons is the ECEC (E electron transfer process, C proton transfer process) sequence involving protonation at the Fe center and one S center. A decrease in the spin density at the metal center during FeH bond formation is indicative of electron transfer from the Fe to the hydrogen and sulfur centers. The d orbital of the Fe center is engaged with the s orbital of a hydrogen atom. But the py orbital of the sulfur atom interacts with the s orbital of hydrogen, culminating in the formation of an SH bond. In the dehydrogenation reaction, H2 formation occurs at the FeH and SH sites.
{"title":"A computational approach to understand stepwise PCET during hydrogen evolution reaction by iron dithiolene catalyst","authors":"Koushik Makhal , Bhabani S. Mallik","doi":"10.1016/j.comptc.2025.115564","DOIUrl":"10.1016/j.comptc.2025.115564","url":null,"abstract":"<div><div>We examined the mechanistic insights into hydrogenation and dehydrogenation reactions, encompassing various conceivable pathways of two-electron and two-proton addition reactions catalyzed by redox Fe dithiolene complexes using computational methods. The investigation considers both ligand-mediated and ligand-metal-mediated reaction paths. The plausible pathway for adding two protons and two electrons is the ECEC (E electron transfer process, C proton transfer process) sequence involving protonation at the Fe center and one S center. A decrease in the spin density at the metal center during Fe<img>H bond formation is indicative of electron transfer from the Fe to the hydrogen and sulfur centers. The d orbital of the Fe center is engaged with the s orbital of a hydrogen atom. But the p<sub>y</sub> orbital of the sulfur atom interacts with the s orbital of hydrogen, culminating in the formation of an S<img>H bond. In the dehydrogenation reaction, H<sub>2</sub> formation occurs at the Fe<img>H and S<img>H sites.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1256 ","pages":"Article 115564"},"PeriodicalIF":3.0,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145622399","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 : 2025-11-05DOI: 10.1016/j.comptc.2025.115585
Zinah H. Obaid, Lafy F. Al-Badry
In this study, the toxic gases such as NO2, SO2, CO2, and CO contribute to air pollution, making their detection essential for environmental monitoring and public safety. The gas adsorption behavior of NO2, SO2, CO2, and CO molecules on Ni- and Cu-doped Janus ZrSSe monolayers was systematically investigated using first-principles computations based on density functional theory (DFT). The results reveal that NO2 exhibits the strongest interaction with both doped surfaces, possessing the most significant recorded adsorption energy for Ni-doped ZrSSe (−4.28 eV), followed by Cu-doped ZrSSe (−3.71 eV). The large difference between the band gaps before and after adsorption certainly generates a high sensitivity to NO2 gas in the Ni-ZrSSe system, which reaches 119.09. These results highlight the potential of Ni-ZrSSe, in particular, as a promising applicant for NO₂ gas sensing applications due to its enhanced adsorption capability.
{"title":"First-principles study of Ni/Cu doped Janus ZrSSe monolayers for selective and high-affinity sensing of industrial pollutant gases","authors":"Zinah H. Obaid, Lafy F. Al-Badry","doi":"10.1016/j.comptc.2025.115585","DOIUrl":"10.1016/j.comptc.2025.115585","url":null,"abstract":"<div><div>In this study, the toxic gases such as NO<sub>2</sub>, SO<sub>2</sub>, CO<sub>2</sub>, and CO contribute to air pollution, making their detection essential for environmental monitoring and public safety. The gas adsorption behavior of NO<sub>2</sub>, SO<sub>2</sub>, CO<sub>2</sub>, and CO molecules on Ni- and Cu-doped Janus ZrSSe monolayers was systematically investigated using first-principles computations based on density functional theory (DFT). The results reveal that NO<sub>2</sub> exhibits the strongest interaction with both doped surfaces, possessing the most significant recorded adsorption energy for Ni-doped ZrSSe (−4.28 eV), followed by Cu-doped ZrSSe (−3.71 eV). The large difference between the band gaps before and after adsorption certainly generates a high sensitivity to NO<sub>2</sub> gas in the Ni-ZrSSe system, which reaches 119.09. These results highlight the potential of Ni-ZrSSe, in particular, as a promising applicant for NO₂ gas sensing applications due to its enhanced adsorption capability.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115585"},"PeriodicalIF":3.0,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474559","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 study, a systematic first-principles investigation of a newly discovered hydride perovskite compound is presented by density functional theory (DFT). The investigation covers the structural, electronic, magnetic, and the phonon properties as a means of evaluating the stability as well as the functionality of the compound. The optimised crystal structure confirms the thermodynamic stability of the compound, and the calculated lattice constants agree well with the expected perovskite symmetry. Electronic band structure as well as density of states (DOS) calculations confirm a half metallic character, which highlights the effect of hydrogen incorporation on electronic behavior. Further, the calculations of the phonon dispersions prove the absence of imaginary frequencies across the Brillouin zone, and thus confirming the dynamic stability of the hydride perovskite, which exhibits profound gravimetric H2 storing capacities. The Rb-Based 5d Transition Metal exhibits gravimetric H2 storing densities of 1.133 wt%, 1.121 wt%, as well as 1.111 wt% for (Ta, W, and Re), respectively. The results reported in this work reveal that this family of hydrogen-rich perovskites offers a potential use as a technology for storing hydrogen as well as for other energy-related purposes.
{"title":"Coupling DFT with PCA for a comprehensive study of Rb-based 5d transition metal hydride perovskites for hydrogen storage applications","authors":"Mohamed Boubchir , Rachid Boubchir , Nadir Mohamed Belmessaoud , Merzoug Kadous , Hafid Aourag , Bachir Bouhafs","doi":"10.1016/j.comptc.2025.115586","DOIUrl":"10.1016/j.comptc.2025.115586","url":null,"abstract":"<div><div>In this study, a systematic first-principles investigation of a newly discovered hydride perovskite compound is presented by density functional theory (DFT). The investigation covers the structural, electronic, magnetic, and the phonon properties as a means of evaluating the stability as well as the functionality of the compound. The optimised crystal structure confirms the thermodynamic stability of the compound, and the calculated lattice constants agree well with the expected perovskite symmetry. Electronic band structure as well as density of states (DOS) calculations confirm a half metallic character, which highlights the effect of hydrogen incorporation on electronic behavior. Further, the calculations of the phonon dispersions prove the absence of imaginary frequencies across the Brillouin zone, and thus confirming the dynamic stability of the hydride perovskite, which exhibits profound gravimetric H<sub>2</sub> storing capacities. The Rb-Based 5d Transition Metal exhibits gravimetric H<sub>2</sub> storing densities of 1.133 wt%, 1.121 wt%, as well as 1.111 wt% for (Ta, W, and Re), respectively. The results reported in this work reveal that this family of hydrogen-rich perovskites offers a potential use as a technology for storing hydrogen as well as for other energy-related purposes.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115586"},"PeriodicalIF":3.0,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145526397","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}
Cardiovascular diseases, particularly coronary heart disease (CHD), have shown a rising prevalence worldwide, underscoring the critical need for the development of innovative and effective drug delivery systems. In this study, first-principles computational techniques were employed to systematically investigate the potential of the two-dimensional material Arsenene/SnSeS as a carrier for the anti-CHD drug aspirin (ASP). Theoretical calculations suggest favorable structural stability of the material and moderate adsorption strength for the drug molecule. Charge transfer analysis indicates a transfer of 0.21 |e| electrons from ASP to the substrate. Furthermore, theoretical simulations show that the optical properties of Arsenene/SnSeS can be tuned by applied strain, with a redshift observed in the optical absorption peak. The computational model also suggests potential temperature-responsive drug release behavior. Collectively, these theoretical results provide valuable insights for the development of novel CHD treatment platforms and provide a foundation for future experimental studies.
{"title":"Theoretical calculation of arsenene/SnSSe as a potential delivery carrier for anti-coronary heart disease drug","authors":"Xiao Zhu, Yuchen Shi, Qinghua Yang, Yanmin Zhao, Liangzhong Zhang, Xiusheng Sheng","doi":"10.1016/j.comptc.2025.115584","DOIUrl":"10.1016/j.comptc.2025.115584","url":null,"abstract":"<div><div>Cardiovascular diseases, particularly coronary heart disease (CHD), have shown a rising prevalence worldwide, underscoring the critical need for the development of innovative and effective drug delivery systems. In this study, first-principles computational techniques were employed to systematically investigate the potential of the two-dimensional material Arsenene/SnSeS as a carrier for the anti-CHD drug aspirin (ASP). Theoretical calculations suggest favorable structural stability of the material and moderate adsorption strength for the drug molecule. Charge transfer analysis indicates a transfer of 0.21 |e| electrons from ASP to the substrate. Furthermore, theoretical simulations show that the optical properties of Arsenene/SnSeS can be tuned by applied strain, with a redshift observed in the optical absorption peak. The computational model also suggests potential temperature-responsive drug release behavior. Collectively, these theoretical results provide valuable insights for the development of novel CHD treatment platforms and provide a foundation for future experimental studies.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115584"},"PeriodicalIF":3.0,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474621","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 : 2025-11-04DOI: 10.1016/j.comptc.2025.115582
Juan E. López-Cervantes, Rosa L. Camacho-Mendoza, Luis A. Zárate-Hernández, Simplicio González-Montiel, Julián Cruz-Borbolla
The present study demonstrates a relationship between the structural and electronic properties of an octahedral Fe₆ cluster and substituted pyridines, by examining parameters such as the frontier molecular orbital gap, electron affinity, ionization potential, chemical hardness, and electron-donating and electron-accepting power, among others. Chemical reactivity was evaluated based on electronic properties and factors influencing metal-ligand interaction. The computational approach employed the Perdew-Burke-Ernzerhof (PBE) functional with the 6–311++G** basis set for organic molecules and LanL2DZ effective core potential for iron atoms. A topological analysis of the electron density revealed closed-shell interaction with partial covalent character formed by the d orbitals of iron and π bonds of substituted pyridines. Adsorption energies ranged from −16.4 to −32.2 kcal/mol, with compounds containing electron-withdrawing groups and benzyl substituents showing the favorable interactions. The interactions between the Fe₆ cluster and substituted pyridines were characterized as η1–η3 coordination type. This approach provided detailed insights into metal-ligand interactions in Fe₆ octahedral clusters, which could be valuable for the design and optimization of novel catalytic materials for applications in organic synthesis, environmental remediation, and energy storage systems.
{"title":"Chemical adsorption and reactivity of pyridine derivatives on octahedral Fe6 cluster: A theoretical DFT approach","authors":"Juan E. López-Cervantes, Rosa L. Camacho-Mendoza, Luis A. Zárate-Hernández, Simplicio González-Montiel, Julián Cruz-Borbolla","doi":"10.1016/j.comptc.2025.115582","DOIUrl":"10.1016/j.comptc.2025.115582","url":null,"abstract":"<div><div>The present study demonstrates a relationship between the structural and electronic properties of an octahedral Fe₆ cluster and substituted pyridines, by examining parameters such as the frontier molecular orbital gap, electron affinity, ionization potential, chemical hardness, and electron-donating and electron-accepting power, among others. Chemical reactivity was evaluated based on electronic properties and factors influencing metal-ligand interaction. The computational approach employed the Perdew-Burke-Ernzerhof (PBE) functional with the 6–311++G** basis set for organic molecules and LanL2DZ effective core potential for iron atoms. A topological analysis of the electron density revealed closed-shell interaction with partial covalent character formed by the d orbitals of iron and π bonds of substituted pyridines. Adsorption energies ranged from −16.4 to −32.2 kcal/mol, with compounds containing electron-withdrawing groups and benzyl substituents showing the favorable interactions. The interactions between the Fe₆ cluster and substituted pyridines were characterized as η<sup>1</sup>–η<sup>3</sup> coordination type. This approach provided detailed insights into metal-ligand interactions in Fe₆ octahedral clusters, which could be valuable for the design and optimization of novel catalytic materials for applications in organic synthesis, environmental remediation, and energy storage systems.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115582"},"PeriodicalIF":3.0,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475070","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 : 2025-11-04DOI: 10.1016/j.comptc.2025.115583
Marisol Ibarra-Rodríguez , M. Esther Sánchez−Castro , Rodrigo Domínguez−García , Mario Sánchez
Adsorption and gas separation are critical processes across diverse industrial sectors, including chemical manufacturing, environmental remediation and semiconductor fabrication. This theoretical study investigates the potential of lanthanum-based coordination complexes, specifically La(mPBCP) and its tricationic counterpart [La(H3mPBCP)]3+, [mPBCP]3− = meta − phenylene−bridged cyclic pyrrole] for the selective capture of biogas components, CO2, CH4, N2, and H2, using dispersion−corrected density functional theory (DFT) at the PBE0-D3/def2-TZVP level. The oxidated species [La(H3mPBCP)]3+ exhibited markedly enhanced adsorption energies, particularly toward CO2 (−28.63 kcal/mol), which is attributed to significant charge transfer interactions from the gas molecules to the lanthanum center, as elucidated by natural bond orbital (NBO) analysis. Structural and electronic analyses reveal a reduced HOMO−LUMO gap and increased electrophilicity of the charged complex, correlating with its adsorption capability. While CO2 and N2 engage through lone−pair donation to the metal center, CH4 exhibit an unconventional chelation−like interaction mode. These findings offer valuable mechanistic insights into the reactivity and stability of lanthanum−based systems, establishing a theoretical framework for the rational design of advanced materials tailored for biogas upgrading and selective gas separation technologies. Notably, this work underscores the critical influence of the lanthanum oxidation state in modulating adsorption affinity and selectivity.
{"title":"Macrocyclic lanthanum complexes for biogas adsorption: A DFT study","authors":"Marisol Ibarra-Rodríguez , M. Esther Sánchez−Castro , Rodrigo Domínguez−García , Mario Sánchez","doi":"10.1016/j.comptc.2025.115583","DOIUrl":"10.1016/j.comptc.2025.115583","url":null,"abstract":"<div><div>Adsorption and gas separation are critical processes across diverse industrial sectors, including chemical manufacturing, environmental remediation and semiconductor fabrication. This theoretical study investigates the potential of lanthanum-based coordination complexes, specifically La(<em>m</em>PBCP) and its tricationic counterpart [La(H<sub>3</sub><em>m</em>PBCP)]<sup>3+</sup>, [<em>m</em>PBCP]<sup>3−</sup> = <em>meta</em> − phenylene−bridged cyclic pyrrole] for the selective capture of biogas components, CO<sub>2</sub>, CH<sub>4</sub>, N<sub>2</sub>, and H<sub>2</sub>, using dispersion−corrected density functional theory (DFT) at the PBE0-D3/def2-TZVP level. The oxidated species [La(H<sub>3</sub><em>m</em>PBCP)]<sup>3+</sup> exhibited markedly enhanced adsorption energies, particularly toward CO<sub>2</sub> (−28.63 kcal/mol), which is attributed to significant charge transfer interactions from the gas molecules to the lanthanum center, as elucidated by natural bond orbital (NBO) analysis. Structural and electronic analyses reveal a reduced HOMO−LUMO gap and increased electrophilicity of the charged complex, correlating with its adsorption capability. While CO<sub>2</sub> and N<sub>2</sub> engage through lone−pair donation to the metal center, CH<sub>4</sub> exhibit an unconventional chelation−like interaction mode. These findings offer valuable mechanistic insights into the reactivity and stability of lanthanum−based systems, establishing a theoretical framework for the rational design of advanced materials tailored for biogas upgrading and selective gas separation technologies. Notably, this work underscores the critical influence of the lanthanum oxidation state in modulating adsorption affinity and selectivity.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115583"},"PeriodicalIF":3.0,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475069","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 : 2025-11-02DOI: 10.1016/j.comptc.2025.115561
K. Deepakvijay, A. Prakasam
The precise modulation of charge transport in organic semiconductors remains a central challenge in the design of high-performance electronic materials. In this study, we present a systematic DFT investigation of eight novel benzidine derivatives, TF2B, TF3B, TO2B, TO4B, TO5B, TIO3B, TIO4B, and TIO5B, functionalized with furan, oxazole, and isoxazole heterocycles at different substitution positions with TPB as reference. We explore how heterocycle type and regioisomeric placement influence molecular planarity, electronic structure, optical absorption, non-covalent interactions, and charge transport properties. Charge transport analysis identifies TO2B as the most promising hole-transport material, with a reorganization energy of 0.258 eV, a hole transfer integral of 0.667 eV, and a hole transfer rate of s−1 outperforming reference materials such as TPB and TPD. TIO4B also demonstrates an excellent hole transfer rate s−1. These findings underscore the critical role of regioisomeric and heterocyclic engineering in optimizing next-generation hole-transport materials in organic electronics.
{"title":"Design of novel benzidine derivatives via regioisomeric furan, oxazole, and isoxazole substitution: quantum study of charge transport","authors":"K. Deepakvijay, A. Prakasam","doi":"10.1016/j.comptc.2025.115561","DOIUrl":"10.1016/j.comptc.2025.115561","url":null,"abstract":"<div><div>The precise modulation of charge transport in organic semiconductors remains a central challenge in the design of high-performance electronic materials. In this study, we present a systematic DFT investigation of eight novel benzidine derivatives, TF2B, TF3B, TO2B, TO4B, TO5B, TIO3B, TIO4B, and TIO5B, functionalized with furan, oxazole, and isoxazole heterocycles at different substitution positions with TPB as reference. We explore how heterocycle type and regioisomeric placement influence molecular planarity, electronic structure, optical absorption, non-covalent interactions, and charge transport properties. Charge transport analysis identifies TO2B as the most promising hole-transport material, with a reorganization energy of 0.258 eV, a hole transfer integral of 0.667 eV, and a hole transfer rate of <span><math><mrow><mn>1.183</mn><mo>×</mo><msup><mn>10</mn><mn>15</mn></msup></mrow></math></span> s<sup>−1</sup> outperforming reference materials such as TPB and TPD. TIO4B also demonstrates an excellent hole transfer rate <span><math><mrow><mn>9.31</mn><mo>×</mo><msup><mn>10</mn><mn>13</mn></msup></mrow></math></span> s<sup>−1</sup>. These findings underscore the critical role of regioisomeric and heterocyclic engineering in optimizing next-generation hole-transport materials in organic electronics.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115561"},"PeriodicalIF":3.0,"publicationDate":"2025-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145475068","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 : 2025-11-01DOI: 10.1016/j.comptc.2025.115581
Junkai Wang, Jingyi Xing
Hydrogen peroxide (H2O2) is a versatile chemical widely used in electronics, medical disinfection, and wastewater treatment. In this work, density functional theory (DFT) calculations were employed to systematically explore the catalytic potential of single transition-metal atoms supported on Mo2CO2 MXene (TM-Mo2CO2) for electrochemical H2O2 production via the two-electron oxygen reduction reaction (2e− ORR) pathway. The results indicate that several transition metals (Ag, Au, Cd, Cu, Fe, Pd, Ti, and Zn) exhibit excellent structural and electrochemical stability on the Mo2CO2 surface. Among these, Ag-Mo2CO2, Cu-Mo2CO2, and Pd-Mo2CO2 preferentially catalyze the 2e− ORR pathway, with Ag-Mo2CO2 showing the most favorable performance—achieving a remarkably low overpotential (η) (0.08 V at both pH = 0 and 13) and a minimal energy barrier (0.17 eV)—significantly outperforming pristine Mo2CO2 in both activity and selectivity toward H2O2 formation. These findings demonstrate the feasibility of MXene-based single-atom catalysts (SACs) for efficient electrochemical H2O2 production and provide theoretical insights to guide the rational design of efficient MXene-supported 2e− ORR catalysts
{"title":"First-principles study of Mo2CO2-supported single-atom catalysts for electrochemical H2O2 production via the 2e−ORR pathway","authors":"Junkai Wang, Jingyi Xing","doi":"10.1016/j.comptc.2025.115581","DOIUrl":"10.1016/j.comptc.2025.115581","url":null,"abstract":"<div><div>Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) is a versatile chemical widely used in electronics, medical disinfection, and wastewater treatment. In this work, density functional theory (DFT) calculations were employed to systematically explore the catalytic potential of single transition-metal atoms supported on Mo<sub>2</sub>CO<sub>2</sub> MXene (TM-Mo<sub>2</sub>CO<sub>2</sub>) for electrochemical H<sub>2</sub>O<sub>2</sub> production via the two-electron oxygen reduction reaction (2e<sup>−</sup> ORR) pathway. The results indicate that several transition metals (Ag, Au, Cd, Cu, Fe, Pd, Ti, and Zn) exhibit excellent structural and electrochemical stability on the Mo<sub>2</sub>CO<sub>2</sub> surface. Among these, Ag-Mo<sub>2</sub>CO<sub>2</sub>, Cu-Mo<sub>2</sub>CO<sub>2</sub>, and Pd-Mo<sub>2</sub>CO<sub>2</sub> preferentially catalyze the 2e<sup>−</sup> ORR pathway, with Ag-Mo<sub>2</sub>CO<sub>2</sub> showing the most favorable performance—achieving a remarkably low overpotential (η) (0.08 V at both pH = 0 and 13) and a minimal energy barrier (0.17 eV)—significantly outperforming pristine Mo<sub>2</sub>CO<sub>2</sub> in both activity and selectivity toward H<sub>2</sub>O<sub>2</sub> formation. These findings demonstrate the feasibility of MXene-based single-atom catalysts (SACs) for efficient electrochemical H<sub>2</sub>O<sub>2</sub> production and provide theoretical insights to guide the rational design of efficient MXene-supported 2e<sup>−</sup> ORR catalysts</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115581"},"PeriodicalIF":3.0,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474620","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 : 2025-11-01DOI: 10.1016/j.comptc.2025.115580
João P. Cachaneski-Lopes , Gabriel G.B. Alves , Didier Bégué , Augusto Batagin-Neto
Organic solar cells (OSCs) have rapidly emerged as a promising alternative to traditional photovoltaic technologies, such as crystalline silicon, due to their potential for low-cost, lightweight, and flexible applications. The development of efficient, non-toxic, and earth-abundant materials has motivated the transition from fullerene-based acceptors to non-fullerene counterparts. While current non-fullerene acceptors offer improved spectral absorption, they still present limitations in terms of absorption bandwidth and exciton dissociation efficiency, which constrain overall device performance. In this work, we designed and computationally evaluated a series of donor and acceptor molecules based on Y6 derivatives and melanin-inspired motifs. Specifically, we investigated the effect of incorporating hydroxyindole-based end groups (EGmel) into the Y6 core structure using density functional theory (DFT). Our findings show that the presence of EGmel broadens optical absorption (red-shift of Δλmax up to ≈ 83.61 nm with gap reduction of up to ΔEgap ≈ −0.28 eV) and enhances electron-donating/acceptance capabilities (up to ΔRD ≈ −0.07 and ΔRA ≈ 0.10), key traits for high-performance OSCs. Furthermore, we assessed a set of melanin-like oligomers as potential donor materials, which showed open-circuit voltage predictions comparable to benchmark donors such as PM6 and D18. These findings underscore the potential of bio-inspired modifications, such as hydroxyindole end groups and indolic donor cores, to improve the performance and sustainability of next-generation organic photovoltaic materials.
{"title":"DFT-guided design of melanin-inspired materials for high-performance organic solar cells","authors":"João P. Cachaneski-Lopes , Gabriel G.B. Alves , Didier Bégué , Augusto Batagin-Neto","doi":"10.1016/j.comptc.2025.115580","DOIUrl":"10.1016/j.comptc.2025.115580","url":null,"abstract":"<div><div>Organic solar cells (OSCs) have rapidly emerged as a promising alternative to traditional photovoltaic technologies, such as crystalline silicon, due to their potential for low-cost, lightweight, and flexible applications. The development of efficient, non-toxic, and earth-abundant materials has motivated the transition from fullerene-based acceptors to non-fullerene counterparts. While current non-fullerene acceptors offer improved spectral absorption, they still present limitations in terms of absorption bandwidth and exciton dissociation efficiency, which constrain overall device performance. In this work, we designed and computationally evaluated a series of donor and acceptor molecules based on Y6 derivatives and melanin-inspired motifs. Specifically, we investigated the effect of incorporating hydroxyindole-based end groups (EG<sub>mel</sub>) into the Y6 core structure using density functional theory (DFT). Our findings show that the presence of EG<sub>mel</sub> broadens optical absorption (red-shift of Δλ<sub>max</sub> up to ≈ 83.61 nm with gap reduction of up to ΔE<sub>gap</sub> ≈ −0.28 eV) and enhances electron-donating/acceptance capabilities (up to ΔR<sub>D</sub> ≈ −0.07 and ΔR<sub>A</sub> ≈ 0.10), key traits for high-performance OSCs. Furthermore, we assessed a set of melanin-like oligomers as potential donor materials, which showed open-circuit voltage predictions comparable to benchmark donors such as PM6 and D18. These findings underscore the potential of bio-inspired modifications, such as hydroxyindole end groups and indolic donor cores, to improve the performance and sustainability of next-generation organic photovoltaic materials.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115580"},"PeriodicalIF":3.0,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474619","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 : 2025-11-01DOI: 10.1016/j.comptc.2025.115575
Shurong Wu , Xia Luo , Shibin Wang , Shengwei Deng , Xing Zhong , Jian-guo Wang
The diffusion and transport of key species within the nano–microporous structures of supported metal catalysts are crucial for their performance. This study investigates an electrocatalytic system for the in-situ co-generation of ozone and hypochlorous acid. Using molecular dynamics simulations, we explore the diffusion of O2, O3, and HClO within TiO2 nanoslits loaded with RuIr alloy nanoparticles, examining the effects of temperature, pressure, and the local pore environment. Results show that self-diffusion coefficients increase with temperature, more significantly for O2 and O3, while elevated pressure suppresses diffusion, especially under confinement. Gas adsorption on the RuIr nanoparticles restricts diffusion at low pressure, but this effect diminishes at higher pressures. In gas mixtures, differing adsorption affinities for the alloy and substrate surfaces alter diffusion behaviors: O2 diffusion is markedly hindered at high alloy loadings, O3 diffusion decreases nonlinearly with particle density, while HClO diffusion is less affected.
{"title":"Molecular diffusion mechanisms of O3, O2, and HClO for synergistic ozone and chlorine evolution","authors":"Shurong Wu , Xia Luo , Shibin Wang , Shengwei Deng , Xing Zhong , Jian-guo Wang","doi":"10.1016/j.comptc.2025.115575","DOIUrl":"10.1016/j.comptc.2025.115575","url":null,"abstract":"<div><div>The diffusion and transport of key species within the nano–microporous structures of supported metal catalysts are crucial for their performance. This study investigates an electrocatalytic system for the in-situ co-generation of ozone and hypochlorous acid. Using molecular dynamics simulations, we explore the diffusion of O<sub>2</sub>, O<sub>3</sub>, and HClO within TiO<sub>2</sub> nanoslits loaded with Ru<img>Ir alloy nanoparticles, examining the effects of temperature, pressure, and the local pore environment. Results show that self-diffusion coefficients increase with temperature, more significantly for O<sub>2</sub> and O<sub>3</sub>, while elevated pressure suppresses diffusion, especially under confinement. Gas adsorption on the Ru<img>Ir nanoparticles restricts diffusion at low pressure, but this effect diminishes at higher pressures. In gas mixtures, differing adsorption affinities for the alloy and substrate surfaces alter diffusion behaviors: O<sub>2</sub> diffusion is markedly hindered at high alloy loadings, O<sub>3</sub> diffusion decreases nonlinearly with particle density, while HClO diffusion is less affected.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1255 ","pages":"Article 115575"},"PeriodicalIF":3.0,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145474560","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}
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