Pub Date : 2026-02-04DOI: 10.1021/acs.jpcc.5c04614
Francesco Zamboni,Niéli Daffé,Jan Dreiser,Jesper Bendix,Lars Diekhöner
Lanthanide complexes Ln[Pt(SAc)4]2 are single-ion magnetic molecules that have recently been shown to exhibit interesting bulk magnetic properties that can be tuned by varying the central Ln atom and the surrounding ligands. We demonstrated that Ho[Pt(SAc)4]2 and Tb[Pt(SAc)4]2 can be adsorbed on crystalline silver and graphite surfaces by electrospray deposition. Their orientation on the surfaces was determined by combining scanning tunneling microscopy and X-ray linear dichroism, and their magnetic moments were measured using X-ray magnetic circular dichroism. Finally, it was inferred that the molecules exhibit distinct magnetic anisotropies, and we studied the influence of the nonmetallic HOPG and the metallic Ag substrates, respectively. It is demonstrated that the Pt(SAc)4 ligands efficiently reduce the interaction of the lanthanide atom with both surfaces, allowing the retention, to some extent, of the magnetic properties of the magnetic center. This can be vital when integrating magnetic molecules in future quantum-based technologies.
{"title":"Magnetism of High-Symmetry Lanthanide Molecular Complexes with Metalloligands Directing Orientational Attachment to Ag and HOPG Surfaces","authors":"Francesco Zamboni,Niéli Daffé,Jan Dreiser,Jesper Bendix,Lars Diekhöner","doi":"10.1021/acs.jpcc.5c04614","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04614","url":null,"abstract":"Lanthanide complexes Ln[Pt(SAc)4]2 are single-ion magnetic molecules that have recently been shown to exhibit interesting bulk magnetic properties that can be tuned by varying the central Ln atom and the surrounding ligands. We demonstrated that Ho[Pt(SAc)4]2 and Tb[Pt(SAc)4]2 can be adsorbed on crystalline silver and graphite surfaces by electrospray deposition. Their orientation on the surfaces was determined by combining scanning tunneling microscopy and X-ray linear dichroism, and their magnetic moments were measured using X-ray magnetic circular dichroism. Finally, it was inferred that the molecules exhibit distinct magnetic anisotropies, and we studied the influence of the nonmetallic HOPG and the metallic Ag substrates, respectively. It is demonstrated that the Pt(SAc)4 ligands efficiently reduce the interaction of the lanthanide atom with both surfaces, allowing the retention, to some extent, of the magnetic properties of the magnetic center. This can be vital when integrating magnetic molecules in future quantum-based technologies.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"41 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111093","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 : 2026-02-04DOI: 10.1021/acs.jpcc.5c05574
Samuel Struzek,Birger Holtermann,Shweta Sharma,Florian Maurer,Jelena Jelic,Anna Zimina,Felix Studt,Yolita M. Eggeler,Jan-Dierk Grunwaldt
Pt through the gas phase in the form of volatile PtO2 has become a topic of interest within recent years due to its application in the production of single atom catalysts. It is furthermore important for oxidation reactions that take place at high temperatures, e.g., CH4 oxidation in order to track noble metal loss. Here, platinum migration is observed on the nanometer scale for mixed Pt/Al2O3 and CeO2 nanoparticles as grinded powders. Furthermore, Pt migration within a reactor in a dual bed of Pt/Al2O3 followed by a bed of sieved CeO2 particles is tracked in situ on the millimeter scale via time and spatially resolved X-ray absorption spectroscopy. It is observed that gaseous PtO2 is first captured at the beginning of the CeO2 bed. When the beginning of the bed appears saturated, PtO2 adsorbs further downstream. Such adsorption behavior has to our knowledge not yet been reported in the literature since it requires time and spatially resolved in situ tracking. Furthermore, preferential adsorption sites of Pt on CeO2 were identified using experimental extended X-ray absorption fine structure data and fitting based on models from Density Functional Theory calculations. They point to geometries as, for example, found in 4-fold hollow sites on CeO2 (110) with additional ligands for stabilization.
{"title":"In Situ Tracking of Pt Migration from Pt/Al2O3 to CeO2 on the Atomic and Reactor Scale","authors":"Samuel Struzek,Birger Holtermann,Shweta Sharma,Florian Maurer,Jelena Jelic,Anna Zimina,Felix Studt,Yolita M. Eggeler,Jan-Dierk Grunwaldt","doi":"10.1021/acs.jpcc.5c05574","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05574","url":null,"abstract":"Pt through the gas phase in the form of volatile PtO2 has become a topic of interest within recent years due to its application in the production of single atom catalysts. It is furthermore important for oxidation reactions that take place at high temperatures, e.g., CH4 oxidation in order to track noble metal loss. Here, platinum migration is observed on the nanometer scale for mixed Pt/Al2O3 and CeO2 nanoparticles as grinded powders. Furthermore, Pt migration within a reactor in a dual bed of Pt/Al2O3 followed by a bed of sieved CeO2 particles is tracked in situ on the millimeter scale via time and spatially resolved X-ray absorption spectroscopy. It is observed that gaseous PtO2 is first captured at the beginning of the CeO2 bed. When the beginning of the bed appears saturated, PtO2 adsorbs further downstream. Such adsorption behavior has to our knowledge not yet been reported in the literature since it requires time and spatially resolved in situ tracking. Furthermore, preferential adsorption sites of Pt on CeO2 were identified using experimental extended X-ray absorption fine structure data and fitting based on models from Density Functional Theory calculations. They point to geometries as, for example, found in 4-fold hollow sites on CeO2 (110) with additional ligands for stabilization.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111250","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 : 2026-02-04DOI: 10.1021/acs.jpcc.6c00339
Xiao Jiang, Xu Cheng, Zhanqi Liu, Liyun Ding, Weihua Han
In our original article, we neglected to cite the following reference that discusses the physics of hole polarons in BiVO4: Hao, Z.; Liu, T. Quasi-Large Hole Polarons in BiVO4: Implications for Photocatalysis and Solar Energy Conversion. arXiv; 2025. 10.48550/arXiv.2502.10622. This article has not yet been cited by other publications.
{"title":"Correction to “First-Principles Study of Polarons in Multiple Crystal Phases of Bismuth Vanadate”","authors":"Xiao Jiang, Xu Cheng, Zhanqi Liu, Liyun Ding, Weihua Han","doi":"10.1021/acs.jpcc.6c00339","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00339","url":null,"abstract":"In our original article, we neglected to cite the following reference that discusses the physics of hole polarons in BiVO<sub>4</sub>: Hao, Z.; Liu, T. Quasi-Large Hole Polarons in BiVO<sub>4</sub>: Implications for Photocatalysis and Solar Energy Conversion. <i>arXiv</i>; 2025. 10.48550/arXiv.2502.10622. This article has not yet been cited by other publications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"83 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122424","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 : 2026-02-04DOI: 10.1021/acs.jpcc.5c08421
Gookyeong Jeong,Abraham Colin-Molina,C. Daniel Frisbie
We investigate the effects of protonation on conductances G in molecular tunnel junctions based on self-assembled monolayers (SAMs). Here, we compare two different molecules where bipyridine dimethanethiols (BPMD2) have protonatable nitrogen atoms, and oligophenylene dimethanethiols (OPMD2) do not. By treating with HBF4 acid, BPMD2 SAMs are partially protonated (∼66% monoprotonation), while OPMD2 remains unchanged, confirmed by X-ray photoelectron spectroscopy and reflection–absorption infrared spectroscopy. Conducting probe atomic force microscopy (CP-AFM) with Au or Pt coated tips is employed to form soft contacts with these SAMs on Au or Pt substrates. We observe that protonation of BPMD2 reduces G by approximately 1 order of magnitude, while OPMD2 showed essentially no change in G. To further understand the cause of the G decrease, we use an off-resonance single-level model (orSLM) analysis and extract the density of states parameters from the experimental current–voltage (I–V) characteristics. This analysis reveals that protonation shifts up the HOMO-Fermi level offset εh by ∼0.2 eV in BPMD2, as might be expected. However, protonation also induces a significant decrease in the metal-orbital coupling Γ, leading to an overall reduction in G. In contrast, OPMD2 junctions exhibit negligible changes in G, εh, and Γ upon treatment with HBF4. Ultraviolet photoelectron spectroscopy (UPS) not only confirms the εh shift for BPMD2 but also reveals an increase in Au/SAM work function Φ by 0.4 eV after protonation. This is consistent with the formation of an interface dipole upon protonation of BPMD2. While further studies are needed for understanding the specific role of the counterions, the collective results show that protonation of SAMs with basic sites can tune both εh and Γ, and they demonstrate the applicability of the orSLM for quantitative analysis of chemically doped molecular tunnel junctions.
{"title":"Protonation-Induced Modulation of HOMO-Fermi Level Offset and Metal-Orbital Coupling in N-Containing Aromatic Self-Assembled Monolayer Tunnel Junctions","authors":"Gookyeong Jeong,Abraham Colin-Molina,C. Daniel Frisbie","doi":"10.1021/acs.jpcc.5c08421","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08421","url":null,"abstract":"We investigate the effects of protonation on conductances G in molecular tunnel junctions based on self-assembled monolayers (SAMs). Here, we compare two different molecules where bipyridine dimethanethiols (BPMD2) have protonatable nitrogen atoms, and oligophenylene dimethanethiols (OPMD2) do not. By treating with HBF4 acid, BPMD2 SAMs are partially protonated (∼66% monoprotonation), while OPMD2 remains unchanged, confirmed by X-ray photoelectron spectroscopy and reflection–absorption infrared spectroscopy. Conducting probe atomic force microscopy (CP-AFM) with Au or Pt coated tips is employed to form soft contacts with these SAMs on Au or Pt substrates. We observe that protonation of BPMD2 reduces G by approximately 1 order of magnitude, while OPMD2 showed essentially no change in G. To further understand the cause of the G decrease, we use an off-resonance single-level model (orSLM) analysis and extract the density of states parameters from the experimental current–voltage (I–V) characteristics. This analysis reveals that protonation shifts up the HOMO-Fermi level offset εh by ∼0.2 eV in BPMD2, as might be expected. However, protonation also induces a significant decrease in the metal-orbital coupling Γ, leading to an overall reduction in G. In contrast, OPMD2 junctions exhibit negligible changes in G, εh, and Γ upon treatment with HBF4. Ultraviolet photoelectron spectroscopy (UPS) not only confirms the εh shift for BPMD2 but also reveals an increase in Au/SAM work function Φ by 0.4 eV after protonation. This is consistent with the formation of an interface dipole upon protonation of BPMD2. While further studies are needed for understanding the specific role of the counterions, the collective results show that protonation of SAMs with basic sites can tune both εh and Γ, and they demonstrate the applicability of the orSLM for quantitative analysis of chemically doped molecular tunnel junctions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"68 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111092","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}
The structure of glasses in the aluminoborophosphate glass system with compositions 40Na2O–40P2O5–(20–x)Al2O3–xB2O3 (0 ≤ x ≤ 20) has been studied by single- and double-resonance solid-state nuclear magnetic resonance (NMR) spectroscopy. The principal network forming units (NFUs) were identified and quantified by high-resolution spectra obtained by magic-angle spinning (MAS) NMR. The boron atoms are predominantly four-coordinated, while the Al species occur in four-, five- and six-fold coordination, and their average connectivity increases with increasing boron content. The connectivities between these NFUs were determined by dipolar recoupling experiments such as 11B{31P} and 27Al{31P} rotational echo double resonance (REDOR) and 31P double-quantum filtering experiments. No significant 27Al–11B interaction was detectable. The results indicate a strong preference for Al–O–P and B–O–P heteroatomic connectivities, whereas a random linkage model clearly does not provide an appropriate description. The glass transition temperature shows a characteristic nonlinear compositional dependence on x, with a maximum near x = 10. This behavior can be modeled by considering the average connectivity density of the network, calculated from the NFU distribution as deduced from the quantitative connectivity analysis. 23Na MAS NMR and 23Na{31P} REDOR results indicate that the sodium ions maintain a constant local environment dominated by the phosphate species, explainable by standard bond-valence concepts.
{"title":"Short- and Medium-Range Order of Sodium Aluminoborophosphate Glasses Studied by Dipolar NMR Spectroscopy","authors":"Mojtaba Abbasi,Henrik Bradtmüller,Hellmut Eckert,Scott Kroeker","doi":"10.1021/acs.jpcc.5c07375","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07375","url":null,"abstract":"The structure of glasses in the aluminoborophosphate glass system with compositions 40Na2O–40P2O5–(20–x)Al2O3–xB2O3 (0 ≤ x ≤ 20) has been studied by single- and double-resonance solid-state nuclear magnetic resonance (NMR) spectroscopy. The principal network forming units (NFUs) were identified and quantified by high-resolution spectra obtained by magic-angle spinning (MAS) NMR. The boron atoms are predominantly four-coordinated, while the Al species occur in four-, five- and six-fold coordination, and their average connectivity increases with increasing boron content. The connectivities between these NFUs were determined by dipolar recoupling experiments such as 11B{31P} and 27Al{31P} rotational echo double resonance (REDOR) and 31P double-quantum filtering experiments. No significant 27Al–11B interaction was detectable. The results indicate a strong preference for Al–O–P and B–O–P heteroatomic connectivities, whereas a random linkage model clearly does not provide an appropriate description. The glass transition temperature shows a characteristic nonlinear compositional dependence on x, with a maximum near x = 10. This behavior can be modeled by considering the average connectivity density of the network, calculated from the NFU distribution as deduced from the quantitative connectivity analysis. 23Na MAS NMR and 23Na{31P} REDOR results indicate that the sodium ions maintain a constant local environment dominated by the phosphate species, explainable by standard bond-valence concepts.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"8 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111094","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}
Forming two-dimensional (2D) alloys provides a unique way to tune the structural parameter and the electronic structure of a material in comparison to their pure counterparts. By taking motivation from this fact, we are presenting a detailed analysis based on first-principles density functional theory calculation for 2D BY1–xZx (Y, Z = P, As, and Sb, but Y ≠ Z) alloys. From a synthesis point of view, it would be interesting to predict (a) How the structural parameters and electronic structure of BY1–xZx alloys are going to change with doping concentration (x)? (b) How will x affect the thermodynamical stability of alloys? and (c) What are the growth temperatures of these alloys? Our calculations reveal that an increase in x decreases the lattice constant of BY1–xZx alloys, which is in accordance with Vegard’s law. Electronic structure calculations predict a direct band gap for pristine BP, BAs, and BSb at high symmetry point K, equal to 1.35, 1.18, and 0.60 eV, respectively. We notice that for BY1–xZx alloys, the band gap remains direct and shows bowing at x = 0.33. There is a sharp fluctuation in edge valence bands during the band alignment of alloys (maximum for BSb1–xAsx, ∼1 eV). However, the edge conduction bands show a relatively small fluctuation, which is the lowest for BAs1–xPx alloys (∼0.02 eV) on increasing x. The absorption coefficient of BY1–xZx alloys as a function of x shifts the peak toward blue. Further, BAs1–xPx alloys exhibit positive enthalpy of mixing and thus can grow by obeying an endothermic reaction. However, BSb1–xPx and BSb1–xAsx alloys, with negative mixing enthalpies, can be grown by an exothermic reaction. The binodal and spinodal decomposition curves predict the growth temperature of BAs1–xPx, BSb1–xPx, and BSb1–xAsx alloys to be −208, 3082, and 1801 K, respectively.
{"title":"First-Principles Insights in Designing Two-Dimensional BY1–xZx (Y, Z = P, As, and Sb, but Y ≠ Z) Alloys: A Potential Candidate for Thin-Film Optoelectronic Devices","authors":"Durgesh Kumar Sharma,Pawan Kumar,Rajeev Ahuja,Sudhir Kumar","doi":"10.1021/acs.jpcc.5c07234","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c07234","url":null,"abstract":"Forming two-dimensional (2D) alloys provides a unique way to tune the structural parameter and the electronic structure of a material in comparison to their pure counterparts. By taking motivation from this fact, we are presenting a detailed analysis based on first-principles density functional theory calculation for 2D BY1–xZx (Y, Z = P, As, and Sb, but Y ≠ Z) alloys. From a synthesis point of view, it would be interesting to predict (a) How the structural parameters and electronic structure of BY1–xZx alloys are going to change with doping concentration (x)? (b) How will x affect the thermodynamical stability of alloys? and (c) What are the growth temperatures of these alloys? Our calculations reveal that an increase in x decreases the lattice constant of BY1–xZx alloys, which is in accordance with Vegard’s law. Electronic structure calculations predict a direct band gap for pristine BP, BAs, and BSb at high symmetry point K, equal to 1.35, 1.18, and 0.60 eV, respectively. We notice that for BY1–xZx alloys, the band gap remains direct and shows bowing at x = 0.33. There is a sharp fluctuation in edge valence bands during the band alignment of alloys (maximum for BSb1–xAsx, ∼1 eV). However, the edge conduction bands show a relatively small fluctuation, which is the lowest for BAs1–xPx alloys (∼0.02 eV) on increasing x. The absorption coefficient of BY1–xZx alloys as a function of x shifts the peak toward blue. Further, BAs1–xPx alloys exhibit positive enthalpy of mixing and thus can grow by obeying an endothermic reaction. However, BSb1–xPx and BSb1–xAsx alloys, with negative mixing enthalpies, can be grown by an exothermic reaction. The binodal and spinodal decomposition curves predict the growth temperature of BAs1–xPx, BSb1–xPx, and BSb1–xAsx alloys to be −208, 3082, and 1801 K, respectively.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"75 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111096","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 : 2026-02-04DOI: 10.1021/acs.jpcc.5c06893
Michael T. Tang,Michal Bajdich,Frank Abild-Pedersen
Driving electrochemical reactions with a bias in an aqueous environment is an attractive approach for sustainable chemical synthesis, but understanding reaction dynamics remains a serious challenge in electrocatalysis. Computational techniques and concepts are necessary to elucidate the underpinnings of creating catalytic sites that are highly active, selective, and stable. Herein, we elucidate the intrusive role of hydroxide ions in the running of electrochemical reactions under alkaline conditions. Through an overhaul of the computational hydrogen electrode (CHE) model, we show that hydroxide ions can adsorb on many late transition metals, even on metals like Cu and Pt, where the OH* binding energy is energetically uphill relative to H2O (l). We provide a computational framework for modeling reaction energetics with OH–* relative to OH–(aq), using HER and CO2R as examples of how to model electroreduction reactions under alkaline conditions.
{"title":"Revamped Electrode Models for Driving Electrochemical Reactions under Alkaline Conditions","authors":"Michael T. Tang,Michal Bajdich,Frank Abild-Pedersen","doi":"10.1021/acs.jpcc.5c06893","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c06893","url":null,"abstract":"Driving electrochemical reactions with a bias in an aqueous environment is an attractive approach for sustainable chemical synthesis, but understanding reaction dynamics remains a serious challenge in electrocatalysis. Computational techniques and concepts are necessary to elucidate the underpinnings of creating catalytic sites that are highly active, selective, and stable. Herein, we elucidate the intrusive role of hydroxide ions in the running of electrochemical reactions under alkaline conditions. Through an overhaul of the computational hydrogen electrode (CHE) model, we show that hydroxide ions can adsorb on many late transition metals, even on metals like Cu and Pt, where the OH* binding energy is energetically uphill relative to H2O (l). We provide a computational framework for modeling reaction energetics with OH–* relative to OH–(aq), using HER and CO2R as examples of how to model electroreduction reactions under alkaline conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"17 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111095","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 : 2026-02-04DOI: 10.1021/acs.jpcc.5c08042
In Jun Park,Kamal Choudhary
As semiconductor technologies continue to scale to the nanoscale, the efficient prediction of material properties becomes increasingly critical. The tight-binding (TB) method is a widely used semiempirical approach that offers a computationally tractable alternative to Density Functional Theory (DFT) for large-scale electronic structure calculations. However, conventional TB models often suffer from limited transferability and lack standardized benchmarking protocols. In this study, we introduce a computational framework (CHIPS-TB) for evaluating and comparing tight-binding parametrizations across diverse material systems relevant to semiconductor design, focusing on properties such as electronic bandgaps, band structures, and bulk modulus. We assess model parametrizations including Density Functional Tight-Binding (DFTB)-based MatSci, PBC, PTBP, SlaKoNet, and TB3PY against OptB88vdW, TBmBJ-DFT, and experimental reference data from the JARVIS-DFT database for 50+ materials pertinent to semiconductor applications. The CHIPS-TB code will be made publicly available on GitHub, and benchmarks will be available on JARVIS-Leaderboard.
{"title":"CHIPS-TB: Evaluating Tight-Binding Models for Metals, Semiconductors, and Insulators","authors":"In Jun Park,Kamal Choudhary","doi":"10.1021/acs.jpcc.5c08042","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08042","url":null,"abstract":"As semiconductor technologies continue to scale to the nanoscale, the efficient prediction of material properties becomes increasingly critical. The tight-binding (TB) method is a widely used semiempirical approach that offers a computationally tractable alternative to Density Functional Theory (DFT) for large-scale electronic structure calculations. However, conventional TB models often suffer from limited transferability and lack standardized benchmarking protocols. In this study, we introduce a computational framework (CHIPS-TB) for evaluating and comparing tight-binding parametrizations across diverse material systems relevant to semiconductor design, focusing on properties such as electronic bandgaps, band structures, and bulk modulus. We assess model parametrizations including Density Functional Tight-Binding (DFTB)-based MatSci, PBC, PTBP, SlaKoNet, and TB3PY against OptB88vdW, TBmBJ-DFT, and experimental reference data from the JARVIS-DFT database for 50+ materials pertinent to semiconductor applications. The CHIPS-TB code will be made publicly available on GitHub, and benchmarks will be available on JARVIS-Leaderboard.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"88 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111280","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 : 2026-02-04DOI: 10.1021/acs.jpcc.6c00179
Yuqi Wu, Jinlu He
Experiments reveal that the steric hindrance of A-site cations significantly affects carrier dynamics in two-dimensional (2D) perovskites. However, these cations simultaneously introduce hydrogen bonding and steric hindrance. Thus, it is essential to decouple these dual effects to understand their respective impacts on carrier dynamics. In this study, we systematically investigate the role of steric hindrance on carrier dynamics through nonadiabatic molecular dynamics simulations in (C8H12N)2PbI4 (S-MBA2PbI4) and (C8H18N)2PbI4 (S-CHEA2PbI4) perovskites. Our results show that while S-MBA and S-CHEA exhibit nearly identical hydrogen bonding strength, they display different steric hindrance. Enhancing the steric hindrance of A-site cations suppresses atomic motion and weakens nonadiabatic coupling, resulting in prolonged hot carrier relaxation and charge recombination times. This study provides critical theoretical insights into how steric hindrance modulates charge carrier dynamics in 2D perovskites. These findings offer valuable guidelines for designing high-performance solar cells and other optoelectronic devices by strategically controlling the molecular steric properties.
{"title":"Steric Hindrance Enhancement Prolongs Charge Carrier Lifetimes in Two-Dimensional Ruddlesden–Popper Perovskites","authors":"Yuqi Wu, Jinlu He","doi":"10.1021/acs.jpcc.6c00179","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c00179","url":null,"abstract":"Experiments reveal that the steric hindrance of A-site cations significantly affects carrier dynamics in two-dimensional (2D) perovskites. However, these cations simultaneously introduce hydrogen bonding and steric hindrance. Thus, it is essential to decouple these dual effects to understand their respective impacts on carrier dynamics. In this study, we systematically investigate the role of steric hindrance on carrier dynamics through nonadiabatic molecular dynamics simulations in (C<sub>8</sub>H<sub>12</sub>N)<sub>2</sub>PbI<sub>4</sub> (<i>S</i>-MBA<sub>2</sub>PbI<sub>4</sub>) and (C<sub>8</sub>H<sub>18</sub>N)<sub>2</sub>PbI<sub>4</sub> (<i>S</i>-CHEA<sub>2</sub>PbI<sub>4</sub>) perovskites. Our results show that while <i>S</i>-MBA and <i>S</i>-CHEA exhibit nearly identical hydrogen bonding strength, they display different steric hindrance. Enhancing the steric hindrance of A-site cations suppresses atomic motion and weakens nonadiabatic coupling, resulting in prolonged hot carrier relaxation and charge recombination times. This study provides critical theoretical insights into how steric hindrance modulates charge carrier dynamics in 2D perovskites. These findings offer valuable guidelines for designing high-performance solar cells and other optoelectronic devices by strategically controlling the molecular steric properties.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"302 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122396","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}
Hydrogen peroxide (H2O2) is an environmentally benign yet versatile oxidizing agent with broad applications across academic and industrial fields, including sterilization, sewage treatment and chemical synthesis. The electrochemical two-electron water oxidation (2e- WOR) pathway as an effective method for in situ electrosynthesis of H2O2, is not only environmentally friendly and economical, but also can be combined with appropriate reduction reactions to achieve the large-scale synthesis of high-value-added chemicals. This paper reports the preparation of three different boron-doped diamond (BDD) electrodes by hot filament chemical vapor deposition (HFCVD) on titanium (Ti) plate/multilayer network Ti woven mesh substrates. The multilayer network BDD electrodes (MN-BDD15 and MN-BDD9) exhibited significantly larger electrochemically active surface areas than the flat plate BDD electrode (BDD9), measuring 28.00 and 16.70 times that of BDD9, respectively. Correspondingly, the electron transfer resistances (Rct) for BDD9, MN-BDD9 and MN-BDD15 were determined to be 57.90, 0.79, and 0.54 Ω, respectively. Notably, the MN-BDD15 electrode demonstrated superior performance, achieving a Faradaic efficiency (FE) of 25.70% at a current density of 20 mA cm–2. Further analysis confirmed that both hydroxyl radical (•OH) production and mass transfer efficiency was dramatically enhanced in MN-BDD15 compared to BDD9. Under identical conditions, the H2O2 yield of MN-BDD15 was 15.00 times higher than that of the BDD9, proving that the multilayer network BDD is a promising high-performance electrode material for efficient electrocatalytic oxidation synthesis of H2O2.
过氧化氢（H2O2）是一种环境友好的多功能氧化剂，在学术和工业领域有着广泛的应用，包括杀菌、污水处理和化学合成。电化学双电子水氧化（2e- WOR）途径作为原位电合成H2O2的有效方法，不仅环保经济，而且可以结合适当的还原反应实现高附加值化学品的大规模合成。采用热丝化学气相沉积（HFCVD）技术在钛（Ti）板/多层网状Ti编织网衬底上制备了三种不同掺硼金刚石（BDD）电极。多层网状BDD电极（MN-BDD15和MN-BDD9）的电化学活性表面积明显大于平板BDD电极（BDD9），分别为BDD9的28.00和16.70倍。相应的，BDD9、MN-BDD9和MN-BDD15的电子转移电阻（Rct）分别为57.90、0.79和0.54 Ω。值得注意的是，MN-BDD15电极表现出优异的性能，在电流密度为20 mA cm-2时，其法拉第效率（FE）达到25.70%。进一步的分析证实，MN-BDD15与BDD9相比，羟基自由基（•OH）的产生和传质效率都得到了显著提高。在相同条件下，MN-BDD15的H2O2产率比BDD9高15.00倍，证明多层网状BDD是一种很有前途的高效电催化氧化合成H2O2的高性能电极材料。
{"title":"Enhanced H2O2 Generation via Two-Electron Water Oxidation on Multilayer Network BDD: Performance and Mechanistic Insights","authors":"Dongtao Lei, Wanlin Yang, Menglin Zhang, Hongxia Chen, Bing Wang, Jian Wang, Wen Zhang, Ying Xiong","doi":"10.1021/acs.jpcc.5c08748","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08748","url":null,"abstract":"Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) is an environmentally benign yet versatile oxidizing agent with broad applications across academic and industrial fields, including sterilization, sewage treatment and chemical synthesis. The electrochemical two-electron water oxidation (2e<sup>-</sup> WOR) pathway as an effective method for in situ electrosynthesis of H<sub>2</sub>O<sub>2</sub>, is not only environmentally friendly and economical, but also can be combined with appropriate reduction reactions to achieve the large-scale synthesis of high-value-added chemicals. This paper reports the preparation of three different boron-doped diamond (BDD) electrodes by hot filament chemical vapor deposition (HFCVD) on titanium (Ti) plate/multilayer network Ti woven mesh substrates. The multilayer network BDD electrodes (MN-BDD<sub>15</sub> and MN-BDD<sub>9</sub>) exhibited significantly larger electrochemically active surface areas than the flat plate BDD electrode (BDD<sub>9</sub>), measuring 28.00 and 16.70 times that of BDD<sub>9</sub>, respectively. Correspondingly, the electron transfer resistances (<i>R</i><sub>ct</sub>) for BDD<sub>9</sub>, MN-BDD<sub>9</sub> and MN-BDD<sub>15</sub> were determined to be 57.90, 0.79, and 0.54 Ω, respectively. Notably, the MN-BDD<sub>15</sub> electrode demonstrated superior performance, achieving a Faradaic efficiency (FE) of 25.70% at a current density of 20 mA cm<sup>–2</sup>. Further analysis confirmed that both hydroxyl radical (<sup>•</sup>OH) production and mass transfer efficiency was dramatically enhanced in MN-BDD<sub>15</sub> compared to BDD<sub>9</sub>. Under identical conditions, the H<sub>2</sub>O<sub>2</sub> yield of MN-BDD<sub>15</sub> was 15.00 times higher than that of the BDD<sub>9</sub>, proving that the multilayer network BDD is a promising high-performance electrode material for efficient electrocatalytic oxidation synthesis of H<sub>2</sub>O<sub>2</sub>.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"302 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122433","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：