Chemphyschem最新文献_第9页

A Hidden Chemical Assembly Mechanism: Reconstruction-by-Reconstruction Cycle Growth in HKUST-1 MOF Layer Synthesis.

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-06 DOI: 10.1002/cphc.202400968

T Koehler, J Schmeink, M Schleberger, F Marlow

引用次数: 0

Geometrical and Electronic Structure of Fluorinated and Non-Fluorinated Platinum(II) Tetraphenylporphyrin Complexes.

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-06 DOI: 10.1002/cphc.202400973

Ivan Yu Kurochkin, Nina I Giricheva, Valentina A Ol'shevskaya, Andrey V Zaitsev, Georgiy V Girichev, Norbert W Mitzel

{"title":"Geometrical and Electronic Structure of Fluorinated and Non-Fluorinated Platinum(II) Tetraphenylporphyrin Complexes.","authors":"Ivan Yu Kurochkin, Nina I Giricheva, Valentina A Ol'shevskaya, Andrey V Zaitsev, Georgiy V Girichev, Norbert W Mitzel","doi":"10.1002/cphc.202400973","DOIUrl":"10.1002/cphc.202400973","url":null,"abstract":"The composition of the saturated vapors of two platinum complexes with the macrocyclic ligands 5,10,15,20-tetraphenylporphyrin (PtTPP) and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (PtTF5PP) and their structures were determined by synchronous gas-phase electron diffraction/mass spectrometry (GED/MS). These porphyrin complexes are those with the heaviest metal atom in the coordination cavity that have been structurally investigated in the gas phase. The mass spectra confirm the presence of a single molecular form of each, PtTPP (T=629 K) and PtTF5PP (T=597 K). Their structures can serve as references for related complexes in the crystalline state or solutions. Differences between the geometries of PtTPP and PtTF5PP in the crystalline and gaseous states include a significant deformation of the tetrapyrrole macrocycle in solid PtTPP. The experimental Pt-N bond lengths of both complexes are in agreement with quantum chemical calculations (DFT/B97D/ECP(Pt)) taking into account relativistic effects. The effect of lanthanide contraction is evident from the similarity of the Pd-N and Pt-N internuclear distances of analogous compounds. The strong electron density transfer from the porphyrin backbone to the metal ion and the resulting low effective positive charge on the platinum atom, studied by NBO and QTAIM methods, helps to rationalize the high catalytic activity of such platinum compounds.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400973"},"PeriodicalIF":2.3,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254779","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}

引用次数: 0

Advances in CO2-assisted oxidative dehydrogenation of light alkanes to light alkenes

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-06 DOI: 10.1002/cphc.202401073

Dr. Siran Zhang, Dr. Chongchong Wu, Dr. Jing Xin, Guoming Yang, Dr. Yongheng Li, Dr. Mengjun Su, Haihong Zhang, Dr. Huiling Zhang, Lianying Wang

{"title":"Advances in CO2-assisted oxidative dehydrogenation of light alkanes to light alkenes","authors":"Dr. Siran Zhang, Dr. Chongchong Wu, Dr. Jing Xin, Guoming Yang, Dr. Yongheng Li, Dr. Mengjun Su, Haihong Zhang, Dr. Huiling Zhang, Lianying Wang","doi":"10.1002/cphc.202401073","DOIUrl":"10.1002/cphc.202401073","url":null,"abstract":"The CO2-assisted oxidative dehydrogenation (ODH) of light alkanes offers a promising route for converting underutilized resources into valuable chemical feedstocks while addressing environmental challenges associated with CO2 emissions. CO2 plays a dual role in ODH by acting as a mild oxidant that enhances product selectivity and catalyst stability while preventing carbon deposition through the Reverse Water-Gas Shift (RWGS) and Boudouard reactions. The review has elucidated a variety of catalyst design and optimization strategies that may guide the future development of novel CO2-assisted ODH catalysts with improved alkane conversion, superior alkene selectivity, and long-term stability. It provides a comprehensive analysis of the structural characteristics, catalytic performances, and reaction mechanisms of typical catalysts, including transition metal catalysts (e. g., Cr-based, Co-based, V-based), metal oxide catalysts (e. g., Ga-based, In-based), noble metal catalysts (e. g., Pt-based, Ru-based), and bimetallic catalysts. Special attention is given to the structure-performance relationship of these catalysts, emphasizing how changes in promoters, supports, and morphology affect critical properties such as redox behavior, acidity-basicity balance, dispersion of active components, and catalyst-support interactions. Finally, future research directions and perspectives for the CO2-assisted ODH of ethane and propane are proposed, with a focus on advancing catalyst design and optimization strategies. This review aims to serve as a comprehensive reference for researchers exploring the potential of CO2-assisted ODH in promoting sustainable production of light alkenes.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363995","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}

引用次数: 0

Microkinetic Modelling of Electrochemical Oxygen Evolution Reaction on Ir(111)@N-Graphene Surface

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-05 DOI: 10.1002/cphc.202400907

Adyasa Priyadarsini, Bhabani S. Mallik

{"title":"Microkinetic Modelling of Electrochemical Oxygen Evolution Reaction on Ir(111)@N-Graphene Surface","authors":"Adyasa Priyadarsini, Bhabani S. Mallik","doi":"10.1002/cphc.202400907","DOIUrl":"10.1002/cphc.202400907","url":null,"abstract":"We have explored the thermodynamics and microkinetic aspects of oxygen evolution catalysis on low loading of Ir(111) on nitrogen-doped graphene at constant potential. The electronic modification induced by N-doping is the reason for the reduced overpotential of OER. The N-induced defect in the charge density is observed with increasing charge-depleted region around the Ir atoms. The lattice contraction shifts the d-band center away from the Fermi level, which increases the barrier for OH* and O* formation on Ir(111) supported on NGr (Ir(111)@NGr). Thus, highly endothermic O* formation reduces the OOH* formation, which is the potential determining step. For comparison, all electronic and binding energy calculations were also performed against Ir NP supported on Gr (Ir(111)@Gr). The stepwise potential-dependent activation barrier (<math></math>\u0000) was obtained using the charge extrapolation method. The third step remains the RDS in all ranges of water oxidation potentials. The potential dependent <math></math>\u0000 is further applied to the Eyring rate equation to obtain the current density (<math></math>\u0000) and correlation between <math></math>\u0000 and pH dependence, i. e., OH− concentration. The microkinetic <math></math>\u0000 progression leads to a Tafel slope value of 30 mV dec−1 at pH=14.0, requiring <math></math>\u0000.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254782","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}

引用次数: 0

A First Principle Study to Understand the Importance of Edge-exposed and Basal Plane Defective MoS₂ Towards Nitrogen Reduction Reaction.

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-05 DOI: 10.1002/cphc.202400866

Yuan-Hui Xiao, Xin-Wei Wu, Lai-Ke Chen, Zi-Wei Ma, Jian-De Lin, Rajkumar Devasenathipathy, De-Yin Wu, Zhong-Qun Tian

{"title":"A First Principle Study to Understand the Importance of Edge-exposed and Basal Plane Defective MoS2 Towards Nitrogen Reduction Reaction.","authors":"Yuan-Hui Xiao, Xin-Wei Wu, Lai-Ke Chen, Zi-Wei Ma, Jian-De Lin, Rajkumar Devasenathipathy, De-Yin Wu, Zhong-Qun Tian","doi":"10.1002/cphc.202400866","DOIUrl":"10.1002/cphc.202400866","url":null,"abstract":"Nitrogen reduction reaction (NRR) as a promising approach to ammonia synthesis has received much attention in recent years. Molybdenum disulfides (MoS2), as one of the most potential candidates for NRR, are extensively investigated. However, the inert basal plane limits the application of MoS2. Herein, by using density functional theory (DFT) calculations, we constructed edge-exposed MoS2 and different kinds of basal plane defects, including anti-site, sulfur vacancy and pore defects, to systematically investigate their influence on the NRR performance. The thermodynamically calculated results revealed that the NRR on edge-exposed MoS2, anti-site defects, sulfur vacancy with three sulfur atoms missing (S3V) and porous defect (D) exhibit great catalytic activity with low limiting potentials. The calculated limiting potentials are -0.43 and -0.47 V at armchair and zigzag edge MoS2, -0.42 and -0.44 V at anti-site defects, -0.49 and -0.67 V at S3V and D. However, by inspecting the thermodynamic properties of the hydrogen evolution reaction, we proposed that the zigzag-end MoS2 and anti-site defects exhibit a better NRR selectivity compared to armchair-end MoS2, S3V and D. Electronic structure calculations reveals that the edge-exposed and basal plane defective MoS2 can improve the conductivity of the material by reducing the band gap. Donation-backdonation mechanism can effectively promote the activation of nitrogen molecule. Our results pave the way to understanding the defective effects of the MoS2 inertness plane for NRR and designing high-performance NRR catalysts.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400866"},"PeriodicalIF":2.3,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143254776","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}

引用次数: 0

Insight into the Coupling of HgS and CuO with Metal-Organic Frameworks Support in Electrocatalytic Oxygen Evolution Reaction

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-05 DOI: 10.1002/cphc.202400956

Mitali Hupele, Ritu Raj, Shikha Rai, Tapasi Sen, Krishna Kanta Haldar

{"title":"Insight into the Coupling of HgS and CuO with Metal-Organic Frameworks Support in Electrocatalytic Oxygen Evolution Reaction","authors":"Mitali Hupele, Ritu Raj, Shikha Rai, Tapasi Sen, Krishna Kanta Haldar","doi":"10.1002/cphc.202400956","DOIUrl":"10.1002/cphc.202400956","url":null,"abstract":"This study investigates the coupling of mercury sulfide (HgS) and copper oxide (CuO) nanoparticles with metal-organic frameworks (MOFs) as a support material for enhancing the electrocatalytic oxygen evolution reaction (OER). The integration of HgS and CuO into the MOF framework aims to leverage the unique electronic and structural properties of both the nanoparticles and the MOFs to improve catalytic performance. Metal-organic frameworks (MOFs), particularly ZIF-67, are investigated for their potential to catalyze water-splitting reactions due to their high porosity and large specific surface areas. The strategic incorporation of HgS and CuO into ZIF-67 significantly enhances its electrocatalytic properties, resulting in remarkable performance metrics: a low overpotential of 246 mV at 10 mA/cm2, a Tafel slope of 123 mV/dec, an expanded electrochemical active surface area (ECSA) of 23.56 cm2, and a reduced charge transfer resistance of 34.86 Ω. This integration enhances porosity and increases active surface area, which is crucial for improved catalytic performance. This investigation introduces an innovative methodology for fabricating highly efficient electrocatalysts, positioning HgS/CuO/ZIF-67 as a promising candidate for oxygen evolution reactions in alkaline media. The findings highlight the potential of this novel nanocomposite in future clean energy applications, particularly in the realm of water-splitting technologies.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143188275","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}

引用次数: 0

Mechanistic Insights into the Photocatalytic Indigo Carmine Dye Decolorization by Co3O4/TiO2

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-04 DOI: 10.1002/cphc.202400688

Mirjam E. de Graaf, Nejc Godec, Bram T. Kappé, Roos L. Grote, Dr. Jitte Flapper, Dr. Eline M. Hutter, Prof. Dr. Bert M. Weckhuysen

{"title":"Mechanistic Insights into the Photocatalytic Indigo Carmine Dye Decolorization by Co3O4/TiO2","authors":"Mirjam E. de Graaf, Nejc Godec, Bram T. Kappé, Roos L. Grote, Dr. Jitte Flapper, Dr. Eline M. Hutter, Prof. Dr. Bert M. Weckhuysen","doi":"10.1002/cphc.202400688","DOIUrl":"10.1002/cphc.202400688","url":null,"abstract":"TiO2 is widely studied as an efficient UV-light photocatalyst for organic compound degradation through reactive oxygen species (ROS) generation. TiO2 can be modified to show photocatalytic activity under visible light illumination by combining with visible-light absorbing metal oxides. Here, we investigated Co3O4/TiO2 composite materials as visible-light absorbing photocatalysts, with various weight loadings of Co3O4, for the decolorization of wastewater pollutant indigo carmine. Under green LED light, 1.4 wt% Co3O4/TiO2 showed the highest decolorization rate compared to other weight loadings and bare TiO2. While UV-Vis spectroscopy indicated that Co3O4/TiO2 composite materials and bare TiO2 cause similar dye decolorization behavior, NMR spectroscopy showed that after 24 h, reaction products were present in the reaction mixture for 1.4 wt% Co3O4/TiO2, while TiO2 showed no reaction products. The lack of photocatalytic activity of Co3O4/zeolite and other Co3O4/oxide composite materials suggests a synergistic effect between Co3O4 and TiO2, where a small amount of Co3O4 enables TiO2 to utilize visible light without compromising the surface area available for ROS creation. Lastly, we emphasize the need to be cautious when drawing conclusions regarding the dye degradation, since we showed that decolorization does not necessarily equate to full degradation, using a unique combination of UV-Vis and nuclear magnetic resonance spectroscopy.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202400688","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143188278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

2H,3H-Decafluoropentane Endorsed Localized High Concentration Electrolyte for Low-Temperature Lithium-Metal Batteries 2H,3H-decafluoropentane endorsed localized high concentration electrolyte for low temperature lithium-metal batteries（用于低温锂金属电池的局部高浓度电解质）。

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-04 DOI: 10.1002/cphc.202400920

Jie Wang, Yubin Liu, Haikuo Lei, Wenbin Sun, Xiaoyu Huang, Yanli Ruan

{"title":"2H,3H-Decafluoropentane Endorsed Localized High Concentration Electrolyte for Low-Temperature Lithium-Metal Batteries","authors":"Jie Wang, Yubin Liu, Haikuo Lei, Wenbin Sun, Xiaoyu Huang, Yanli Ruan","doi":"10.1002/cphc.202400920","DOIUrl":"10.1002/cphc.202400920","url":null,"abstract":"A lithium-metal battery's electrochemical performance is affected by the kinetics of desolvation and ion transport at low temperatures. Here, we propose a low-temperature lithium-metal battery electrolyte. 1,2-Dimethoxyethane (DME) is used as the solvent, 2H,3H-decafluoropentane (HFC) as the diluent, and a high concentration of lithium bis(fluorosulfonyl)imide (LiFSI) as the solute. The addition of HFC diluent increases the number of anions bound to lithium ions and decreases the number of solvents in the solvation structure, which is conducive to the desolvation process at low temperatures. In addition, the anion-dominated solvation structure is conducive to the formation of an inorganic rich solid electrolyte interface (SEI), which effectively enhances the compatibility of LHCE-HFC electrolyte with lithium metal. The LHCE-HFC achieves ultra-high coulombic efficiency of lithium metal anode in Li||Cu batteries (99.31 %) and Li||Li batteries (1080 h) that have strong fluorine content in the interface. The Li||LiFePO4 (LFP) cells provide a discharge-specific capacity of 92.1 mAh g−1 at 0.2 C at −20 °C and capacity retention of 89.6 % after 200 cycles.","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 8","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143188270","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}

引用次数: 0

Cover Feature: Multi-Layer Kesterite-Based Photocathodes for NH3 Photosynthesis from N2 Reduction Reaction (ChemPhysChem 3/2025)

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-04 DOI: 10.1002/cphc.202580302

Juliana Ferreira de Brito, Marina Medina, Hugo Leandro Sousa Santos, Mileny dos Santos Araujo, Marcos Antônio Santana Andrade Jr., Lucia Helena Mascaro

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Front Cover: Absorption and Excited-State Coherences of Cryogenically Cold Retinal Protonated Schiff Base in Vacuo (ChemPhysChem 3/2025)

IF 2.3 3区化学

Chemphyschem Pub Date : 2025-02-04 DOI: 10.1002/cphc.202580301

Nikolaj Klinkby, Anne P. Rasmussen, Anders G. S. Lauridsen, Prof. Lars H. Andersen

引用次数: 0