Chemphyschem最新文献

{"title":"Recent Progress of Round-the-Clock Photocatalytic System in Environmental and Energy Applications: A Review.","authors":"Bo Li, Xiao-Jing Liu, Hao-Wen Zhu, Hua-Peng Guan, Rui-Tang Guo","doi":"10.1002/cphc.202401144","DOIUrl":"10.1002/cphc.202401144","url":null,"abstract":"<p><p>The prevailing overdependence on fossil fuels contributes to energy supply instability and pronounced price volatility. The combustion of these fuels emits considerable greenhouse gases and pollutants, further deteriorating the climate and environment. In response, Round-the-Clock Photocatalytic Systems (RTCPs) have emerged as a viable technological solution, attracting significant research interest due to their convenience, sustainability, and environmental benefits etc. which act as \"photo-batteries\" facilitate catalytic processes in the absence of light, offering continuous operation. Given the considerable potential of RTCPs, a timely examination of recent advancements is essential to optimize efforts. This review delineates the fundamental mechanisms of RTCPs, explores innovative strategies and current developments, and addresses the challenges of scaling up production. It aims to provide new insights and serve as a foundational reference for future research on RTCPs.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401144"},"PeriodicalIF":2.3,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143398477","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}

{"title":"Two-Step Reduction Pathway of Copper(II) by Oleylamine for the Nucleation of Cu(0) Nanoparticles: A Joint Modelling and Experimental Study.","authors":"Maya Guillaumont, Stéphanie Halbert, Alexy P Freitas, Valérie Briois, Sophie Carenco, Hélène Gérard","doi":"10.1002/cphc.202401027","DOIUrl":"10.1002/cphc.202401027","url":null,"abstract":"<p><p>Oleylamine is widely used in the synthesis of colloidal nanoparticles, as a solvent, as a stabilizing agent, and sometimes as a reducing agent. For example, metallic nanoparticles are obtained through reduction when Ni(II) and Pd(II) precursors are used or through disproportionation in the case of Ni(I) or Co(I). A similar dichotomy is observed for Cu precursors, with an additional complexity due to the nature of the precursor salt. In the present article, we report a combined DFT evaluation of possible reduction paths for Cu(II) and Cu(I) reduction by oleylamine, including the competition with Cu(I) disproportionation, and X-ray Absorption Spectroscopy monitoring of the oxidation state of copper(II) acetylacetonate in oleylamine. We show that the reduction of copper(II) acetylacetonate goes through a two-steps process, with the intermediate formation of Cu(I) complexes. The role of phosphine ligands is demonstrated as well as the relevance of these findings in case alternative copper sources such as copper halogen salts.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401027"},"PeriodicalIF":2.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381721","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}

{"title":"Investigation of CoB/SBA-15 Catalyst for Efficient Hydrogen Generation via Sodium Borohydride Hydrolysis.","authors":"Hao Yu, Mukendi Archip Tshimanga, Tshimanga Landry Wa Tshimanga, Meng Gao","doi":"10.1002/cphc.202401104","DOIUrl":"10.1002/cphc.202401104","url":null,"abstract":"<p><p>Hydrolysis of NaBH₄ has garnered great concern in the production of hydrogen. Four different cobalt loadings (5 wt.%, 10 wt.%, 12.5 wt.% and 15 wt.%) were impregnated on SBA-15 molecular sieve. The effect of Co loading on the catalytic performance of the CoB/SBA-15 catalysts for NaBH₄ hydrolysis using the drainage method was studied. Characterizations using XRD, SEM, XPS, and N₂ adsorption-desorption were analytically conducted to examine the physiochemical properties of the CoB/SBA-15 catalyst. The catalytic activity test revealed that the optimum Co loading was 10 wt.% at which the maximum rate of hydrogen production was 153.0 mL/min⋅gcat, higher than the other samples. In addition, the effect of Co loaded, catalyst amount, and temperature were examined. Furthermore, the stability of the catalyst was maintained after five cycles. Cobalt-based catalysts are a promising catalytic system for hydrogen generation by hydrolysis of NaBH₄.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401104"},"PeriodicalIF":2.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143390225","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}

{"title":"Approaching the Lower Temporal Limit of Laser-Produced Plasma Sources for Table-Top Soft X-Ray NEXAFS Measurements.","authors":"Danika Nimlos, Alejandro Arellano, Scott Kevin Cushing","doi":"10.1002/cphc.202400857","DOIUrl":"10.1002/cphc.202400857","url":null,"abstract":"<p><p>The increasing popularity of time-resolved X-ray absorption measurements for understanding dynamics in molecular and material systems has led to many advances in table-top sources for pulsed X-rays. We report on a table-top laser-produced plasma (LPP) source that can perform soft X-ray (SXR), near-edge X-ray absorption fine structure (NEXAFS) measurements using a laser source with 23 ps pulse duration. The spectrometer's key specifications, such as brilliance, resolution, and stability, are characterized against the more commonly used longer-pulse-duration LPP sources. The 23 ps laser produced approximately an order of magnitude weaker SXR flux than the 8 ns laser for a higher power density due to the smaller total energy absorbed by the plasma. The increased repetition rate, as well as the use of a high line-density X-grating, and a self-referencing scheme still allowed for NEXAFS measurements of Si₃N₄ and TiO₂ thin films with 2.5 minute acquisition times, a resolving power of E/ΔE=424, and a signal-to-noise ratio of 100. It was observed that degradation of the gas jet nozzle led to long-term instability of the source, which can be remediated using alternative nozzle designs. This work demonstrates the feasibility of achieving higher temporal resolution in future time-resolved X-ray absorption measurements using table-top LPP sources.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400857"},"PeriodicalIF":2.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143390223","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}

{"title":"Proton Changes the Rules of the Game: Insight into the Nature of \"Proton Sponges\".","authors":"Beata Kizior, Halina Szatylowicz, Tadeusz M Krygowski, Jarosław J Panek, Wiktor Zierkiewicz, Aneta Jezierska","doi":"10.1002/cphc.202400972","DOIUrl":"10.1002/cphc.202400972","url":null,"abstract":"<p><p>There are cases when a small change, such as capture of a simple particle, has a significant impact on the molecular properties. This indeed happens with the \"proton sponges\". It is shown how the substituent effect (SE) and the presence of an intramolecular hydrogen bond modulate the properties of 1,8-bis(dimethylamino)naphthalene (DMAN), its protonated form (DMANH⁺) and their 4-X substituted derivatives, based on the geometric, electronic structure and energetic parameters. For this purpose, the following substituents have been chosen: X=H, NO, NO₂, CN, CHO, Cl, F, CH₃, OCH₃, OH and NH₂, placed in the para position (C4 carbon atom) relative to the N(CH₃)₂ group, thus breaking the symmetry of the molecules. The study was performed using Density Functional Theory (DFT) at the B3LYP/6-311++G(d,p) level of theory. The Harmonic Oscillator Model of Aromaticity (HOMA) index was applied to study changes in the aromaticity of the naphthalene moiety. The strength of the intramolecular hydrogen bond (HB) was estimated by Espinosa-Molins-Lecomte (EML) equation. The Quantum Theory of Atoms in Molecules (QTAIM) and Interaction Region Indicator (IRI) were employed to investigate differences in electronic structure and non-covalent interactions caused by substitution. Finally, the Substituent Effect Stabilization Energy (SESE) and Charge of the Substituent Active Region (cSAR) were computed to evaluate the substituent effect characteristics. Natural Bond Orbital (NBO) analysis was carried out to evaluate the SE influence on the lone pair of nitrogen atoms (N1, N2). We have shown that the presence of a strong intramolecular HB significantly weakens the substituent effect. For electron-donating (ED) substituents, the SE effect was found to have a greater influence than hydrogen bonding in the DMANH⁺ series. The opposite result was obtained for electron-withdrawing (EW) substituents - the SE was estimated to be twice weaker than in the ED case.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400972"},"PeriodicalIF":2.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143390226","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}

{"title":"A Theoretical Investigation on the Structural, Electronic and Photocatalytic Properties of BaTaO₂N Adsorbed with Metal Cocatalysts.","authors":"Xin Zhou, Keyu Zhou, Huan Zhang, Xinyi Sun","doi":"10.1002/cphc.202401131","DOIUrl":"10.1002/cphc.202401131","url":null,"abstract":"<p><p>We have performed DFT calculations to study the adsorption of single metal atoms (M=Ti, V, Cr, Mn, Fe, Co, Ni, Cu) on both BaO- and TaON-terminated surfaces of cis-BaTaO₂N (001). We have identified the most stable adsorption configuration of each case and explored the relative stability, structural deformations, charge transfer, work function, density of states and mechanism of photocatalytic HER. For BaO termination, all of the adatoms bind covalently on top of the surface oxygens. For TaON termination, the metal atoms are located at the fourfold hollow site. The single metal atoms tend to exist on TaON-termination while they are apt to aggregate on BaO-termination. The formation of impurity states in the band gap is mostly originated from the adatom. When electrons are transferred from the adatom to the surface, the conduction band of semiconductor becomes partially occupied. The charge gained from the BaO termination or transferred to the TaON termination reduces with the increase in electronegativity of metal adatoms. The attachment of metal atoms on the BaO termination is favorable to the improvement of HER activity. While the TaON termination adsorbed with Ti, V and Cr may have better or comparable performance of HER compared with the pure surface.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401131"},"PeriodicalIF":2.3,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381644","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}

{"title":"Revealing Mechanisms of Lithium-Mediated Nitrogen Reduction Reaction from First-Principles Simulations","authors":"Chengyu Zhou,&nbsp;Qing Zhao","doi":"10.1002/cphc.202401097","DOIUrl":"10.1002/cphc.202401097","url":null,"abstract":"<p>Recently, lithium-mediated nitrogen reduction reaction (Li-NRR) in nonaqueous electrolytes has proven to be an environmentally friendly and feasible route for ammonia electrosynthesis, revealing tremendous economic and social advantages over the industrial Haber-Bosch process which consumes enormous fossil fuels and generates massive carbon dioxide emissions, and direct electrocatalytic nitrogen reduction reaction (NRR) which suffers from sluggish kinetics and poor faradaic efficiencies. However, reaction mechanisms of Li-NRR and the role of solid electrolyte interface (SEI) layer in activating N₂ remain unclear, impeding its further development. Here, using electronic structure theory, we discover a nitridation-coupled reduction mechanism and a nitrogen cycling reduction mechanism on lithium and lithium nitride surfaces, respectively, which are major components of SEI in experimental characterization. Our work reveals divergent pathways in Li-NRR from conventional direct electrocatalytic NRR, highlights the role of surface reconstruction in improving reactivity, and sheds light on further enhancing efficiency of ammonia electrosynthesis.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":"26 7","pages":""},"PeriodicalIF":2.3,"publicationDate":"2025-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202401097","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143381647","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}

{"title":"¹²⁷I Solid-State NMR Spectroscopy of Organic Periodates Featuring Halogen Bonded IO₄ ^- ⋅ ⋅ ⋅ IO₄ ^- Adducts.","authors":"Roberta Beccaria, Andrea Pizzi, Giuseppe Resnati, David L Bryce","doi":"10.1002/cphc.202401030","DOIUrl":"10.1002/cphc.202401030","url":null,"abstract":"<p><p>Hydroxyanions and oxyanions can overcome electrostatic repulsion between like charges to form supramolecular architectures whose formation is driven by non-covalent interactions such as hydrogen bonds and halogen bonds (HaB). We report here a ¹²⁷I solid-state nuclear magnetic resonance (SSNMR) study of a series of six organic periodates including compounds which feature I ⋅ ⋅ ⋅ O HaB between pairs of IO₄ ^- anions and control samples which do not feature HaB. ¹²⁷I SSNMR spectra of powdered samples acquired under stationary conditions at 9.4, 11.7, and 21.1 T are simulated using an exact diagonalization of the Zeeman-quadrupolar Hamiltonian to provide the isotropic chemical shift, ¹²⁷I nuclear quadrupolar coupling constant (C_Q), and quadrupolar asymmetry parameter for each compound. One of the HaB compounds, 4-(pyrrolidin-1-yl)pyridinium periodate, is characterized by the largest C_Q(¹²⁷I) value measured to date for a periodate anion, 52.70 MHz. Control organic periodates which do not have HaBs have C_Q(¹²⁷I) values that are much lower than those seen in the halogen-bonded systems, thereby easily differentiating between these two sets of compounds. The C_Q(¹²⁷I) values for those compounds featuring only halogen-bonded periodate anions correlate with the shear strain of the anion, which may be attributed to the influence of the HaB on the local geometry. More rigorous correlations between structure and the ¹²⁷I NMR data are confounded by the presence of dynamics in some of the samples.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202401030"},"PeriodicalIF":2.3,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363993","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}

{"title":"Progress and Perspectives of Lithium Isotope Separation.","authors":"Pengbing He, Qionghua Xie, Jinyu Wang, Guocheng Yao, Liangshi Wang","doi":"10.1002/cphc.202400999","DOIUrl":"10.1002/cphc.202400999","url":null,"abstract":"<p><p>Stabilized lithium isotopes (⁶Li, ⁷Li) play an important role in related fields such as energy and defense. With the advancement of nuclear technology, the demand for lithium isotopes is expected to increase significantly. Although the separation of lithium amalgam is effective, it poses greater pollution risks. Therefore, it is very important to establish an efficient, green and sustainable lithium isotope separation method. Lithium isotopes are extremely difficult to isolate, but the discovery of their differences in migration (diffusion) rates, optical excitation, magnetic field response, and chemical binding has enable their potential separation lithium isotopes. Among the various lithium isotope separation methods developed, electrochemical migration stands out as a technique with industrial potential due to its high single-stage separation factor. Hence, this paper focuses on the research progress of lithium isotope separation methods with significant industrial potential. It elucidates the merits and challenges of various techniques, explores key obstacles to their industrialization. Finally, a method for separating lithium isotopes using solid electrolytes is described in the context of lithium-ion battery technology and related research on lithium isotope separation. Despite being in its infancy, this method warrants further research and experimentation.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400999"},"PeriodicalIF":2.3,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363997","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}

{"title":"DFT Study of the Mechanism of Selective Hydrogenation of Acetylene by Rhodium Single-Atom Catalyst Supported on HY Zeolite.","authors":"Melisa Su Yordanlı, Roberto Escobar, Jessica Meza, Deniz Akgül, Yuxin Zhao, Alper Uzun, F Ahu Akin, Viktorya Aviyente, Abdurrahman C Atesin, Tülay A Ateşin","doi":"10.1002/cphc.202400867","DOIUrl":"10.1002/cphc.202400867","url":null,"abstract":"<p><p>The selectivity of acetylene hydrogenation by the Rh single-atom catalyst (SAC) supported on HY zeolite was investigated using density functional theory (DFT) and a 5/83T quantum mechanics/molecular mechanics (QM/MM) embedded cluster model. The calculated activation barrier (ΔG^≠) for the oxidative addition of dihydrogen to the Rh metal center (15.9 kcal/mol) is lower in energy than that for the σ-bond metathesis of dihydrogen to the Rh-C bond (22.7 kcal/mol) and the Rh-O bond (28.4 kcal/mol). The activation barriers of the oxidative addition of subsequent dihydrogen molecules are significantly higher than that of the oxidative addition of the first dihydrogen molecule. These findings align with the experimentally observed activity and selectivity of the atomically dispersed Rh catalyst supported on HY zeolite. Natural bond orbital (NBO), molecular orbital (MO) and fuzzy bond order analyses were used to examine the interaction between the Rh metal center and acetylene versus ethylene ligands. The occupancies of the Rh lone pairs, π-bonding and π*-antibonding orbitals of acetylene and ethylene are consistent with the expected stronger interaction between the Rh metal center and acetylene compared to ethylene on the HY zeolite support.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400867"},"PeriodicalIF":2.3,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143363996","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}