Article
Chemistry, Physical
Shenzhen Xu, Emily A. Carter
Summary: Research has shown that CO2 photoelectroreduction on GaP electrodes can efficiently produce methanol through the hydride transfer (HT) mechanism. However, HT may induce hydrogen evolution as a side reaction, leading to reduced selectivity.
Article
Chemistry, Inorganic & Nuclear
Jingjing Wei, Yijing Wang, Xinyi Li, Xue Zhang, Yongjun Liu
Summary: In this study, the catalytic mechanism of 2,5-Dihydroxypyridine dioxygenase (NicX) was elucidated using combined quantum mechanics/molecular mechanics (QM/MM) calculations. The results revealed a three-step reaction involving the attack of a superoxo group on the pyridine ring, dissociation of a bond, and ring-opening of a seven-membered-ring lactone. The substrate undergoes electron transfer to the Fe-coordinated dioxygen, leading to the formation of the final product.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xia Zhao, Wen-Yan Tong, Xiaotai Wang
Summary: This study investigates the detailed mechanism of CuH-catalyzed hydroarylation of alkenes with polyfluoroarenes involving C-F bond functionalization. The research reveals that the regioselectivity is determined by a combination of orbital and dispersion interactions induced by the aryl alkene substrate. Additionally, the benzyl ligand facilitates a cupratropic shift, allowing for nucleophilic aromatic substitution. Noncovalent interactions play a crucial role in the regioselectivity of C-F bond cleavage.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Xia Zhao, Wen-Yan Tong, Xiaotai Wang
Summary: This study investigates the detailed workings of copper-catalyzed hydroarylation of alkenes with polyfluoroarenes, focusing on C-F bond functionalization. The results show that the regioselectivity of the reaction is influenced by a combination of orbital and dispersion interactions induced by the aryl alkene substrate. The mechanistic insights obtained from this study can have significant implications for the development of new transition metal-catalyzed hydroarylation and C-F functionalization reactions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Daehan Lee, Sunghan Choi, Min Su Choe, So-Yoen Kim, Kyutai Park, Chul Hoon Kim, Ho-Jin Son, Sang Ook Kang
Summary: The catalytic performance of the half-metallocene Ir(III) complex in photochemical CO2 reduction was evaluated in both homogeneous and heterogeneous systems. Modification of the catalyst and photosensitizer led to the formation of mixed homogeneous and heterogeneous ternary hybrid systems, revealing two different catalytic routes for CO2 reduction. Experimental and theoretical studies suggested that the homogeneous catalysis involves a Cp*Ir-III-H intermediate, while the heterogeneous catalysis undergoes multiple electron transfer pathways.
Article
Chemistry, Applied
Masahiro Sai, Hiroaki Kurouchi
Summary: In this study, the first KHMDS-catalyzed Michael additions of allylic alcohols to alpha,beta-unsaturated amides were reported. The reaction proceeds smoothly with only 5 mol% of KHMDS to afford a variety of 1,5-ketoamides in high yields. Mechanistic investigations revealed that the in-situ generation of the enolate from the allylic alcohol through a tunneling-assisted 1,2-hydride shift is crucial for the success of this transformation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Jieun Hyun, Hyeongjin Kim, Bonggeun Shong, Yo-Sep Min
Summary: Pyridine-catalyzed atomic layer deposition (ALD) of SiO2 from hexachlorodisilane and water was studied. Self-limiting growth of SiO2 by catalytic ALD has been achieved when both half-reactions are catalyzed by pyridine. The unexpected growth of SiO2, when only one half-reaction was catalyzed, was caused by the presence of residual pyridine that had not yet desorbed from the previous half-reaction. The retardation of catalyst desorption was more prominent on the OH-terminated SiO2 surface than on the Cl-terminated surface, which is related to the significantly higher desorption energy of pyridine species on the hydroxyl surface calculated using density functional theory.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Alexandros Paparakis, Roland C. C. Turnell-Ritson, Joshua S. S. Sapsford, Andrew E. E. Ashley, Martin Hulla
Summary: Selective N-formylation of amines via CO2 hydrogenation catalyzed by Lewis acids is an efficient and highly selective synthetic strategy, enabling high-yield conversion of amines with functionalities such as alkenes and amides while preventing catalyst decomposition. Increasing steric hindrance with alkyl substituents can enhance conversion rates and prevent undesired reactions.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Xue-Jiao Chen, Yi-Meng Chen, Song Yu, Teng-Xiang Huang, Shuifen Xie, De-Yin Wu, Zhong-Qun Tian
Summary: The study found that pyridine and pyridinium can interact with the Pt electrode in different ways. While pyridine species had no effect on the CER, pyridinium can enrich near the electrode in a CO2-saturated solution at negative potentials and act as a proton relay in the hydrogen evolution reaction.
Article
Materials Science, Multidisciplinary
Jingli Shi, Baotian Wang, Gan Li, Hailiang Wang, Xianggang Kong, Tao Gao, Wenhua Luo
Summary: The interface interaction behavior and mechanism between CO2 molecule and PuH2 (100), (110), and (111) surfaces were investigated using the GGA + U method. The results indicate the presence of both strong chemical adsorption and weak physical adsorption between CO2 and PuH2 surfaces. The adsorption energy results suggest that CO2 may have relatively strong reactivity with the (110) surface. The adsorption configurations reveal the formation of Pu-O and Pu-C bonds on the hydride surface due to the capture of CO2 by surface Pu atoms.
Article
Chemistry, Physical
Jing Li, Wei Guan
Summary: This study investigated the mechanism of a divalent nickel hydride complex catalyzed anti-Markovnikov reductive cross-coupling reaction using density functional theory, revealing the key steps and electronic processes involved.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2021)
Article
Chemistry, Physical
Haiguang Gao, Yingyan Zhao, Xu Zhang, Baozhou Zhao, Zhen Jia, Yana Liu, Xiaohui Hu, Yunfeng Zhu
Summary: This study introduces solid-solution MAX phase TiVAlC catalyst directly into the MgH2 system to improve its hydrogen storage performance. The excellent catalytic activity of TiVAlC catalyst can be explained by abundant electron transfer at external and internal interfaces. The influence of impurity phase on the overall activity of catalysts has also been studied, providing a unique method for designing composite catalyst to improve hydrogen storage performance of MgH2.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Physical
Hyoju Choi, Ruibin Wang, Suyeon Kim, Dongwook Kim, Mu-Hyun Baik, Sehoon Park
Summary: PPh3 in combination with [Rh(cod)Cl](2) as a precatalyst can catalyze the double hydroboration of pyridine, giving N-Bpin-1,2,3,4-tetrahydropyridines with sp(3) C-B bond in 60-90% combined yields. The ratio of G and R in the final products varies depending on the phosphine ligands used, and the resting state of the Rh species in solution is proposed to be Rh(PPh3)Cl(H)(Bpin)(Py)(n).
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Xue-Ting Fan, Xiao-Jian Wen, Jun Cheng
Summary: This study investigates the mechanism of pyridine-catalyzed CO2 reduction on a GaP photoelectrode using first-principles molecular dynamics. The results suggest that CO2 activation through the formation of PyCO2 on the GaP surface may be the key to lowering the overpotential, providing important theoretical insights for the development of efficient catalysts for CO2 reduction.
Article
Chemistry, Multidisciplinary
Lei Zhou, Chenfei Yao, Wentao Ma, Jinling Hu, Youting Wu, Zhibing Zhang, Xingbang Hu
Summary: The polymerization method was used to prepare the PCAAC-Ir catalyst, which showed excellent stability and activity in CO2 hydrogenation reaction, with a yield 38.7 times higher than the un-polymerized CAAC-Ir. Moreover, the catalyst performs well in water and can be easily recycled without significant loss of activity.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Multidisciplinary Sciences
Robert B. Wexler, Emily A. Carter
Summary: This study used DFT to investigate the factors controlling species oxidation selectivity in seawater electrolysis and found that the metal redox activity determines the strength of oxygen chemisorption. The study also revealed a strong correlation between oxygen and chlorine chemisorption, posing a fundamental challenge for seawater electrode material design.
ADVANCED THEORY AND SIMULATIONS
(2023)
Article
Chemistry, Physical
Antonia E. Papasergio, Greta Ugolotti, Enrico Sassoni, Martina Lessio
Summary: Surface treatments involving the in situ formation of a passivating calcium phosphate layer have been developed to improve the acid-resistance of marble. The addition of alcohol to the treatment improves the coverage of the calcium phosphate layer, but the reason behind this improvement is still unclear. Computational and experimental studies suggest that the interaction of organic additives with the marble surface does not play a major role in determining the treatment outcomes, indicating the need for further investigation of other factors for the design of improved treatments.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Claudia S. Cox, Eve Slavich, Lauren K. Macreadie, Laura K. McKemmish, Martina Lessio
Summary: UiO-66 is a highly studied metal-organic framework with exceptional stability and potential applications. Defective UiO-66, formed by missing linkers or clusters, enhances catalytic and adsorptive performance. This review provides a comprehensive overview of the literature and a meta-analysis to understand the synthesis parameters and structural outcomes. The analysis identifies relationships between parameters and provides recommendations for future experimental work.
CHEMISTRY OF MATERIALS
(2023)
Editorial Material
Chemistry, Physical
Emily A. Carter, Mark A. Johnson, Stephen R. Leone
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Biographical-Item
Chemistry, Physical
Emily A. Carter, Mark A. Johnson, Stephen R. Leone
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Lesheng Li, Marcos Calegari F. Andrade, Roberto Car, Annabella Selloni, Emily A. Carter
Summary: In this study, the influence of different TiS2 surface terminations on its interface with water was revealed through deep potential molecular dynamics simulations. Zigzag-L was identified as the only interface that favors water dissociation thermodynamically and kinetically, with the coexistence of four-fold-coordinated Ti and one-fold-coordinated S atoms on the surface playing a crucial role in proton transfer. This work provides new insights for the future design and optimization of TiS2-based CDI devices for water desalination.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Biographical-Item
Chemistry, Physical
Emily A. Carter, Mark A. Johnson, Stephen R. Leone
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Jin Cai, Qing Zhao, Wei-You Hsu, Chungseok Choi, Yang Liu, John Mark P. Martirez, Chih Chen, Jin Huang, Emily A. Carter, Yu Huang
Summary: A highly (111)-oriented Cu foil electrocatalyst with dense twin boundaries (tw-Cu) is demonstrated to exhibit high selectivity towards CH4 in the electrochemical carbon dioxide reduction reaction. The tw-Cu catalyst achieves a high Faradaic efficiency of 86.1 +/- 5.3% for CH4 production. Theoretical studies suggest that tw-Cu reduces the reduction barrier for the rate-determining hydrogenation of CO compared to planar Cu(111), leading to the observed high CH4 selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
John Mark P. Martirez, Emily A. Carter
Summary: Simulations of carbon dioxide in water can help understand its impact on aquatic environments and advance carbon capture and utilization technologies. Only by using quantum mechanical simulations and rare-event sampling, combined with energy corrections, can the theoretical results closely match experimental data. These multilevel simulations can serve as benchmarks for simpler models and provide insights into their potential errors.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jan-Niklas Boyn, Emily A. Carter
Summary: The dehydration dynamics of aqueous Ca2+ and Mg2+ cations are important in chemical and biological phenomena and have particular relevance in carbon capture techniques. This study investigates the dehydration process of these cations using rare event sampling and provides insights into the effect of pH on their stability.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Matthew Teusner, Uttam Mittal, Martina Lessio, Bernt Johannessen, Jitendra Mata, Neeraj Sharma
Summary: We report the use of copper tartrate, an inexpensive and off-the-shelf metal-carboxylate, as a high-capacity anode material for lithium-ion batteries, achieving a specific capacity of 744 mA h g(-1) when cycled at 50 mA g(-1). Advanced techniques, including XAS, XRD, SANS, and USANS, were used to investigate the structure-performance relationship of the electrode and uncover an unusual capacity gain with cycling.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Jierui Zhang, Francesco Paesani, Martina Lessio
Summary: Studies have shown that incorporating hydrophilic functional groups into the UiO-66 metal-organic framework (MOF) can improve its water uptake ability at low relative humidity (RH). This computational study provides insights into the adsorption mechanism of water in UiO-66 and its functionalized derivatives, revealing the preferential interaction sites and the formation of localized water clusters inside the octahedral pores. The presence of functional groups allows water to cluster in the pores at lower RH, making the MOF a more efficient water harvester.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Robert B. Wexler, Gopalakrishnan Sai Gautam, Robert T. Bell, Sarah Shulda, Nicholas A. Strange, Jamie A. Trindell, Joshua D. Sugar, Eli Nygren, Sami Sainio, Anthony H. McDaniel, David Ginley, Emily A. Carter, Ellen B. Stechel
Summary: This study demonstrates the synthesis of the perovskite Ca2/3Ce1/3Ti1/3Mn2/3O3, which has high phase purity, stability, and desirable redox thermodynamics for solar thermochemical H2 production (STCH) with a predicted average neutral oxygen vacancy formation energy of 3.30 eV. Experimental results indicate that this material has comparable or greater H2 production capacity than other promising metal oxide perovskites. Quantum-based modeling reveals that Ce4+ reduction dominates the redox activity of Ca2/3Ce1/3Ti1/3Mn2/3O3, and X-ray absorption spectroscopy measurements confirm reversible Ce4+ to Ce3+ reduction. The refinement of Ce stoichiometry has the potential to further enhance the performance of this material.
ENERGY & ENVIRONMENTAL SCIENCE
(2023)
Article
Chemistry, Physical
Ziyang Wei, John Mark P. Martirez, Emily A. Carter
Summary: This article introduces the random phase approximation (RPA) as a method for treating electron correlation, which has been shown to outperform standard density functional theory (DFT) approximations in cases such as extended surfaces. By using sub-system embedding schemes, the RPA can be used to simulate heterogeneous reactions at a reduced computational cost. The authors explore two embedded RPA approaches, periodic emb-RPA and cluster emb-RPA, and validate them in the H-2 dissociative adsorption on Cu(111) surface, finding that cluster emb-RPA accurately reproduces the energy profile while significantly reducing computational cost.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Jan-Niklas Boyn, Emily A. Carter
Summary: The dehydration of aqueous calcium and magnesium cations is a fundamental process controlling their reactivity and plays a crucial role in carbon capture techniques. Understanding the dehydration dynamics of these cations is important for utilizing seawater as a source of carbon storage through the formation of carbonate minerals. However, there is limited atomic-scale understanding of the dehydration process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)