Article
Chemistry, Multidisciplinary
Marta Meneghello, Alexandre Uzel, Marianne Broc, Rita R. Manuel, Axel Magalon, Christophe Leger, Ines A. C. Pereira, Anne Walburger, Vincent Fourmond
Summary: Metal-based formate dehydrogenases are enzymes that require molybdenum or tungsten ions to catalyze the conversion between formate and CO2. The coordination of the metal ion in the active form prevents direct binding of formate to the metal. The study's findings provide strong evidence for the hypothesis that the oxidation of formate occurs in the second coordination sphere of the metal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mina R. Narouz, Patricia De La Torre, Lun An, Christopher J. Chang
Summary: By decorating iron porphyrins with imidazolium pendants, a family of multifunctional secondary coordination sphere groups is developed to enhance catalytic performance in synthetic systems. In the electrochemical CO2 reduction reaction (CO2RR), these imidazolium units promote multiple synergistic effects to increase CO2RR activity. The study also reveals that through-space charge effects have a stronger impact on catalytic CO2RR performance than hydrogen bonding in this context.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Nilakshi Devi, Caroline K. Williams, Ashwin Chaturvedi, Jianbing ''Jimmy'' Jiang
Summary: The study introduces an iron porphyrin catalyst, FePEG8T, which shows excellent activity, stability, and selectivity in electrocatalytic reduction of CO2 to CO. Control experiments confirm the contribution of triazole units on high catalytic activity. Long-term electrolysis demonstrates high catalyst stability.
ACS APPLIED ENERGY MATERIALS
(2021)
Article
Chemistry, Physical
Lin-Jun Zhu, Duan-Hui Si, Fa-Xue Ma, Meng-Jiao Sun, Teng Zhang, Rong Cao
Summary: This paper reports the use of a copper-supramolecular pair as a crystalline molecular catalyst to promote the formation of multicarbon products. Experimental and theoretical studies reveal the collaboration of paired Cu sites in activating the CO2 substrate and facilitating the coupling of adsorbed CO species. Van der Waals interactions between the substrate and the secondary coordination sphere also play a crucial role in multicarbon product selectivity.
Article
Chemistry, Physical
Xueqi Pang, Sumit Verma, Chao Liu, Daniel V. Esposito
Summary: Bicarbonate electrolysis is a promising method for electrochemical CO2 conversion using aqueous carbon capture solutions. The membrane-free electrolyzer concept presented in this study addresses the challenges of membrane degradation and scaling up, leading to higher CO2 utilization rates.
Article
Energy & Fuels
Oriol Gutierrez-Sanchez, Bert de Mot, Nick Daems, Metin Bulut, Jan Vaes, Deepak Pant, Tom Breugelmans
Summary: This study successfully captured and converted carbon dioxide from air into organic acids and CO, providing new opportunities for improving the economic feasibility and industrial implementation of CCU technologies.
Article
Energy & Fuels
Oriol Gutierrez-Sanchez, Bert de Mot, Nick Daems, Metin Bulut, Jan Vaes, Deepak Pant, Tom Breugelmans
Summary: Integrating alkaline capture of CO2 from air with electrochemical conversion of the obtained (bi)carbonate solution is a promising strategy in CCU technologies, providing a new opportunity for upscaling the electrochemical conversion of CO2 and enhancing the economic feasibility.
Article
Chemistry, Physical
Ian Sullivan, Andrey Goryachev, Ibadillah A. Digdaya, Xueqian Li, Harry A. Atwater, David A. Vermaas, Chengxiang Xiang
Summary: Electrochemical CO2 conversion into fuels or chemicals and CO2 capture from point or dilute sources are two important processes to address the gigaton challenges in reducing greenhouse gas emissions. Both processes are energy intensive, but synergistic coupling between them can improve energy efficiency and reduce costs, by eliminating the need for CO2 transport and storage or capture media regeneration.
Article
Chemistry, Multidisciplinary
Sayontani Sinha Roy, Kallol Talukdar, Jonah W. Jurss
Summary: A series of molecular Mn catalysts with aniline groups were developed for electrochemical and photochemical CO2 reduction, with catalyst 1-Mn showing the highest efficiency. The proximity of the aniline groups to the active site is crucial in determining catalytic performance, with high faradaic efficiencies achieved using trifluoroethanol as a proton source and a shift in product selectivity observed under photocatalytic conditions.
Article
Multidisciplinary Sciences
Lei Fan, Xiaowan Bai, Chuan Xia, Xiao Zhang, Xunhua Zhao, Yang Xia, Zhen-Yu Wu, Yingying Lu, Yuanyue Liu, Haotian Wang
Summary: In this study, a CO2/carbonate mediation approach was used to steer the pathway of electrochemical water oxidation reaction from oxygen evolution to hydrogen peroxide generation. This approach achieved high selectivity of hydrogen peroxide synthesis, along with good activity and durability.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Reza Khakpour, Daniel Lindberg, Kari Laasonen, Michael Busch
Summary: CO2 reduction is usually conducted at neutral pH, but most studies only focus on the contribution of CO2 while neglecting carbonate species. Using DFT modelling, this study explores the potential contribution of carbonate species to CO2 reduction activity and finds that carbonic acid and bicarbonate are the most likely reactants regardless of pH and reactor setup.
Article
Chemistry, Multidisciplinary
Yong Yang, Ziyun Zhang, Zhenyu Zhang, Chao Tang, Xiaoyong Chang, Lele Duan
Summary: In this study, a Re-based tricarbonyl catalyst Re1 with a spiro center and a phenol group was reported, which showed improved stability due to the large steric spiro group. The phenol group in the second coordination sphere promoted the protonation of CO2 reduction intermediates, enhancing the electrocatalytic CO2 reduction activity of Re1. Mechanistic studies revealed that the doubly reduced complex Re1b was active for CO2 addition.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Giulia Marcandalli, Mariana C. O. Monteiro, Akansha Goyal, Marc T. M. Koper
Summary: The electrochemical reduction of CO2 faces challenges such as low energy and Faradaic efficiencies due to concurrent electrochemical reactions and solution acid-base reactions. Recent studies have shown that the nature of the electrolyte, specifically pH and cation identity, plays a crucial role in tuning the efficiency of CO2RR to CO in aqueous solutions.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Multidisciplinary
Mengran Li, Kailun Yang, Maryam Abdinejad, Chuan Zhao, Thomas Burdyny
Summary: This review provides an overview of the fundamentals and recent progress in advancing integrated CO2 conversion in amine-based capture media. The mechanisms for CO2 absorption and electrochemical conversion are discussed, and recent advances in improving efficiency are summarised.
Article
Chemistry, Physical
Anthony R. Ramuglia, Vishal Budhija, Khoa H. Ly, Michael Marquardt, Matthias Schwalbe, Inez M. Weidinger
Summary: The newly synthesized iron porphyrin complex Py2XPFe contains a bispyridylamine-based hanging unit, which serves as a hydrogen bonding site to facilitate proton transfer and increase the rate of catalysis in electrocatalytic CO2 reduction reactions. The hanging group beneficially impacts the rate of catalysis when compared to the non-functionalized analog TMPFe, and the addition of weak Bronsted acids further enhances the catalytic activity of Py2XPFe.
Article
Chemistry, Multidisciplinary
Matthias Loipersberger, Delmar G. A. Cabral, Daniel B. K. Chu, Martin Head-Gordon
Summary: This study uses density functional theory to elucidate the different catalytic pathways of Co and Fe catalysts in the reduction of CO2 to CO. The Co catalyst shows metal-ligand bonding interaction, while the Fe catalyst maintains a Lewis acidic metal center throughout the reduction process, resulting in different reaction mechanisms and kinetics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
James Shee, Matthias Loipersberger, Diptarka Hait, Joonho Lee, Martin Head-Gordon
Summary: This work provides a detailed perspective on electron correlation in transition metal complexes, highlighting the presence of static correlation in linear molecules and some complex complexes, while emphasizing the importance of dynamic correlation in interactions involving organometallic species. The analysis suggests that theories using MP2 correlation energies may not be adequate in describing chemical bonds with non-negligible inter-electron pair correlation.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Matthias Loipersberger, Luke W. Bertels, Joonho Lee, Martin Head-Gordon
Summary: This work systematically assesses the influence of reference orbitals, regularization, and scaling on the performance of second- and third-order Moller-Plesset perturbation theory wave function methods for noncovalent interactions (NCIs). The study found that the use of kappa-regularization significantly improves energetics for both MP2 and OOMP2 methods, and that scaled MP3 using kappa-OOMP2 reference orbitals provides significantly more accurate results for NCIs. High-quality density functional reference orbitals also significantly improve the results of MP2.5 for NCI over a Hartree-Fock orbital reference.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Multidisciplinary
Murielle F. Delley, Eva M. Nichols, James M. Mayer
Summary: Understanding the effects of applied potentials and electrolyte solution conditions on interfacial proton transfers at electrode surfaces is crucial for electrochemical technologies. Measurements of the applied potential, electrolyte pD, and concentration determined the relative surface populations of acidic and basic forms of molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Rishi G. Agarwal, Scott C. Coste, Benjamin D. Groff, Abigail M. Heuer, Hyunho Noh, Giovanny A. Parada, Catherine F. Wise, Eva M. Nichols, Jeffrey J. Warren, James M. Mayer
Summary: This paper provides an update and revision to a 2010 review on proton-coupled electron transfer (PCET) reagent thermochemistry, correcting systematic errors and presenting updated tables of thermochemical values. It discusses new conclusions and opportunities arising from the assembled data and techniques, emphasizing the importance of updated thermochemical cycles in PCET reactions for calculation and measurement of Gibbs free energies. Additionally, the paper introduces several emerging fields in PCET thermochemistry, highlighting the diversity of research being conducted in this rapidly growing field.
Article
Chemistry, Physical
James Shee, Matthias Loipersberger, Adam Rettig, Joonho Lee, Martin Head-Gordon
Summary: The study explores three physically justified forms of single-parameter regularization for noncovalent interactions and transition metal thermochemistry, aiming to improve accuracy without increasing costs.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Matthias Loipersberger, Jeffrey S. Derrick, Christopher J. Chang, Martin Head-Gordon
Summary: This study combines computational and experimental methods to uncover two mechanistic pathways for the electrochemical conversion of CO2 into CO catalyzed by [Fe(tpyPY2Me)](2+) ([Fe](2+)). The findings provide insights into the exceptional performance of the catalyst and offer suggestions for designing improved platforms through ligand framework modifications.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Murielle F. Delley, Eva M. Nichols, James M. Mayer
Summary: The identity of electrolyte cations and the applied potential can significantly affect the interfacial acidity, electric fields, and SAM heterogeneity. Large cations such as tetrabutylammonium (TBA+) exhibit stronger electric fields and a more pH-responsive SAM compared to small cations. The insights on electrolyte cation effects are of fundamental interest for various electrochemical applications.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Patricia De La Torre, Jeffrey S. Derrick, Andrew Snider, Peter T. Smith, Matthias Loipersberger, Martin Head-Gordon, Christopher J. Chang
Summary: This study demonstrates the role of metal-ligand exchange coupling in determining the efficiency of photocatalytic CO2 reduction. The iron complex with maximized exchange coupling shows higher CO2 reduction activity and selectivity compared to the cobalt complex.
Editorial Material
Chemistry, Multidisciplinary
Eva M. Nichols
Summary: The electrochemical reduction of phosphate salts shows potential for sustainable production of elemental phosphorus.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Kevin Carter-Fenk, Meili Liu, Leila Pujal, Matthias Loipersberger, Maria Tsanai, Robert M. Vernon, Julie D. Forman-Kay, Martin Head-Gordon, Farnaz Heidar-Zadeh, Teresa Head-Gordon
Summary: Accurate potential energy models of proteins must consider the different types of noncovalent interactions, including the ubiquitous π-π contacts. Neutral π-π interactions are mainly governed by Pauli repulsion and London dispersion, while π-anion and π-cation interactions exhibit different behaviors in polar and nonpolar environments.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kaeden Teindl, Brian O. O. Patrick, Eva M. M. Nichols
Summary: This study investigates the contribution of proton transfer driving forces in molecular catalysts for electrochemical CO2 reduction. By synthesizing a series of catalysts with tunable pK(a) and varying acidity of exogenous acids, it is found that the kinetics of catalytic turnover are more sensitive to variations in SCS pK(a) when using more acidic exogenous acids and to variations in exogenous acid pK(a) when SCS acidity is increased.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yuezhi Mao, Matthias Loipersberger, Kareesa J. Kron, Jeffrey S. Derrick, Christopher J. Chang, Shaama Mallikarjun Sharada, Martin Head-Gordon
Summary: ALMO-EDA(solv) is a computational method that allows for the study of intermolecular interactions in solution by incorporating solvent effects. By applying this method to model complexes related to CO2 reduction catalysis, it was shown that substituents can have significant impacts on the stability of molecular structures. This extension of ALMO-EDA provides a valuable tool for understanding intermolecular interactions and their effects on chemical reactivity in solution.