Article
Chemistry, Physical
Jiaji Zhang, Raffaele Borrelli, Yoshitaka Tanimura
Summary: In this study, a detailed theoretical model of photo-induced proton-coupled electron transfer (PPCET) processes was developed to analyze the dynamics and efficiency of the reaction. By employing hierarchical equations of motion, the quantum dynamics of the PPCET process under an interaction with a non-Markovian environment was studied, providing insights into the transition pathways through transient absorption spectroscopy (TAS) and two-dimensional resonant electronic-vibrational spectroscopy (2DREVS) signals.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Applied
Hamid Ghorbani Shiraz, Mikhail Vagin, Tero-Petri Ruoko, Viktor Gueskine, Krzysztof Karon, Mieczyslaw Lapkowski, Tobias Abrahamsson, Thomas Ederth, Magnus Berggren, Xavier Crispin
Summary: Green hydrogen is considered a key clean energy carrier, and liquid organic hydrogen carriers (LOHCs) are explored as a low-cost and safe solution for hydrogen transport. Electrochemical hydrogen storage (EHS) using proton-coupled electron transfer (PCET) is investigated as a method to extract hydrogen from LOHCs. The study validates this concept through a model reaction.
JOURNAL OF ENERGY CHEMISTRY
(2022)
Article
Electrochemistry
Jeongmin Yeo, Jinho Chang
Summary: Understanding the electrochemical mechanism of serotonin oxidation is crucial for accurate sensing applications. Electrochemical signals can provide detailed mechanistic information about reactive serotonin intermediates. The oxidation of a serotonin radical intermediate, SH·, was studied using voltammetric kinetic discrimination (VKD) in a buffered system at neutral pH. The results showed different voltammograms at different scan rates, indicating the involvement of proton-coupled electron transfers (PCETs) and the instability of reactive serotonin intermediates.
ELECTROCHIMICA ACTA
(2022)
Article
Chemistry, Multidisciplinary
Yusuke Yoneda, S. Jimena Mora, James Shee, Brian L. Wadsworth, Eric A. Arsenault, Diptarka Hait, Gerdenis Kodis, Devens Gust, Gary F. Moore, Ana L. Moore, Martin Head-Gordon, Thomas A. Moore, Graham R. Fleming
Summary: This study investigates the photoinduced PCET dynamics of a biomimetic model system using various spectroscopic techniques and computational methods, providing insights into the complex dynamics and synergistic motions involved in the process. Specifically, the evolution of the 2DEV line shape, sensitive to the mixing of vibronic states, is interpreted through accurate computational modeling of the charge separated state, revealing a gradual change in electron density distribution associated with a dihedral twist occurring on a 120 fs time scale.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Nanoscience & Nanotechnology
Honghong Duan, Fan Cao, Hongxing Hao, Hongtao Bian, Liping Cao
Summary: The study explores the construction of artificial photofunctional systems with energy and electron transfer functions via a host-guest approach using a tetraphenylethene-based octacationic cage and fluorescent dyes. The cage traps various dyes within its hydrophobic cavity to form 1:1 host-guest complexes via CH-pi, pi-pi, and/or electrostatic interactions in solution. Efficient energy transfer and ultrafast photoinduced electron transfer between the cage and dyes are competitive processes in artificial photofunctional systems.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Materials Science, Multidisciplinary
Zetian Yang, Jonas J. Joos, Jieqi Hu, David van der Heggen, Tim Pier, Maxime Delaey, Henk Vrielinck, Thomas Justel, Philippe F. Smet, Dirk Poelman
Summary: This study demonstrates a design approach for wavelength-specific light dosimeters based on photo-induced redox processes of certain lanthanides in phosphate compounds, enabling selective monitoring of UV and visible light doses. The reduction process is induced through ligand-to-metal charge transfer excitation, while the oxidation process is achieved through excitation of the involved hole traps or 4f(N)-4f(N-1)5d(1) transitions of the created divalent dopants. The dose and wavelength-dependent redox processes allow for tailored spectral sensitivity of the dosimeter, making it suitable for personal solar UV radiation monitoring.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Ankita Bhattacharya, S. K. Firoz Islam
Summary: The study investigates the band structure modulation and spin-Hall effect of an irradiated two-dimensional heavy-hole system with k(3)-Rashba spin-orbit coupling. It is found that under illumination, the band structure becomes anisotropic and additional spin-degeneracy points emerge in the energy dispersion, solely determined by the incident light's amplitude. When these points occur near the Fermi level, a resonance in spin-Hall conductivity is observed, while away from the degeneracy points, the average spin polarization is rotated by the light. Additionally, the effects of k(3)-Dresselhaus spin-orbit coupling are discussed.
Article
Chemistry, Multidisciplinary
Niklas von Wolff, Marc Robert
Summary: Electron serves as the ultimate redox reagent for building and reshaping molecular structures. Understanding and controlling the parameters involved in dissociative electron transfer (DET) reactivity and its coupling with proton transfer are crucial for enhancing selectivity, kinetics, and energy efficiency in molecular chemistry. Various applications, such as photoredox catalysis, CO2 reduction, and alcohol oxidation, highlight the broad range of processes encompassed by DET pathways and demonstrate the importance of studying the driving force-rate relationships for future developments in energy efficient catalytic schemes in redox organic chemistry.
Article
Chemistry, Multidisciplinary
Mirco Natali, Agnese Amati, Nicola Demitri, Elisabetta Iengo
Summary: Aromatic amino acids such as l-tyrosine and l-tryptophan play a role in mediating electron transfer reactions in natural systems. This study prepared and characterized two novel conjugates based on porphyrin chromophores and l-tryptophan as electron/proton donor. Photophysical investigation showed different quenching mechanisms operating upon visible-light excitation, highlighting the unique role of l-tryptophan in proton-coupled electron transfer.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Tai-Che Chou, Diana Temerova, Chi-Chi Wu, Sheng-Ming Tseng, Igor O. Koshevoy, Pi-Tai Chou
Summary: In this study, a clean photoinduced intramolecular aryl shift reaction was discovered for imidazolyl-quinoline derivatives, producing thermally reversible photoproducts. The slow reaction rates were found to be associated with a transition free energy of ~5.0 kcal/mol. This discovery provides a new pathway in synthetic chemistry and has potential applications in solar-chemical storage under appropriate design strategies.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Zhongneng Zhou, Zijing Chen, Xiu-Wen Kang, Yalin Zhou, Bingyao Wang, Siwei Tang, Shuhua Zou, Yifei Zhang, Qiaoyu Hu, Fang Bai, Bei Ding, Dongping Zhong
Summary: In this study, the photocycle of the FMN-Gln-Tyr motif in the BLUF domain of OaPAC was investigated using computational simulations. The results show that forward PCET is concerted, while only the wild-type protein proceeds with an ultrafast reverse PCET process.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Multidisciplinary
Kohsuke Ohmatsu, Haruka Fujimori, Kodai Minami, Kosuke Nomura, Mari Kiyokawa, Takashi Ooi
Summary: Thioamidate ions are introduced as competent cocatalysts for multisite proton-coupled electron transfer catalysis. The high pK(a) values of their conjugate acids contribute to the effectiveness of these anions. The combined use of stable tetrabutylammonium thioamidate and an appropriate Ir-based photosensitizer enables the C-H alkylation of various C-H donors, including simple cyclic alkanes, under visible-light irradiation.
Article
Chemistry, Multidisciplinary
Clorice R. Reinhardt, Elvira R. Sayfutyarova, Jiayun Zhong, Sharon Hammes-Schiffer
Summary: Ribonucleotide reductase (RNR) is an essential enzyme in DNA synthesis, with the active form of E. coli Ia RNR consisting of two subunits, alpha and beta, involved in a series of proton-coupled electron transfer (PCET) reactions. Quantum mechanical/molecular mechanical simulations suggest thermodynamically favored forward radical transfer in the pre-turnover state and backward radical transfer in the post-turnover state between Y731 and Y730. The simulations also propose that E623 plays a key role in influencing the directionality of PCET and predict the impact of mutation of E623 on catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Deguang Zhang, Wenbo Liu, Runwei Wang, Zongtao Zhang, Shilun Qiu
Summary: Constructing a hierarchical TiO2@Mo2C/C photocatalyst with in-situ method enhances photocatalytic activity and stability by promoting charge separation and utilization. The unique method of in-situ construction can be helpful in obtaining functional integrating catalysts for proton-coupled electron transfers (PCETs) photocatalytic reactions.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Nanoscience & Nanotechnology
Junji Fujimoto, Florian Lange, Satoshi Ejima, Tomonori Shirakawa, Holger Fehske, Seiji Yunoki, Sadamichi Maekawa
Summary: By utilizing response theory, the paper calculates the charge current vortex generated by spin pumping at a point-like contact in a system with Rashba spin-orbit coupling. The oscillatory behavior of the charge current as a function of distance from the spin pumping source is observed, which is supported by numerical simulations. The introduction of the SOC Hamiltonian on the lattice as the generator of the spin current is a significant aspect of their calculations.
Article
Chemistry, Physical
Heng Rao, Julien Bonin, Marc Robert
JOURNAL OF PHYSICAL CHEMISTRY C
(2018)
Article
Chemistry, Multidisciplinary
Heng Rao, Chern-Hooi Lim, Julien Bonin, Garret M. Miyake, Marc Robert
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Multidisciplinary
Bing Ma, Gui Chen, Claire Fave, Lingjing Chen, Ryo Kuriki, Kazuhiko Maeda, Osamu Ishitani, Tai-Chu Lau, Julien Bonin, Marc Robert
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Physical
Ruwen Wang, Etienne Boutin, Nicolas Barreau, Fabrice Odobel, Julien Bonin, Marc Robert
Summary: The challenge of converting CO2 into valuable compounds, such as fuels, using renewable energy sources and sustainable compounds is being addressed through artificial photosynthesis research. One promising approach involves solar-assisted electrochemical processes where electrons are supplied by a photovoltaic cell. A PV-EC system has been developed that can reduce CO2 to CO and then convert it to methanol with limited bias voltage. The efficiency of this CO2-to-CH3OH reaction is around 28% under ideal conditions.
Review
Chemistry, Inorganic & Nuclear
Alessandro Perazio, Grace Lowe, Roberto Gobetto, Julien Bonin, Marc Robert
Summary: This review focuses on recent advances in photocatalytic CO2 reduction using heterogenized molecular catalysts. It discusses the chemistry of attaching catalysts to different supports to produce hybrid materials and explores the impact on photocatalytic performance, as well as the potential future impact of these systems on solar fuels research.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Bing Ma, Matias Blanco, Laura Calvillo, Lingjing Chen, Gui Chen, Tai-Chu Lau, Goran Drazic, Julien Bonin, Marc Robert, Gaetano Granozzi
Summary: The cobalt quaterpyridine complexes covalently linked to graphene surfaces with carboxylic acid groups showed high activity and exceptional stability in visible-light-driven CO2 catalytic conversion, with the ability to control product selectivity without compromising efficiency.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Sara Navarro-Jaen, Mirella Virginie, Julien Bonin, Marc Robert, Robert Wojcieszak, Andrei Y. Khodakov
Summary: This review compares different pathways for CO2 reduction to methanol and discusses the advantages and drawbacks of various catalysts, concluding that heterogeneous hydrogenation catalysis and electrocatalysis show the most promise for large-scale methanol synthesis from CO2.
NATURE REVIEWS CHEMISTRY
(2021)
Article
Chemistry, Physical
Martin Kientz, Grace Lowe, Blaine G. McCarthy, Garret M. Miyake, Julien Bonin, Marc Robert
Summary: We have evaluated six phenoxazine derivatives as visible light photosensitizers for the photochemical reduction of CO2 to CO with an iron porphyrin catalyst in organic media. The phenoxazine core was functionalized with electron-donating or -withdrawing groups to modify the photophysical properties. Our observation shows that there is no correlation between the production of CO and the excited state potential of the phenoxazine, but a clear correlation can be made between the oxidation potentials of the phenoxazine and the production of CO. This indicates that the process was limited by photosensitizer regeneration and that electron transfers not directly related to the catalyst activation could play a key role in homogeneous photocatalytic systems.
Article
Energy & Fuels
Ifan E. L. Stephens, Karen Chan, Alexander Bagger, Shannon W. Boettcher, Julien Bonin, Etienne Boutin, Aya K. Buckley, Raffaella Buonsanti, Etosha R. Cave, Xiaoxia Chang, See Wee Chee, Alisson H. M. da Silva, Phil de Luna, Oliver Einsle, Balazs Endrodi, Maria Escudero-Escribano, Jorge V. Ferreira de Araujo, Marta C. Figueiredo, Christopher Hahn, Kentaro U. Hansen, Sophia Haussener, Sara Hunegnaw, Ziyang Huo, Yun Jeong Hwang, Csaba Janaky, Buddhinie S. Jayathilake, Feng Jiao, Zarko P. Jovanov, Parisa Karimi, Marc T. M. Koper, Kendra P. Kuhl, Woong Hee Lee, Zhiqin Liang, Xuan Liu, Sichao Ma, Ming Ma, Hyung-Suk Oh, Marc Robert, Beatriz Roldan Cuenya, Jan Rossmeisl, Claudie Roy, Mary P. Ryan, Edward H. Sargent, Paula Sebastian-Pascual, Brian Seger, Ludmilla Steier, Peter Strasser, Ana Sofia Varela, Rafael E. Vos, Xue Wang, Bingjun Xu, Hossein Yadegari, Yuxiang Zhou
Summary: This article reviews recent progress in electrochemical CO2 reduction, discusses the challenges towards commercialization, and highlights opportunities for further research. The goal is to establish a low- or zero-emission carbon cycle.
JOURNAL OF PHYSICS-ENERGY
(2022)
Article
Chemistry, Physical
Marcella Bonchio, Julien Bonin, Osamu Ishitani, Tong-Bu Lu, Takeshi Morikawa, Amanda J. Morris, Erwin Reisner, Debashrita Sarkar, Francesca M. Toma, Marc Robert
Summary: Visible-light-driven conversion of CO2 to fuels and valuable compounds has been highly active in recent years. However, these processes and catalytic systems are still in early stages of development, with fundamental mechanistic challenges needing to be addressed. Collaborative efforts are needed to explore various approaches and establish robust practices to advance our understanding of these necessary processes.
Article
Chemistry, Physical
Srinivasulu Parshamoni, Cedric Viravaux, Marc Robert, Caroline Mellot-Draznieks, Gui Chen, Pierre Mialane, Anne Dolbecq, Julien Bonin
Summary: In this study, cobalt complexes were immobilized in two different metal-organic frameworks (MOFs) and characterized through solid state characterization techniques and density functional theory calculations. The resulting composite materials showed efficient and selective reduction of CO2 to CO under visible-light irradiation, with the favorable environment provided by the MOF scaffold.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Review
Chemistry, Multidisciplinary
E. Boutin, L. Merakeb, B. Ma, B. Boudy, M. Wang, J. Bonin, E. Anxolabehere-Mallart, M. Robert
CHEMICAL SOCIETY REVIEWS
(2020)
Review
Chemistry, Inorganic & Nuclear
Elodie Anxolabehere-Mallart, Julien Bonin, Claire Fave, Marc Robert
DALTON TRANSACTIONS
(2019)
Article
Chemistry, Multidisciplinary
Heng Rao, Julien Bonin, Marc Robert
Article
Chemistry, Multidisciplinary
Heng Rao, Julien Bonin, Marc Robert
CHEMICAL COMMUNICATIONS
(2017)