From the reduction of dinitrogen to the oxidation of water, the chemical transformations catalysed by metalloenzymes underlie global geochemical and biochemical cycles. These reactions represent some of the most kinetically and thermodynamically challenging processes known and require the complex choreography of the fundamental building blocks of nature, electrons and protons, to be carried out with utmost precision and accuracy. The rate-determining step of catalysis in many metalloenzymes consists of a protein structural rearrangement, suggesting that nature has evolved to leverage macroscopic changes in protein molecular structure to control subatomic changes in metallocofactor electronic structure. The proton-coupled electron transfer mechanisms operative in nitrogenase, photosystem II and ribonucleotide reductase exemplify this interplay between molecular and electronic structural control. We present the culmination of decades of study on each of these systems and clarify what is known regarding the interplay between structural changes and functional outcomes in these metalloenzyme linchpins.
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http://dx.doi.org/10.1038/s41570-024-00646-7 | DOI Listing |
Nat Commun
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
Direct carbonylation of CH to CHCOOH provides a promising pathway for upgrading of natural gas to transportable liquid chemicals, in which high-efficiency CH activation and controllable C-C coupling are both critical but challenging. Herein, we report that highly efficient photo-driven carbonylation of CH with CO and O to CHCOOH is achieved over MoS-confined Rh-Zn atomic-pair in conjunction with TiO. It delivers a high CHCOOH productivity of 152.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, China.
Light-driven direct conversion of methane to formic acid is a promising approach to convert methane to value-added chemicals and promote sustainability. However, this process remains challenging due to the complex requirements for multiple protons and electrons. Herein, we report the design of WO-based photocatalysts modified with Pt active sites to address this challenge.
View Article and Find Full Text PDFEnviron Sci Technol
January 2025
The Key Lab of Pollution Control and Ecosystem Restoration in Industry Clusters, Ministry of Education, School of Environment and Energy, South China University of Technology, Guangzhou 510006, China.
Electrocatalytic nitrate reduction reaction (NORR) to harmless nitrogen (N) presents a viable approach for purifying NO-contaminated wastewater, yet most current electrocatalysts predominantly produce ammonium/ammonia (NH/NH) due to challenges in facilitating N-N coupling. This study focuses on identifying metal catalysts that preferentially generate N and elucidating the mechanistic origins of their high selectivity. Our evaluation of 16 commercially available metals reveals that only Pb, Sn, and In demonstrated substantial N selectivity (79.
View Article and Find Full Text PDFACS Omega
December 2024
Faculty of Health Science, University of Ss. Cyril and Methodius, 91701 Trnava, Slovakia.
Nat Commun
January 2025
Max Planck Institute of Colloids and Interfaces, Colloid Chemistry Department, Am Mühlenberg 1, 14476, Potsdam, Germany.
Covalent semiconductors of the carbon nitride family are among the most promising systems to realize "artificial photosynthesis", that is exploiting synthetic materials which use sunlight as an energy source to split water into its elements or converting CO into added value chemicals. However, the role of surface interactions and electronic properties on the reaction mechanism remain still elusive. Here, we use in-situ spectroscopic techniques that enable monitoring surface interactions in carbon nitride under artificial photosynthetic conditions.
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