Transition-metal-exchanged zeolites perform remarkable chemical reactions from low-temperature methane to methanol oxidation to selective reduction of NOx pollutants. As with metalloenzymes, metallozeolites have impressive reactivities that are controlled in part by interactions outside the immediate coordination sphere. These second-sphere effects include activating a metal site through enforcing an "entatic" state, controlling binding and access to the metal site with pockets and channels, and directing radical rebound vs cage escape. This review explores these effects with emphasis placed on but not limited to the selective oxidation of methane to methanol with a focus on copper and iron active sites, although other transition-metal-ion zeolite reactions are also explored. While the actual active-site geometric and electronic structures are different in the copper and iron metallozeolites compared to the metalloenzymes, their second-sphere interactions with the lattice or the protein environments are found to have strong parallels that contribute to their high activity and selectivity.

Transition metal catalysis is of utmost importance for the development of sustainable processes in academia and industry. The activity and selectivity of metal complexes are typically the result of the interplay between ligand and metal properties. As the ligand can be chemically altered, a large research focus has been on ligand development. More recently, it has been recognized that further control over activity and selectivity can be achieved by using the "second coordination sphere", which can be seen as the region beyond the direct coordination sphere of the metal center. Hydrogen bonds appear to be very useful interactions in this context as they typically have sufficient strength and directionality to exert control of the second coordination sphere, yet hydrogen bonds are typically very dynamic, allowing fast turnover. In this review we have highlighted several key features of hydrogen bonding interactions and have summarized the use of hydrogen bonding to program the second coordination sphere. Such control can be achieved by bridging two ligands that are coordinated to a metal center to effectively lead to supramolecular bidentate ligands. In addition, hydrogen bonding can be used to preorganize a substrate that is coordinated to the metal center. Both strategies lead to catalysts with superior properties in a variety of metal catalyzed transformations, including (asymmetric) hydrogenation, hydroformylation, C-H activation, oxidation, radical-type transformations, and photochemical reactions.

Gases like H2, N2, CO2, and CO are increasingly recognized as critical feedstock in "green" energy conversion and as sources of nitrogen and carbon for the agricultural and chemical sectors. However, the industrial transformation of N2, CO2, and CO and the production of H2 require significant energy input, which renders processes like steam reforming and the Haber-Bosch reaction economically and environmentally unviable. Nature, on the other hand, performs similar tasks efficiently at ambient temperature and pressure, exploiting gas-processing metalloenzymes (GPMs) that bind low-valent metal cofactors based on iron, nickel, molybdenum, tungsten, and sulfur. Such systems are studied to understand the biocatalytic principles of gas conversion including N2 fixation by nitrogenase and H2 production by hydrogenase as well as CO2 and CO conversion by formate dehydrogenase, carbon monoxide dehydrogenase, and nitrogenase. In this review, we emphasize the importance of the cofactor/protein interface, discussing how second and outer coordination sphere effects determine, modulate, and optimize the catalytic activity of GPMs. These may comprise ionic interactions in the second coordination sphere that shape the electron density distribution across the cofactor, hydrogen bonding changes, and allosteric effects. In the outer coordination sphere, proton transfer and electron transfer are discussed, alongside the role of hydrophobic substrate channels and protein structural changes. Combining the information gained from structural biology, enzyme kinetics, and various spectroscopic techniques, we aim toward a comprehensive understanding of catalysis beyond the first coordination sphere.

Two-dimensional (2D) ultrathin silica films have the potential to reach technological importance in electronics and catalysis. Several well-defined 2D-silica structures have been synthesized so far. The silica bilayer represents a 2D material with SiO2 stoichiometry. It consists of precisely two layers of tetrahedral [SiO4] building blocks, corner connected via oxygen bridges, thus forming a self-saturated silicon dioxide sheet with a thickness of ∼0.5 nm. Inspired by recent successful preparations and characterizations of these 2D-silica model systems, scientists now can forge novel concepts for realistic systems, particularly by atomic-scale studies with the most powerful and advanced surface science techniques and density functional theory calculations. This Review provides a solid introduction to these recent developments, breakthroughs, and implications on ultrathin 2D-silica films, including their atomic/electronic structures, chemical modifications, atom/molecule adsorptions, and catalytic reactivity properties, which can help to stimulate further investigations and understandings of these fundamentally important 2D materials.

This Review provides an overview of the emerging concepts of catalysts, membranes, and membrane electrode assemblies (MEAs) for water electrolyzers with anion-exchange membranes (AEMs), also known as zero-gap alkaline water electrolyzers. Much of the recent progress is due to improvements in materials chemistry, MEA designs, and optimized operation conditions. Research on anion-exchange polymers (AEPs) has focused on the cationic head/backbone/side-chain structures and key properties such as ionic conductivity and alkaline stability. Several approaches, such as cross-linking, microphase, and organic/inorganic composites, have been proposed to improve the anion-exchange performance and the chemical and mechanical stability of AEMs. Numerous AEMs now exceed values of 0.1 S/cm (at 60-80 °C), although the stability specifically at temperatures exceeding 60 °C needs further enhancement. The oxygen evolution reaction (OER) is still a limiting factor. An analysis of thin-layer OER data suggests that NiFe-type catalysts have the highest activity. There is debate on the active-site mechanism of the NiFe catalysts, and their long-term stability needs to be understood. Addition of Co to NiFe increases the conductivity of these catalysts. The same analysis for the hydrogen evolution reaction (HER) shows carbon-supported Pt to be dominating, although PtNi alloys and clusters of Ni(OH)2 on Pt show competitive activities. Recent advances in forming and embedding well-dispersed Ru nanoparticles on functionalized high-surface-area carbon supports show promising HER activities. However, the stability of these catalysts under actual AEMWE operating conditions needs to be proven. The field is advancing rapidly but could benefit through the adaptation of new in situ techniques, standardized evaluation protocols for AEMWE conditions, and innovative catalyst-structure designs. Nevertheless, single AEM water electrolyzer cells have been operated for several thousand hours at temperatures and current densities as high as 60 °C and 1 A/cm2, respectively.

Chitin, a fascinating biopolymer found in living organisms, fulfills current demands of availability, sustainability, biocompatibility, biodegradability, functionality, and renewability. A feature of chitin is its ability to structure into hierarchical assemblies, spanning the nano- and macroscales, imparting toughness and resistance (chemical, biological, among others) to multicomponent materials as well as adding adaptability, tunability, and versatility. Retaining the inherent structural characteristics of chitin and its colloidal features in dispersed media has been central to its use, considering it as a building block for the construction of emerging materials. Top-down chitin designs have been reported and differentiate from the traditional molecular-level, bottom-up synthesis and assembly for material development. Such topics are the focus of this Review, which also covers the origins and biological characteristics of chitin and their influence on the morphological and physical-chemical properties. We discuss recent achievements in the isolation, deconstruction, and fractionation of chitin nanostructures of varying axial aspects (nanofibrils and nanorods) along with methods for their modification and assembly into functional materials. We highlight the role of nanochitin in its native architecture and as a component of materials subjected to multiscale interactions, leading to highly dynamic and functional structures. We introduce the most recent advances in the applications of nanochitin-derived materials and industrialization efforts, following green manufacturing principles. Finally, we offer a critical perspective about the adoption of nanochitin in the context of advanced, sustainable materials.

Converting solar energy to fuels has attracted substantial interest over the past decades because it has the potential to sustainably meet the increasing global energy demand. However, achieving this potential requires significant technological advances. Polymer photoelectrodes are composed of earth-abundant elements, e.g. carbon, nitrogen, oxygen, hydrogen, which promise to be more economically sustainable than their inorganic counterparts. Furthermore, the electronic structure of polymer photoelectrodes can be more easily tuned to fit the solar spectrum than inorganic counterparts, promising a feasible practical application. As a fast-moving area, in particular, over the past ten years, we have witnessed an explosion of reports on polymer materials, including photoelectrodes, cocatalysts, device architectures, and fundamental understanding experimentally and theoretically, all of which have been detailed in this review. Furthermore, the prospects of this field are discussed to highlight the future development of polymer photoelectrodes.

Advances in synthetic carbohydrate chemistry have dramatically improved access to common glycans. However, many novel methods still fail to adequately address challenges associated with chemical glycosylation and glycan synthesis. Since a challenge of glycosylation has remained, scientists have been frequently returning to the traditional glycosyl donors. This review is dedicated to glycosyl halides that have played crucial roles in shaping the field of glycosciences and continue to pave the way toward our understanding of chemical glycosylation.

Despite tremendous efforts in the past two years, our understanding of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), virus-host interactions, immune response, virulence, transmission, and evolution is still very limited. This limitation calls for further in-depth investigation. Computational studies have become an indispensable component in combating coronavirus disease 2019 (COVID-19) due to their low cost, their efficiency, and the fact that they are free from safety and ethical constraints. Additionally, the mechanism that governs the global evolution and transmission of SARS-CoV-2 cannot be revealed from individual experiments and was discovered by integrating genotyping of massive viral sequences, biophysical modeling of protein-protein interactions, deep mutational data, deep learning, and advanced mathematics. There exists a tsunami of literature on the molecular modeling, simulations, and predictions of SARS-CoV-2 and related developments of drugs, vaccines, antibodies, and diagnostics. To provide readers with a quick update about this literature, we present a comprehensive and systematic methodology-centered review. Aspects such as molecular biophysics, bioinformatics, cheminformatics, machine learning, and mathematics are discussed. This review will be beneficial to researchers who are looking for ways to contribute to SARS-CoV-2 studies and those who are interested in the status of the field.