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"Selectivity"
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Steering CO₂ electroreduction pathway toward ethanol via surface-bounded hydroxyl species-induced noncovalent interaction
Selective electroreduction of carbon dioxide (CO2RR) into ethanol at an industrially relevant current density is highly desired. However, it is challenging because the competing ethylene production pathway is generally more thermodynamically favored. Herein, we achieve a selective and productive ethanol production over a porous CuO catalyst that presents a high ethanol Faradaic efficiency (FE) of 44.1 ± 1.0% and an ethanol-to-ethylene ratio of 1.2 at a large ethanol partial current density of 501.0 ± 15.0 mA cm−2, in addition to an extraordinary FE of 90.6 ± 3.4% for multicarbon products. Intriguingly, we found a volcano-shaped relationship between ethanol selectivity and nanocavity size of porous CuO catalyst in the range of 0 to 20 nm. Mechanistic studies indicate that the increased coverage of surface-bounded hydroxyl species (*OH) associated with the nanocavity size-dependent confinement effect contributes to the remarkable ethanol selectivity, which preferentially favors the *CHCOH hydrogenation to *CHCHOH (ethanol pathway) via yielding the noncovalent interaction. Our findings provide insights in favoring the ethanol formation pathway, which paves the path toward rational design of ethanol-oriented catalysts.
Journal Article
Controlled growth of a high selectivity interface for seawater electrolysis
Overall seawater electrolysis is an important direction for the development of hydrogen energy conversion. The key issues include how to achieve high selectivity, activity, and stability in seawater electrolysis reactions. In this report, the heterostructures of graphdiyne-RhOₓ-graphdiyne (GDY/RhOₓ/GDY) were constructed by in situ-controlled growth of GDY on RhOx nanocrystals. A double layer interface of sp-hybridized carbon-oxide-Rhodium (sp-C∼O-Rh) was formed in this system. The microstructures at the interface are composed of active sites of sp-C∼O-Rh. The obvious electron-withdrawing surface enhances the catalytic activity with orders of magnitude, while the GDY outer of the metal oxides guarantees the stability. The electron-donating and withdrawing sp-C∼O-Rh structures enhance the catalytic activity, achieving high-performance overall seawater electrolysis with very small cell voltages of 1.42 and 1.52 V at large current densities of 10 and 500 mA cm−2 at room temperatures and ambient pressures, respectively. The compositional and structural superiority of the GDY-derived sp-C-metal-oxide active center offers great opportunities to engineer tunable redox properties and catalytic performance for seawater electrolysis and beyond. This is a typical successful example of the rational design of catalytic systems.
Journal Article
Recent Approaches for Cleaving the C─C Bond During Ethanol Electro‐Oxidation Reaction
Direct ethanol fuel cells (DEFCs) play an indispensable role in the cyclic utilization of carbon resources due to its high volumetric energy density, high efficiency, and environmental benign character. However, owing to the chemically stable carbon‐carbon (C─C) bond of ethanol, its incomplete electrooxidation at the anode severely inhibits the energy and power density output of DEFCs. The efficiency of C─C bond cleaving on the state‐of‐the‐art Pt or Pd catalysts is reported as low as 7.5%. Recently, tremendous efforts are devoted to this field, and some effective strategies are put forward to facilitate the cleavage of the C─C bond. It is the right time to summarize the major breakthroughs in ethanol electrooxidation reaction. In this review, some optimization strategies including constructing core–shell nanostructure with alloying effect, doping other metal atoms in Pt and Pd catalysts, engineering composite catalyst with interface synergism, introducing cascade catalytic sites, and so on, are systematically summarized. In addition, the catalytic mechanism as well as the correlations between the catalyst structure and catalytic efficiency are further discussed. Finally, the prevailing limitations and feasible improvement directions for ethanol electrooxidation are proposed. The major breakthroughs of C─C bond cleavage strategies in ethanol electrooxidation reaction including construction of core–shell nanostructure with alloying effect, doping other metal atoms in Pt and Pd catalysts, engineering composite catalyst with interface synergism, and introducing cascade catalytic sites are systematically summarized. In addition, the prevailing limitations and feasible improvement directions for ethanol electrooxidation are proposed.
Journal Article
Chiral-induced spin selectivity in the formation and recombination of radical pairs: cryptochrome magnetoreception and EPR detection
That the rates and yields of reactions of organic radicals can be spin dependent is well known in the context of the radical pair mechanism (RPM). Less well known, but still well established, is the chiral-induced spin selectivity (CISS) effect in which chiral molecules act as spin filters that preferentially transmit electrons with spins polarized parallel or antiparallel to their direction of motion. Starting from the assumption that CISS can arise in electron transfer reactions of radical pairs, we propose a simple way to include CISS in conventional models of radical pair spin dynamics. We show that CISS can (a) increase the sensitivity of radical pairs to the direction of a weak external magnetic field, (b) change the dependence of the magnetic field effect on the reaction rate constants, and (c) destroy the field-inversion symmetry characteristic of the RPM. We argue that CISS polarization effects could be observable by EPR (electron paramagnetic resonance) of oriented samples either as differences in continuous wave, time-resolved spectra recorded with the spectrometer field parallel or perpendicular to the CISS quantization axis or as signals in the in-phase channel of an out-of-phase ESEEM (electron spin echo envelope modulation) experiment. Finally we assess whether CISS might be relevant to the hypothesis that the magnetic compass of migratory songbirds relies on photochemically-formed radical pairs in cryptochrome flavoproteins. Although CISS effects offer the possibility of evolving a more sensitive or precise compass, the associated lack of field-inversion symmetry has not hitherto been observed in behavioural experiments. In addition, it may no longer be safe to assume that the observation of a polar magnetic compass response in an animal can be used as evidence against a radical pair sensory mechanism.
Journal Article
Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction
The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surfaceadsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations (methyl₄N⁺, ethyl₄N⁺, propyl₄N⁺, and butyl₄N⁺), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of methyl₄N⁺ and ethyl₄N⁺ cations, whereas this product is not synthesized in propyl₄N⁺- and butyl₄N⁺-containing electrolytes. Surface-enhanced infrared absorption spectroscopy (SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process.
Journal Article
Activation mechanism of the β 2 -adrenergic receptor
A third of marketed drugs act by binding to a G-protein-coupled receptor (GPCR) and either triggering or preventing receptor activation. Although recent crystal structures have provided snapshots of both active and inactive functional states of GPCRs, these structures do not reveal the mechanism by which GPCRs transition between these states. Here we propose an activation mechanism for the β 2 -adrenergic receptor, a prototypical GPCR, based on atomic-level simulations in which an agonist-bound receptor transitions spontaneously from the active to the inactive crystallographically observed conformation. A loosely coupled allosteric network, comprising three regions that can each switch individually between multiple distinct conformations, links small perturbations at the extracellular drug-binding site to large conformational changes at the intracellular G-protein-binding site. Our simulations also exhibit an intermediate that may represent a receptor conformation to which a G protein binds during activation, and suggest that the first structural changes during receptor activation often take place on the intracellular side of the receptor, far from the drug-binding site. By capturing this fundamental signaling process in atomic detail, our results may provide a foundation for the design of drugs that control receptor signaling more precisely by stabilizing specific receptor conformations.
Journal Article
Structural basis for replicase polyprotein cleavage and substrate specificity of main protease from SARS-CoV-2
The main protease (Mpro) of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is a key enzyme, which extensively digests CoV replicase polyproteins essential for viral replication and transcription, making it an attractive target for antiviral drug development. However, the molecular mechanism of how Mpro of SARS-CoV-2 digests replicase polyproteins, releasing the nonstructural proteins (nsps), and its substrate specificity remain largely unknown. Here, we determine the high-resolution structures of SARS-CoV-2 Mpro in its resting state, precleavage state, and postcleavage state, constituting a full cycle of substrate cleavage. The structures show the delicate conformational changes that occur during polyprotein processing. Further, we solve the structures of the SARS-CoV-2 Mpro mutant (H41A) in complex with six native cleavage substrates from replicase polyproteins, and demonstrate that SARS-CoV-2 Mpro can recognize sequences as long as 10 residues but only have special selectivity for four subsites. These structural data provide a basis to develop potent new inhibitors against SARS-CoV-2.
Journal Article