Performance enhancement and mechanism of electroenhanced peroxymonosulfate activation by single-atom Fe catalyst modified electrodes.

Peroxymonosulfate-based electrochemical advanced oxidation processes (PMS-EAOPs) have great potential for sustainable water purification, so an in-depth understanding of its catalytic mechanism is imperative to facilitate its practical application. Herein, the performance enhancement and mechanism of electroenhanced PMS activation by single-atom Fe catalyst modified carbon felt was investigated. Compared with the anode, the cathode exhibited faster bisphenol A degradation (kcathode = 0.073 vs. kanode = 0.015 min-1), increased PMS consumption (98.8 vs. 10.3%), and an order of magnitude reduction of Fe dissolution (0.068 vs. 0.787 mg L-1). Mass transfer is a key factor limiting PMS activation, while the electrostriction of water in the hydrophobic region caused by cathode electric field (CEF) significantly increased mass transfer coefficient (km, cathode = 1.49 × 10-4 vs. km, anode = 2.68 × 10-5 m s-1). The enhanced activation of PMS is a synergistic result between electroactivation and catalyst-activation, which is controlled by the applied current density. 1O2 and direct electron transfer are the main active species and activation pathway, which achieve high degradation efficiency over pH 3 to 10. Density functional theory calculations prove CEF increases the adsorption energy, lengthens the O-O bond in PMS, and promotes charge transfer. A flow-through convection unit achieves sustainable operation with high removal efficiency (99.5% to 97.5%), low electrical energy consumption (0.15 kWh log-1 m-3), and low Fe leaching (0.81% of the total single atom Fe). This work reveals the critical role of electric fields in modulating Fenton-like catalytic activity, which may advance the development of advanced oxidation processes and other electrocatalytic applications.

Electrifying HCOOH synthesis from CO2 building blocks over Cu-Bi nanorod arrays.

Precise electrochemical synthesis of commodity chemicals and fuels from CO2 building blocks provides a promising route to close the anthropogenic carbon cycle, in which renewable but intermittent electricity could be stored within the greenhouse gas molecules. Here, we report state-of-the-art CO2-to-HCOOH valorization performance over a multiscale optimized Cu-Bi cathodic architecture, delivering a formate Faradaic efficiency exceeding 95% within an aqueous electrolyzer, a C-basis HCOOH purity above 99.8% within a solid-state electrolyzer operated at 100 mA cm-2 for 200 h and an energy efficiency of 39.2%, as well as a tunable aqueous HCOOH concentration ranging from 2.7 to 92.1 wt%. Via a combined two-dimensional reaction phase diagram and finite element analysis, we highlight the role of local geometries of Cu and Bi in branching the adsorption strength for key intermediates like *COOH and *OCHO for CO2 reduction, while the crystal orbital Hamiltonian population analysis rationalizes the vital contribution from moderate binding strength of η2(O,O)-OCHO on Cu-doped Bi surface in promoting HCOOH electrosynthesis. The findings of this study not only shed light on the tuning knobs for precise CO2 valorization, but also provide a different research paradigm for advancing the activity and selectivity optimization in a broad range of electrosynthetic systems.

Prebiotic chemical reactivity in solution with quantum accuracy and microsecond sampling using neural network potentials.

While RNA appears as a good candidate for the first autocatalytic systems preceding the emergence of modern life, the synthesis of RNA oligonucleotides without enzymes remains challenging. Because the uncatalyzed reaction is extremely slow, experimental studies bring limited and indirect information on the reaction mechanism, the nature of which remains debated. Here, we develop neural network potentials (NNPs) to study the phosphoester bond formation in water. While NNPs are becoming routinely applied to nonreactive systems or simple reactions, we demonstrate how they can systematically be trained to explore the reaction phase space for complex reactions involving several proton transfers and exchanges of heavy atoms. We then propagate at moderate computational cost hundreds of nanoseconds of a variety of enhanced sampling simulations with quantum accuracy in explicit solvent conditions. The thermodynamically preferred reaction pathway is a concerted, dissociative mechanism, with the transient formation of a metaphosphate transition state and direct participation of water solvent molecules that facilitate the exchange of protons through the nonbridging phosphate oxygens. Associative-dissociative pathways, characterized by a much tighter pentacoordinated phosphate, are higher in free energy. Our simulations also suggest that diprotonated phosphate, whose reactivity is never directly assessed in the experiments, is significantly less reactive than the monoprotonated species, suggesting that it is probably never the reactive species in normal pH conditions. These observations rationalize unexplained experimental results and the temperature dependence of the reaction rate, and they pave the way for the design of more efficient abiotic catalysts and activating groups.

Embedding electronic perpetual motion into single-atom catalysts for persistent Fenton-like reactions.

In our quest to leverage the capabilities of the emerging single-atom catalysts (SACs) for wastewater purification, we confronted fundamental challenges related to electron scarcity and instability. Through meticulous theoretical calculations, we identified optimal placements for nitrogen vacancies (Nv) and iron (Fe) single-atom sites, uncovering a dual-site approach that significantly amplified visible-light absorption and charge transfer dynamics. Informed by these computational insights, we cleverly integrated Nv into the catalyst design to boost electron density around iron atoms, yielding a potent and flexible photoactivator for benign peracetic acid. This exceptional catalyst exhibited remarkable stability and effectively degraded various organic contaminants over 20 cycles with self-cleaning properties. Specifically, the Nv sites captured electrons, enabling their swift transfer to adjacent Fe sites under visible light irradiation. This mechanism accelerated the reduction of the formed "peracetic acid-catalyst" intermediate. Theoretical calculations were used to elucidate the synergistic interplay of dual mechanisms, illuminating increased adsorption and activation of reactive molecules. Furthermore, electron reduction pathways on the conduction band were elaborately explored, unveiling the production of reactive species that enhanced photocatalytic processes. A six-flux model and associated parameters were also applied to precisely optimize the photocatalytic process, providing invaluable insights for future photocatalyst design. Overall, this study offers a molecule-level insight into the rational design of robust SACs in a photo-Fenton-like system, with promising implications for wastewater treatment and other high-value applications.

Dual factors required for cytochrome-P450-mediated hydrocarbon ring contraction in bacterial gibberellin phytohormone biosynthesis.

Cytochromes P450 (CYPs) are heme-thiolate monooxygenases that prototypically catalyze the insertion of oxygen into unactivated C-H bonds but are capable of mediating more complex reactions. One of the most remarked-upon alternative reactions occurs during biosynthesis of the gibberellin A (GA) phytohormones, involving hydrocarbon ring contraction with coupled aldehyde extrusion of ent-kaurenoic acid to form the first gibberellin intermediate. While the unusual nature of this reaction has long been noted, its mechanistic basis has remained opaque. Building on identification of the relevant CYP114 from bacterial GA biosynthesis, detailed structure-function studies are reported here, including development of in vitro assays as well as crystallographic analyses both in the absence and presence of substrate. These structures provided insight into enzymatic catalysis of this unusual reaction, as exemplified by identification of a key role for the "missing" acid from an otherwise highly conserved acid-alcohol pair of residues. Notably, the results demonstrate that ring contraction requires dual factors, both the use of a dedicated ferredoxin and absence of the otherwise conserved acidic residue, with exclusion of either limiting turnover to just the initiating and more straightforward hydroxylation. The results provide detailed insight into the enzymatic structure-function relationships underlying this fascinating reaction and support the use of a semipinacol mechanism for the unusual ring contraction reaction.

A metal-free carbon catalyst for oxidative dehydrogenation of aryl cyclohexenes to produce biaryl compounds.

A metal-free route based on a carbon catalyst to synthesize biphenyls through oxidative dehydrogenation (ODH) of phenyl cyclohexene has been investigated. Among the samples examined, an air-oxidized active carbon exhibits the best activity with a 9.1 × 10-2 h-1 rate constant, yielding 74% biphenyl in 28 h at 140 °C under five bar O2 in anisole. The apparent activation energy is measured as 54.5 kJ⋅mol-1. The extended reaction scope, consisting of 15 differently substituted phenyl cyclohexenes, shows the wide applicability of the proposed method. The catalyst's good recyclability over six runs suggests this ODH method as a promising route to access the biaryl compounds. In addition, the reaction mechanism is investigated with a combination of X-ray photoelectron spectroscopy, functional group blocking, and model compounds of carbon catalysts and is proposed to be based on the redox cycle of the quinoidic groups on the carbon surface. Additional experiments prove that the addition of the catalytic amount of acid (methanesulfonic acid) accelerates the reaction. In addition, Hammett plot examination suggests the formation of a carbonium intermediate, and its possible structure is outlined.

Preparation of methanediamine (CH2(NH2)2)-A precursor to nucleobases in the interstellar medium.

Although methanediamine (CH2(NH2)2) has historically been the subject of theoretical scrutiny, it has never been isolated to date. Here, we report the preparation of methanediamine (CH2(NH2)2)-the simplest diamine. Low-temperature interstellar analog ices composed of ammonia and methylamine were exposed to energetic electrons which act as proxies for secondary electrons produced in the track of galactic cosmic rays. These experimental conditions, which simulate the conditions within cold molecular clouds, result in radical formation and initiate aminomethyl (CH2NH2) and amino ([Formula: see text]2) radical chemistry. Exploiting tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReToF-MS) to make isomer-specific assignments, methanediamine was identified in the gas phase upon sublimation, while its isomer methylhydrazine (CH3NHNH2) was not observed. The molecular formula was confirmed to be CH6N2 through the use of isotopically labeled reactants. Methanediamine is the simplest molecule to contain the NCN moiety and could be a vital intermediate in the abiotic formation of heterocyclic and aromatic systems such as nucleobases, which all contain the NCN moiety.

Visualization of mutagenic nucleotide processing by Escherichia coli MutT, a Nudix hydrolase.

Escherichia coli MutT prevents mutations by hydrolyzing mutagenic 8-oxo-2'-deoxyguanosine 5'-triphosphate (8-oxo-dGTP) in the presence of Mg2+ or Mn2+ ions. MutT is one of the most studied enzymes in the nucleoside diphosphate-linked moiety X (Nudix) hydrolase superfamily, which is widely distributed in living organisms. However, the catalytic mechanisms of most Nudix hydrolases, including two- or three-metal-ion mechanisms, are still unclear because these mechanisms are proposed using the structures mimicking the reaction states, such as substrate analog complexes. Here, we visualized the hydrolytic reaction process of MutT by time-resolved X-ray crystallography using a biological substrate, 8-oxo-dGTP, and an active metal ion, Mn2+. The reaction was initiated by soaking MutT crystals in a MnCl2 solution and stopped by freezing the crystals at various time points. In total, five types of intermediate structures were refined by investigating the time course of the electron densities in the active site as well as the anomalous signal intensities of Mn2+ ions. The structures and electron densities show that three Mn2+ ions bind to the Nudix motif of MutT and align the substrate 8-oxo-dGTP for catalysis. Accompanied by the coordination of the three Mn2+ ions, a water molecule, bound to a catalytic base, forms a binuclear Mn2+ center for nucleophilic substitution at the ß-phosphorus of 8-oxo-dGTP. The reaction condition using Mg2+ also captured a structure in complex with three Mg2+ ions. This study provides the structural details essential for understanding the three-metal-ion mechanism of Nudix hydrolases and proposes that some of the Nudix hydrolases share this mechanism.

Unveiling the mechanism for selective cleavage of C-C bonds in sugar reactions on tungsten trioxide-based catalysts.

Conversion of naturally occurring sugars, the most abundant biomass resources on Earth, to fuels and chemicals provides a sustainable and carbon-neutral alternative to the current fossil resource-based processes. Tungsten-based catalysts (e.g., WO3) are efficient for selectively cleaving C-C bonds of sugars to C2,3 oxygenate intermediates (e.g., glycolaldehyde) that can serve as platform molecules with high viability and versatility in the synthesis of various chemicals. Such C-C bond cleavage follows a mechanism distinct from the classical retro-aldol condensation. Kinetic, isotope 13C-labeling, and spectroscopic studies and theoretical calculations, reveal that the reaction proceeds via a surface tridentate complex as the critical intermediate on WO3, formed by chelating both α- and ß-hydroxyls of sugars, together with the carbonyl group, with two adjacent tungsten atoms (W-O-W) contributing to the ß-C-C bond cleavage. This mechanism provides insights into sugar chemistry and enables the rational design of catalytic sites and reaction pathways toward the efficient utilization of sugar-based feedstocks.

Mechanistic analysis of carbon-carbon bond formation by deoxypodophyllotoxin synthase.

Deoxypodophyllotoxin contains a core of four fused rings (A to D) with three consecutive chiral centers, the last being created by the attachment of a peripheral trimethoxyphenyl ring (E) to ring C. Previous studies have suggested that the iron(II)- and 2-oxoglutarate-dependent (Fe/2OG) oxygenase, deoxypodophyllotoxin synthase (DPS), catalyzes the oxidative coupling of ring B and ring E to form ring C and complete the tetracyclic core. Despite recent efforts to deploy DPS in the preparation of deoxypodophyllotoxin analogs, the mechanism underlying the regio- and stereoselectivity of this cyclization event has not been elucidated. Herein, we report 1) two structures of DPS in complex with 2OG and (±)-yatein, 2) in vitro analysis of enzymatic reactivity with substrate analogs, and 3) model reactions addressing DPS's catalytic mechanism. The results disfavor a prior proposal of on-pathway benzylic hydroxylation. Rather, the DPS-catalyzed cyclization likely proceeds by hydrogen atom abstraction from C7', oxidation of the benzylic radical to a carbocation, Friedel-Crafts-like ring closure, and rearomatization of ring B by C6 deprotonation. This mechanism adds to the known pathways for transformation of the carbon-centered radical in Fe/2OG enzymes and suggests what types of substrate modification are likely tolerable in DPS-catalyzed production of deoxypodophyllotoxin analogs.

Rational Design of Quasi-1D Multicore-Shell MnSe@N-Doped Carbon Nanorods as High-Performance Anode Material for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are considered one of the promising candidates for energy storage devices due to the low cost and low redox potential of sodium. However, their implementation is hindered by sluggish kinetics and rapid capacity decay caused by inferior conductivity, lattice deterioration, and volume changes of conversion-type anode materials. Herein, we report the design of a multicore-shell anode material based on manganese selenide (MnSe) nanoparticle encapsulated N-doped carbon (MnSe@NC) nanorods. Benefiting from the conductive multicore-shell structure, the MnSe@NC anodes displayed prominent rate capability (152.7 mA h g-1 at 5 A g-1) and long lifespan (132.7 mA h g-1 after 2000 cycles at 5 A g-1), verifying the essence of reasonable anode construction for high-performance SIBs. Systematic in situ microscopic and spectroscopic methods revealed a highly reversible conversion reaction mechanism of MnSe@NC. Our study proposes a promising route toward developing advanced transition metal selenide anodes and comprehending electrochemical reaction mechanisms toward high-performance SIBs.

Construction of an Electron Capture and Transfer Center for Highly Efficient and Selective Solar-Light-Driven CO2 Conversion.

Exploring high-efficiency photocatalysts for selective CO2 reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe2 nanosheet was incorporated on g-C3N4 to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO2 photoreduction. Quasi in situ X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe2 could capture electrons, which are further transferred to the surface for activating active sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe2/PCN (protonated C3N4) photocatalyst. As an outcome, the optimized VSe2/PCN composite achieved 97% selectivity for solar-light-driven CO2 conversion to CO with a high rate of 16.3 µmol·g-1·h-1, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO2 conversion.

A biosynthetic aspartate N-hydroxylase performs successive oxidations by holding intermediates at a site away from the catalytic center.

Nitrosuccinate is a biosynthetic building block in many microbial pathways. The metabolite is produced by dedicated L-aspartate hydroxylases that use NADPH and molecular oxygen as co-substrates. Here, we investigate the mechanism underlying the unusual ability of these enzymes to perform successive rounds of oxidative modifications. The crystal structure of Streptomyces sp. V2 L-aspartate N-hydroxylase outlines a characteristic helical domain wedged between two dinucleotide-binding domains. Together with NADPH and FAD, a cluster of conserved arginine residues forms the catalytic core at the domain interface. Aspartate is found to bind in an entry chamber that is close to but not in direct contact with the flavin. It is recognized by an extensive H-bond network that explains the enzyme's strict substrate-selectivity. A mutant designed to create steric and electrostatic hindrance to substrate binding disables hydroxylation without perturbing the NADPH oxidase side-activity. Critically, the distance between the FAD and the substrate is far too long to afford N-hydroxylation by the C4a-hydroperoxyflavin intermediate whose formation is confirmed by our work. We conclude that the enzyme functions through a catch-and-release mechanism. L-aspartate slides into the catalytic center only when the hydroxylating apparatus is formed. It is then re-captured by the entry chamber where it waits for the next round of hydroxylation. By iterating these steps, the enzyme minimizes the leakage of incompletely oxygenated products and ensures that the reaction carries on until nitrosuccinate is formed. This unstable product can then be engaged by a successive biosynthetic enzyme or undergoes spontaneous decarboxylation to produce 3-nitropropionate, a mycotoxin.

Mechanistic study of the Ni-catalyzed hydroalkylation of 1,3-dienes: The origins of regio- and enantioselectivities and a further rational design.

The development of the catalytic regio- and enantioselective hydrofunctionalization of 1,3-dienes remains a challenge and requires deep insight into the reaction mechanisms. We herein thoroughly studied the reaction mechanism of the Ni-catalyzed hydroalkylation of 1,3-dienes with ketones by density functional theory (DFT) calculations. It reveals that the reaction is initiated by stepwise oxidative addition of EtO-H followed by 1,3-diene migratory insertion to generate the alkylnickel(II) intermediate, rather than the experimentally proposed ligand-to-ligand hydrogen transfer (LLHT) mechanism. In addition, we rationalized the role of t BuOK in the subsequent addition of enolate of ketone and transmetalation process. Based on the whole catalysis, the CC reductive elimination step, turns out to be the rate- and enantioselectivity-determining step. Furthermore, we disclosed the origins of the regio- and enantioselectivity of the product, and found that the 1,2-selectivity lies in the combination effects of the ligand-substrate electrostatic interactions, orbital interactions and Pauli repulsions, while the enantioselectivity mainly arises from substrate-ligand steric repulsions. Based on mechanistic study, new biaryl bisphosphine ligands affording higher enantioselectivity were designed, which will help to improve current catalytic systems and develop new transition-metal-catalyzed hydroalkylations.

Mechanistic insights into the role of cyclodextrin in the regioselective radical CH trifluoromethylation of aromatic compounds.

The regioselective radical CH trifluoromethylation of aromatic compounds have been shown to proceed in good yield and high regioselectivity when cyclodextrin (CD) is present. Yet, the reaction mechanism and the role of CD during the reaction have remained obscure. To this end, here we performed density functional theory (DFT) calculations to the conformations obtained by semiempirical quantum mechanical molecular dynamics calculations to reveal the reaction mechanism and the role of CD in controlling regioselectivity. The results show that metal salt increases the yield but do not affect the regioselectivity, which we further confirmed by an experiment. In contrast, multiple CD-substrate complex conformations and reaction pathways were obtained, and CD was shown to contribute to improving the regioselectivity by stabilizing the intermediate state via encapsulation. The present study indicates that CDs can increase the regioselectivity by stabilizing the intermediate and product states while only marginally affecting the transition state.

A new chapter in the never ending story of cycloadditions: The puzzling case of SO2 and acetylene.

A comprehensive study of the different classes of cycloaddition reactions ([3+2], [2+2], and [2+1]) of SO2 to acetylene and ethylene has been performed using density functional theory (DFT) and composite wavefunction methods. The [3+2] cycloaddition reaction, that was previously explored in the context of the cycloaddition of thioformaldehyde S-methylide (TSM) to ethylene and acetylene, proceeds in a concerted way to the formation of stable heterocycles. In this paper, we extend our study to the [2+2] and [2+1] cycloadditions of SO2 to acetylene, which would produce 1,1-oxathiete-2-oxide and thiirene-1,1-dioxide, respectively. One of the main conclusions is that cyclic 1,1-oxathiete-2-oxide can open through a relatively easy breaking of the SO single bond and rearrange toward sulfinyl acetaldehyde (SA). The SA molecule can easily undergo several internal rearrangements, which eventually lead to sulfenic acid and sulfoxide derivatives of ethenone, 1,2,3-dioxathiole, and CO plus sulfinylmethane. The most probable path, however, produces 2-thioxoacetic acid, whose derivatives (or those of the corresponding acetate) are usually obtained by Willgerodt-Kindler-type sulfuration of acetates. This product can in turn decompose, leading to the final products CO2 and H2CS. Comparison of this decomposition path with that of 2-amino-2-thioxoacetic acid shows that the process occurs through different H-transfer processes.

Recent Research on Iridium-Based Electrocatalysts for Acidic Oxygen Evolution Reaction from the Origin of Reaction Mechanism.

As the anode reaction of proton exchange membrane water electrolysis (PEMWE), the acidic oxygen evolution reaction (OER) is one of the main obstacles to the practical application of PEMWE due to its sluggish four-electron transfer process. The development of high-performance acidic OER electrocatalysts has become the key to improving the reaction kinetics. To date, although various excellent acidic OER electrocatalysts have been widely researched, Ir-based nanomaterials are still state-of-the-art electrocatalysts. Hence, a comprehensive and in-depth understanding of the reaction mechanism of Ir-based electrocatalysts is crucial for the precise optimization of catalytic performance. In this review, the origin and nature of the conventional adsorbate evolution mechanism (AEM) and the derived volcanic relationship on Ir-based electrocatalysts for acidic OER processes are summarized and some optimization strategies for Ir-based electrocatalysts based on the AEM are introduced. To further investigate the development strategy of high-performance Ir-based electrocatalysts, several unconventional OER mechanisms including dual-site mechanism and lattice oxygen mediated mechanism, and their applications are introduced in detail. Thereafter, the active species on Ir-based electrocatalysts at acidic OER are summarized and classified into surface Ir species and O species. Finally, the future development direction and prospect of Ir-based electrocatalysts for acidic OER are put forward.

Constructing Asymmetric Charge Polarized NiCo Prussian Blue Analogue for Promoted Electrocatalytic Methanol to Formate Conversion.

The highly selective electrochemical conversion of methanol to formate is of great significance for various clean energy devices, but understanding the structure-to-property relationship remains unclear. Here, the asymmetric charge polarized NiCo prussian blue analogue (NiCo PBA-100) is reported to exhibit remarkable catalytic performance with high current density (210 mA cm-2 @1.65 V vs RHE) and Faraday efficiency (over 90%). Meanwhile, the hybrid water splitting and Zinc-methanol-battery assembled by NiCo PBA-100 display the promoted performance with decent stability. X-ray absorption spectroscopy (XAS) and operando Raman spectroscopy indicate that the asymmetric charge polarization in NiCo PBA leads to more unoccupied states of Ni and occupied states of Co, thereby facilitating the rapid transformation of the high-active catalytic centers. Density functional theory calculations combining operando Fourier transform infrared spectroscopy demonstrate that the final reconstructed catalyst derived by NiCo PBA-100 exhibits rearranged d band properties along with a lowered energy barrier of the rate-determining step and favors the desired formate production.

Vanadium Hexacyanoferrate Prussian Blue Analogs for Aqueous Proton Storage: Excellent Electrochemical Properties and Mechanism Insights.

The significant attraction toward aqueous proton batteries (APBs) is attributable to their expedited kinetics, elevated safety profile, and economical feasibility. Nevertheless, their practical implement is significantly blocked by the unsatisfactory energy density due to the limited cathode materials. Herein, vanadium hexacyanoferrate Prussian blue analog (VOHCF) is introduced as a potentially favorable cathode material for APBs. The findings demonstrate that this VOHCF electrode exhibits a notable reversible capacity of 102.7 mAh g-1 and exceptional cycling stability, with 95.4% capacity retention over 10 000 cycles at 10 A g-1 . It is noteworthy that this is the detailed instance of VOHCF being proposed as a cathode for APBs. Combining the in situ characterization techniques and theoretical simulations, the origins of excellent proton storage performance are revealed as the multiple redox mechanisms with double active centers of ─C≡N group and V═O bond in VOHCF as well as the robust structure stability. A proton full cell with excellent performance is further achieved by coupling the VOHCF cathode and diquinoxalino[2,3-a:2',3'-c] phenazine (HATN) anode, demonstrating the great potential of VOHCF in practical applications. This work could provide fundamental understanding to the development of feasible cathode materials for proton storage device.

Halogen-Site Regulation in Cs3Bi2X9 Quantum Dots for Efficient and Selective Oxidation of Benzyl Alcohol Driven by Solar Light.

Sluggish charge kinetics and low selectivity limit the solar-driven selective organic transformations under mild conditions. Herein, an efficient strategy of halogen-site regulation, based on the precise control of charge transfer and molecule activation by rational design of Cs3Bi2X9 quantum dots photocatalysts, is proposed to achieve both high selectivity and yield of benzyl-alcohol oxidation. In situ PL spectroscopy study reveals that the Bi─Br bonds formed in the form of Br-associated coordination can enhance the separation and transfer of photoexcited carriers during the practical reaction. As the active center, the exclusive Bi─Br covalence can benefit the benzyl-alcohol activation for producing carbon-centered radicals. As a result, the Cs3Bi2Br9 with this atomic coordination achieves a conversion ratio of 97.9% for benzyl alcohol and selectivity of 99.6% for aldehydes, which are 56.9- and 1.54-fold higher than that of Cs3Bi2Cl9. Combined with quasi-in situ EPR, in situ ATR-FTIR spectra, and DFT calculation, the conversion of C6H5-CH2OH to C6H5-CH2* at Br-related coordination is revealed to be a determining step, which can be accelerated via halogen-site regulation for enhancing selectivity and photocatalytic efficiency. The mechanistic insights of this research elucidate how halogen-site regulation in favor of charge transfer and molecule activation toward efficient and selective oxidation of benzyl alcohol.