Modulating the Reaction Configuration by Breaking the Structural Symmetry of Active Sites for Efficient Photocatalytic Reduction of Low‐concentration CO₂

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Aug. 29, 2023

Photocatalytic conversion of low-concentration CO2 is considered as a promising way to simultaneously mitigate the environmental and energy issues. However, weak adsorption tough activation process seriously compromise CO production, due chemical inertness molecule formed fragile metal-C/O bond. Herein, we designed fabricated oxygen vacancy contained Co3 O4 hollow nanoparticles on ordered macroporous N-doped carbon framework (Vo-HCo3 /OMNC) towards photoreduction . In situ spectra ab initio molecular dynamics simulations reveal that constructed able break local structural symmetry Co-O-Co sites. The formation asymmetric active site switches configuration from single-site linear model multiple-sites bending one with highly stable configuration, enhancing binding polarization molecules. As result, Vo-HCo3 /OMNC shows unprecedent activity in photocatalytic (10 % /Ar) under laboratory light source or even natural sunlight, affording syngas yield 337.8 95.2 mmol g-1 h-1 , respectively, an apparent quantum up 4.2 %.

Language: Английский

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Open-Framework Vanadate as Efficient Ion Exchanger for Uranyl Removal

Environmental Science & Technology, Journal Year: 2024, Volume and Issue: 58(21), P. 9456 - 9465

Published: May 15, 2024

The elimination of uranium from radioactive wastewater is crucial for the safe management and operation environmental remediation. Here, we present a layered vanadate with high acid/base stability, [Me2NH2]V3O7, as an excellent ion exchanger capturing uranyl highly complex aqueous solutions. material possesses indirect band gap, ferromagnetic characteristic flower-like morphology comprising parallel nanosheets. structure [Me2NH2]V3O7 predominantly upheld by H-bond interaction between anionic framework [V3O7]nn– intercalated [Me2NH2]+. [Me2NH2]+ within can be readily exchanged UO22+. exhibits exchange capacity (qm = 176.19 mg/g), fast kinetics (within 15 min), removal efficiencies (>99%), good selectivity against excess interfering ions. It also displays activity UO22+ over wide pH range (2.00–7.12). More importantly, has capability to effectively remove low-concentration uranium, yielding residual U concentration 13 ppb, which falls below EPA-defined acceptable limit 30 ppb in typical drinking water. efficiently separate Cs+ or Sr2+ achieving highest separation factors (SFU/Cs 589 SFU/Sr 227) date. BOMD DFT calculations reveal that driving force dominated [V3O7]nn–, whereas rate influenced mobility Our experimental findings indicate considered promising scavenger Additionally, simulation results provide valuable mechanistic interpretations serve reference designing novel exchangers.

Language: Английский

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Automated Quantification of Hydroxyl Reactivities: Prediction of Glycosylation Reactions

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(22), P. 12413 - 12423

Published: Feb. 26, 2021

Abstract The stereoselectivity and yield in glycosylation reactions are paramount but unpredictable. We have developed a database of acceptor nucleophilic constants (Aka) to quantify the nucleophilicity hydroxyl groups influenced by steric, electronic structural effects, providing connection between experiments computer algorithms. subtle reactivity differences among on various carbohydrate molecules can be defined Aka, which is easily accessible simple convenient automation system assure high reproducibility accuracy. A diverse range donors acceptors with well‐defined promoters were organized processed designed software program “GlycoComputer” for prediction without involving sophisticated computational processing. importance Aka was further verified random forest algorithm, applicability tested synthesis Lewis skeleton show that accurately estimated.

Language: Английский

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Mimicry of the proton wire mechanism of enzymes inside a supramolecular capsule enables β-selective O-glycosylations

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(9), P. 985 - 994

Published: July 7, 2022

Language: Английский

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Recent Advances in Stereoselective Chemical O-Glycosylation Reactions

Frontiers in Molecular Biosciences, Journal Year: 2022, Volume and Issue: 9

Published: June 14, 2022

Carbohydrates involving glycoconjugates play a pivotal role in many life processes. Better understanding toward glycobiological events including the structure–function relationship of these biomolecules and for diagnostic therapeutic purposes tailor-made vaccine development synthesis structurally well-defined oligosaccharides (OS) become important. Efficient chemical glycosylation high yield stereoselectivity is however challenging depends on fine tuning protection profile to get matching glycosyl donor–acceptor reactivity along with proper use other important external factors like catalyst, solvent, temperature, activator, additive. So far, methods have been reported several reviews also. In present review, we will concentrate our discussion recent trend α- β-selective reactions during past decade.

Language: Английский

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Type-II van der Waals heterostructures of GeC, ZnO and Al2SO monolayers for promising optoelectronic and photocatalytic applications

International Journal of Hydrogen Energy, Journal Year: 2023, Volume and Issue: 48(65), P. 25354 - 25365

Published: April 5, 2023

Language: Английский

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Accelerating explicit solvent models of heterogeneous catalysts with machine learning interatomic potentials

Chemical Science, Journal Year: 2023, Volume and Issue: 14(31), P. 8338 - 8354

Published: Jan. 1, 2023

Realistically modelling how solvents affect catalytic reactions is a longstanding challenge due to its prohibitive computational cost. Typically, an explicit atomistic treatment of the solvent molecules needed together with molecular dynamics (MD) simulations and enhanced sampling methods. Here, we demonstrate utility machine learning interatomic potentials (MLIPs), coupled active learning, enable fast accurate adsorption on heterogeneous catalysts. MLIPs trained on-the-fly were able accelerate ab initio MD by up 4 orders magnitude while reproducing high fidelity geometrical features water in bulk at metal-water interfaces. Using these ML-accelerated simulations, accurately predicted key quantities such as energies CO*, OH*, COH*, HCO*, OCCHO* Cu surfaces free energy barriers C-H scission ethylene glycol over Pd surfaces, validated calculations. We envision that will pave way towards detailed realistic studies solvated catalysts large time- length-scales.

Language: Английский

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Stereospecific alkenylidene homologation of organoboronates by SNV reaction

Nature, Journal Year: 2024, Volume and Issue: 631(8020), P. 328 - 334

Published: May 23, 2024

Language: Английский

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Glycosidase mechanisms: Sugar conformations and reactivity in endo- and exo-acting enzymes

Current Opinion in Chemical Biology, Journal Year: 2023, Volume and Issue: 74, P. 102282 - 102282

Published: March 15, 2023

The enzymatic breakdown of carbohydrates plays a critical role in several biological events and enables the development sustainable processes to obtain bioproducts biofuels. In this scenario, design efficient inhibitors for glycosidases that can act as drug targets engineering carbohydrate-active enzymes with tailored catalytic properties is remarkable importance. To guide rational approaches, it necessary elucidate enzyme molecular mechanisms, particular understanding how microenvironment modulates conformational space explored by substrate. Computer simulations, especially those based on ab initio methods, have provided suitable atomic description carbohydrate conformations reactions glycosidase families. review, we will focus active-site topology (pocket or cleft) mode cleavage (endo exo) affect mechanisms adopted glycosidases, substrate along reaction coordinate.

Language: Английский

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Unraveling the promoter effect and the roles of counterion exchange in glycosylation reaction

Science Advances, Journal Year: 2023, Volume and Issue: 9(42)

Published: Oct. 18, 2023

The stereoselectivity of glycosidic bond formation continues to pose a noteworthy hurdle in synthesizing carbohydrates, primarily due the simultaneous occurrence S

Language: Английский

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