Abstract Cobalt coordinated covalent organic frameworks have attracted increasing interest in the field of CO 2 photoreduction to CO, owing their high electron affinity and predesigned structures. However, achieving conversion efficiency is challenging since most Co related coordination environments facilitate fast recombination photogenerated electron-hole pairs. Here, we design two kinds Co-COF catalysts with oxygen atoms find that after tuning environment, reported framework catalyst Co-O...

Covalent organic frameworks (COFs) hold the potential in converting CO2 with water into value-added fuels and O2 to save deteriorating ecological environment. However, reaching high yield selectivity is a grand challenge under metal-, photosensitizer-, or sacrificial reagent-free conditions. Here, inspired by microstructures of natural leaves, we designed triazine-based COF membranes integration steady light-harvesting sites, efficient catalytic center, fast charge/mass transfer...

Precise control of the structure and spatial distance Lewis acid (LA) base (LB) sites in a porous system to construct efficient solid frustrated pair (FLP) catalyst is vital for industrial application but remains challenging. Herein, we constructed FLP polyoxometalate (POM)-based metal-organic framework (MOF) by introducing coordination-defect metal nodes surface-basic POM with abundant oxygen (LB). The well-defined unique conformation defective POM-based MOF ensure that between LA LB at...

Single-atom catalysts on supported silicomolybdic acid for CO 2 electroreduction.

Metal-nitrogen-carbon catalysts, as promising alternative to platinum-based catalysts for oxygen reduction reaction (ORR), are still highly expected achieve better performance by modulating the composition and spatial structure of active site. Herein, we constructed non-planar nest-like [Fe2 S2 ] cluster sites in N-doped carbon plane. Adjacent double Fe atoms effectively weaken O-O bond forming a peroxide bridge-like adsorption configuration, introduction S breaks planar coordination...

Abstract Stabilizing specific intermediates to produce CH 4 remains a main challenge in solar‐driven CO 2 reduction. Herein, g‐C 3 N is modified with saturated and lacunary phosphotungstates (PW x , =12, 11, 9) tailor the reduction pathway yield high selectivity. Increased lacuna of leads higher selectivity, superior selectivity 80 % 40.8 μmol ⋅ g −1 h evolution rate for PW 9 /g‐C . Conversely, alone show negligible production. The conversion follows tandem catalytic process. initially...

The construction of single-atom catalysts (SACs) using polyoxometalates (POMs) as supports has attracted significant attention. Specifically, POMs possess the unique ability to reversibly accept and donate electrons; yet, potential benefits this distinctive characteristic on activity single atoms have remained unexplored. In study, we employ density functional theory (DFT) calculations investigate synthesis CH3COOH from CO, CH4, H2O catalyzed by POM-supported SAC M1/POM (M = Pt, Rh, Ru, Pd,...

The inherent sluggish kinetics of the conventional four-electron transfer pathway fundamentally limits oxygen reduction reaction (ORR) efficiency. While electronic structure modulation offers potential solutions, developing effective catalytic regulation strategies remains challenging due to elusive structure-activity correlations. In this study, Fe4 cluster sites are engineered with dual parallel electron channels that enable concurrent O─O bond cleavage and atom protonation. This unique...

The design and synthesis of polynuclear metal cluster-based coordination cages is considerable interest due to their appealing structural characteristics potential applications. Herein, we report a calix[4]resorcinarene-based [Co12] cage, [Co12(TPC4R-I)2(1,3-BDC)10(μ3-OH)4(H2O)10(DMF)2]·7DMF·23H2O (1), assembled with 2 bowl-shaped calix[4]resorcinarenes (TPC4R-I), 10 angular 1,3-benzenedicarboxylates (1,3-BDC), 12 Co(II) cations. Remarkably, it shown be highly efficient recyclable...

The iron catalyst (POM-Fe) could combine with chloride ions to form a supramolecular aggregate FeMo 6 ·Cl, which was used in the oxidation of alcohols carboxylic acids under mild conditions and can tolerate 40 substrates moderate high yield.

Abstract Metal‐nitrogen‐carbon catalysts, as promising alternative to platinum‐based catalysts for oxygen reduction reaction (ORR), are still highly expected achieve better performance by modulating the composition and spatial structure of active site. Herein, we constructed non‐planar nest‐like [Fe 2 S ] cluster sites in N‐doped carbon plane. Adjacent double Fe atoms effectively weaken O−O bond forming a peroxide bridge‐like adsorption configuration, introduction breaks planar coordination...

Carbon dioxide (CO

In this work, the mechanism of water oxidation catalyzed by an Ru-based complex [Ru(L)]+ (L = 5,5-chelated 2-carboxyl-phen, 2,2';6',2''-terpyridine) was studied density functional theory (DFT) calculations. [Ru(L)]+, a carboxyl group is included in second coordination sphere and plays important role catalytic process. activation stage catalysis, proposed as promising proton acceptor to promote transfer, which results active RuV[double bond, length m-dash]O species. Then, O-O bond formation...

The performance of MnII/III-monosubstituted heteropolytungstates [MnIII(H2O)GeW11O39]5- ([GT-MnIII-OH2]5-, where GT = GeW11O39) and [MnII(H2O)GeW11O39]6- ([GT-MnII-OH2]6-) as water oxidation catalysts at pH 9 was explored using density functional theory calculations. counterion effect fully considered, in which five six Na+ ions were included the calculations for catalyzed by [GT-MnIII-OH2]5- [GT-MnII-OH2]6-, respectively. process catalysis divided into three elemental stages: (i) oxidative...

With rapid industrial development, the increasing energy consumption has led to severe environmental pollution.

The geometrical and electronic structures of [M 6 O[Formula: see text]][Formula: text] (M [Formula: Mo, W, text]; M V, Nb, Ta, text]) their derivatives were investigated by using density functional theory methods. results indicate that the structure [V is not different from other Lindqvist-type anions. energy gap between highest occupied molecular orbital (HOMO) lowest unoccupied (LUMO) (HOMO[Formula: text]LUMO gap) smaller than those same charge anions, [Nb [Ta text]. In addition, larger...

Recently, the catalytic activity of Lindqvist-type hexamolybdate [Mo6O19]2– in oxidation an aniline derivative (LPhNH2, L = substituent) was demonstrated by Wei and co-workers (Angew. Chem. Int. Ed. 2021, 60, 6382–6385). Herein, taking phenylamine (PhNH2) to azobenzene (PhNNPh) as a model reaction, we report density functional theory investigation mechanism illustrate critical experimental phenomena. During once preassociation PhNH2 takes place, electron transfer proton immediately proceed...

Abstract Precise control of the structure and spatial distance Lewis acid (LA) base (LB) sites in a porous system to construct efficient solid frustrated pair (FLP) catalyst is vital for industrial application but remains challenging. Herein, we constructed FLP polyoxometalate (POM)‐based metal–organic framework (MOF) by introducing coordination‐defect metal nodes surface‐basic POM with abundant oxygen (LB). The well‐defined unique conformation defective POM‐based MOF ensure that between LA...

Polyoxometalates (POMs) have a broad array of applied platforms with well-characterized catalysis to achieve N–H bond activation. Herein, the mechanism Anderson-type POM-based catalyst [FeIIIMoVI6O18{(OCH2)3CNH2}2]3– ([TrisFeIIIMoVI6O18]3–, Tris = {(OCH2)3CNH2}2) for activation hydrazine (PhHNNHPh) was investigated by density functional theory calculations. The results reveal that [TrisFeIIIMoVI6O18]3– as active species is responsible continuous abstraction two electrons and protons PhHNNHPh...

Abstract Stabilizing specific intermediates to produce CH 4 remains a main challenge in solar‐driven CO 2 reduction. Herein, g‐C 3 N is modified with saturated and lacunary phosphotungstates (PW x , =12, 11, 9) tailor the reduction pathway yield high selectivity. Increased lacuna of leads higher selectivity, superior selectivity 80 % 40.8 μmol ⋅ g −1 h evolution rate for PW 9 /g‐C . Conversely, alone show negligible production. The conversion follows tandem catalytic process. initially...