Ultralow-Energy-Barrier H_(2)O_(2)Dissociation on Coordinatively Unsaturated Metal Centers in Binary Ce-Fe Prussian Blue Analogue for Efficient and Stable Photo-Fenton Catalysis

The low intrinsic activity of Fenton catalytic site and high demand for light-energy input inhibit the organic-pollution control efficiency of photo-Fenton process.Here,through structural design with density functional theory(DFT)calculations,Ce is predicted to enable the construction of coordinatively unsaturated metal centers(CUCs)in Prussian blue analogue(PBA),which can strongly adsorb H_(2)O_(2)and donate sufficient electrons for directly splitting the O-O bond to produceOH.Using a substitution-co-assembly strategy,binary Ce-Fe PBA is then prepared,which rapidly degrades sulfamethoxazole with the pseudo-first-order kinetic rate constant exceeding reported values by 1-2 orders of magnitude.Meanwhile,the photogenerated electrons reduce Fe(Ⅲ)and Ce(Ⅳ)to promote the metal valence cycle in CUCs and make sulfamethoxazole degradation efficiency only lose 6.04%in 5 runs.Overall,by introducing rare earth metals into transition metal-organic frameworks,this work guides the whole process for highly active CUCs from design and construction to mechanism exploration with DFT calculations,enabling ultrafast and stable photo-Fenton catalysis.

Tuning active sites in MoS_(2)-based catalysts via H_(2)O_(2)etching to enhance hydrodesulfurization performance

A H_(2)O_(2)etching strategy was adopted to introduce coordinatively unsaturated sites(CUS)on MoS_(2)-based catalysts for dibenzothiophene(DBT)hydrodesulfurization(HDS).The CUS concentrations on MoS_(2) slabs were finely regulated by changing the concentrations of H_(2)O_(2)solution.With the increasing H_(2)O_(2)concentrations(0.1–0.3 mol/L),The CUS concentrations on MoS_(2) slabs increased gradually.However,the high-concentration H_(2)O_(2)etching(0.5 mol/L)increased the MoOxSy and MoO_(3) contents on MoS_(2) slabs compared to etching with the H_(2)O_(2)concentration of 0.3 mol/L,which led to the less CUS concentration in the sulfided Mo–H-0.5 catalyst than in the sulfided Mo–H-0.3 catalyst.A microstructure-activity correlation indicated that the CUS introduced by H_(2)O_(2)etching on MoS_(2) slabs significantly enhanced DBT HDS.Different Co loadings were further introduced into Mo–H-0.3,which had the most CUS concentration,and the corresponding 0.2-CoMo catalyst with the highest CoMoS content(3.853 wt%)exhibited the highest reaction rate constant of 6.95×10^(−6)mol g^(−1)s^(−1)among these CoMo catalysts.

过渡金属表面的成键特性及与几何结构的关联

提出了按第一与第二近邻微环境分类表面原子的方法,根据表面原子与体相原子近邻微环境的差异提出了表面原子轨道成键强度的概念,编写了相应的计算程序.这样,金属表面的化学吸附与催化性能可直观地与表面原子的几何特性相联系.这一方法也有助于建立过渡金属表面与原子簇的化学活性的关联.

Coordinatively unsaturated single Co atoms immobilized on C_(2)N for efficient oxygen reduction reaction

Developing cost-effective and high-efficiency oxygen reduction reaction(ORR)catalysts is imperative for promoting the substantial progress of fuel cells and metal-air batteries.The coordination and geometric engineering of single-atom catalysts(SACs)occurred the promising approach to overcome the thermodynamics and kinetics problems in high-efficiency electrocatalysis.Herein,we rationally constructed atomically dispersed Co atoms on porous N-enriched graphene material C_(2)N(CoSA-C2N)for efficient oxygen reduction reaction(ORR).Systematic characterizations demonstrated the active sites for CoSA-C2N is as identified as coordinatively unsaturated Co-N_(2)moiety,which exhibits ORR intrinsic activity.Structurally,the porous N-enriched graphene framework in C_(2)N could effectively increase the accessibility to the active sites and promote mass transfer rate,contributing to improved ORR kinetics.Consequently,CoSA-C_(2)N exhibited superior ORR performance in both acidic and alkaline conditions as well as impressive long-term durability.The coordination and geometric engineering of SACs will provide a novel approach to advanced catalysts for energy related applications.

High-Index Faceted Nanocrystals as Highly Efficient Bifunctional Electrocatalysts for High-Performance Lithium-Sulfur Batteries

Precisely regulating of the surface structure of crystalline materials to improve their catalytic activity for lithium polysulfides is urgently needed for high-performance lithium-sulfur(Li-S)batteries.Herein,high-index faceted iron oxide(Fe_(2)O_(3))nanocrystals anchored on reduced graphene oxide are developed as highly efficient bifunctional electrocatalysts,effectively improving the electrochemical performance of Li-S batteries.The theoretical and experimental results all indicate that high-index Fe_(2)O_(3)crystal facets with abundant unsaturated coordinated Fe sites not only have strong adsorption capacity to anchor polysulfides but also have high catalytic activity to facilitate the redox transformation of polysulfides and reduce the decomposition energy barrier of Li_(2)S.The Li-S batteries with these bifunctional electrocatalysts exhibit high initial capacity of 1521 mAh g^(-1)at 0.1 C and excellent cycling performance with a low capacity fading of 0.025%per cycle during 1600 cycles at 2 C.Even with a high sulfur loading of 9.41 mg cm^(-2),a remarkable areal capacity of 7.61 mAh cm^(-2)was maintained after 85 cycles.This work provides a new strategy to improve the catalytic activity of nanocrystals through the crystal facet engineering,deepening the comprehending of facet-dependent activity of catalysts in Li-S chemistry,affording a novel perspective for the design of advanced sulfur electrodes.

Controllable defect engineering based on cobalt metal-organic framework for boosting oxygen evolution reaction

Defect engineering on metal-organic frameworks(MOFs)provides high flexibility to rationally design advanced oxygen evolution reaction(OER)catalysts with low overpotential and high stability.However,fundamental understanding the effect of defect concentration on catalytic OER activity is still quite ambiguous.Herein,the Co-MOF-Dx catalysts with regulated oxygen defects concentration are deliberately constructed via coupling one-pot solvothermal synthesis with NaBH_(4)chemical reduction process.Experimental findings propose that the oxygen defect concentration within Co-MOF-Dx gradually increases with raising the NaBH_(4)content,which could provide a flexible platform to tailor the electronic structure around active Co site and optimize adsorption/desorption capacity of oxygen intermediates.When the introduction content of NaBH_(4)is up to 5 mg,the resulting abundant unsaturated coordination defects could endow the Co-MOF-D5 catalyst with optimized electronic structure and more exposed active sites for improving charge transfer and adsorption/desorption capacity.It is found that the optimized Co-MOF-D5 can drive the current density of 10 mA cm^(-2)only at a low overpotential of 300 mV with the small Tafel slope of 53.1 mV dec^(-1)in alkaline medium.This work sheds light on the way for the development of high-performance MOF catalysts via modulating defect concentration.

Effect of yttrium on catalytic performance of Y-doped TiO_(2) catalysts for propane dehydrogenation

Defective bulk catalysts based on TiO_(2) have superior catalytic performance for propane dehydrogenation(PDH).The oxygen vacancy concentration and the number of active sites on the catalyst surface can be effectively tuned by doping metal in TiO_(2).Herein,yttrium(Y)-doped titanium dioxide(nY/TiO_(x))catalysts were in-situ synthesized via the coprecipitation method to study the effect of rare earth metal Y doping on the structure of TiO_(2) and the catalytic performance for PDH.Experimental results demonstrate that Ydoped TiO_(2) exhibits higher catalytic activity,propylene selectivity and stability than bare TiO_(2).Full characterizations with X-ray diffraction(XRD),high-resolution transmission electron microscope(HRTEM),X-ray photoelectron spectroscopy(XPS),infrared spectroscopy of pyridine adsorption(Py-IR),temperature-programmed desorption of ammonia(NH_(3)-TPD),H_(2) temperature-programmed reduction(H_2-TPR),and Raman techniques on these catalysts reveal that Y^(3+)can enter TiO_(2) lattice,and the lattice stability of the catalyst can be enhanced by replacing Ti^(4+)to form Y-O-Ti structure.Meanwhile,the introduction of an appropriate amount of Y can obviously promote the PDH reaction by adjusting the acidity of the catalyst,improving the release capacity of TiO_(2) lattice oxygen and increasing the formation of active centers.Nevertheless,excessive Y doping will lead to pore clogging,and the exposure of active sites will be reduced,resulting in the degradation of catalytic performance.

Constructing a stable cobalt-nitrogen-carbon air cathode from coordinatively unsaturated zeolitic-imidazole frameworks for rechargeable zinc-air batteries

Zeolitic-imidazole frameworks(ZIFs)derivations have widely emerged as an efficient air cathode of zinc-air batteries(ZABs)due to excellent bifunctional oxygen electrocatalysis performance.However,they are not stable enough for long-term operation of rechargeable ZABs because of weak association with current collector,especially under bending conditions for flexible ZAB devices.Here,we show that by purposely designing coordinatively unsaturated ZIFs via a facile morphology regulation,which can be chemically linked on acid-treated carbon cloth,a stable Co-N-C air cathode is therefore derived where Co nanoparticles(NPs)are uniformly confined within the Co-N-C matrix on carbon cloth(Co/Co-N-C/CC).Specifically,when without being stabilized from carbon cloth,the pyrolysis of ZIFs with different unsaturated coordination levels has a negligible impact on the bifunctional oxygen-catalyzed performance.The optimal Co/Co-N-C/CC catalyst assembled ZAB possesses a large open circuit voltage of 1.415 V and a high peak power density of 163 mW·cm^(−2) as well as excellent cycling durability upon 630 discharge–charge cycles with 61%voltage efficiency remained,largely exceeding those of a benchmark Pt/C-IrO_(2) catalyst assembled ZAB.The synergy between Co NPs and active Co-N-C sites via electronic interaction induces the outstanding bifunctional oxygen-catalyzed activity and cathode performance.The present work highlights the importance of unsaturated coordination structures in ZIFs precursors for the performance of derived nanostructures in integrated electrodes.

Study on mechanism of low-temperature oxidation of n-hexanal catalysed by 2D ultrathin Co_(3)O_(4) nanosheets

Achieving high catalytic performance with lower possible cost and higher energetic efficiency is critical for catalytic oxidation of volatile organic compounds(VOCs).However,traditional thermocatalysts generally undergo low catalytic activity and fewer active sites.Herein,this paper synthesizes nearly all-surface-atomic,ultrathin two-dimensional(2D)Co_(3)O_(4) nanosheets to address these problems through offering a numerous active sites and high electron mobility.The 2D Co_(3)O_(4) nanosheets(1.70 nm)exhibit catalyzation to the total oxidation of n-hexanal at the lower temperature of r90%=202℃,and at the space velocity of 5.0×10^(4) h^(-1).It is over 1.2 and 6 times higher catalytic activity than that of 2D CoO nanosheets(1.71 nm)and bulk Co_(3)O_(4) counterpart,respectively.Transient absorption spectroscopy analysis shows that the oxygen vacancy defect traps electrons,thereby preventing the recombination with holes,increasing the lifetime of electrons,and making electron-holes reach a nondynamic equilibrium.The longer the electron lifetime is,the easier the oxygen vacancy defects capture electrons.Furthermore,the defects combine with oxygen to form active oxygen components.Compared with the lattice oxygen involved in the reaction of bulk Co_(3)O_(4),the nanosheets change the catalytic reaction path,which effectively reduces the activation energy barrier from 34.07 to 27.15 kJ/mol.The changed surface disorder,the numerous coordinatively-unsaturated Co atoms and the high ratio of O_(ads)/O_(lat) on the surface of 2D Co_(3)O_(4) nanosheets are responsible for the catalytic performance.

Interfacial defective Ti^(3+) on Ti/TiO_(2) as visible-light responsive sites with promoted charge transfer and photocatalytic performance

Defect sites on oxide semiconductors play a crucial role in promoting photocatalytiperformance and mod-ulating the bandgap structure of photocatalysts.However,the role of interfacial coordinatively unsatu-rated defect sites between metal and oxide in photocatalysis is still under debate.So,we designed an experiment to probe the role of interfacial coordinatively unsaturated defect sites.In this work,a se-ries of Ti/TiO_(2) photocatalysts with varying concentrations of interfacial Ti^(3+)sites were prepared through an epitaxial growth method under hydrothermal conditions.Through experimental and computational investigations,the roles of interfacial defect sites were discussed in detail.On the one hand,the inter-facial coordinatively unsaturated Ti^(3+)sites could act as visible-light-responsive sites in photocatalytic reactions due to the overlap and hybridization of multiple electronic orbitals.On the other hand,the Ti/TiO_(2) interface exhibited a certain degree of metallic character near the Fermi level because of the par-tial delocalization and redistribution of electrons,facilitating the charge migration and separation across the metal-oxide interface.Consequently,the obtained Ti/TiO_(2) catalysts showed notably enhanced charge transfer efficiency and visible light photocatalytic activity compared to their pristine counterparts.This work may provide a new perspective to interfacial defect engineering in classic metal/oxide heterojunc-tion photocatalysts and figure a more precise direction to synthesize higher effective photocatalysts for environmental governance.