Anion intercalated layered-double-hydroxide structure for efficient photocatalytic NO remove

Due to the easily controllable interlayer anions, metal cation composition proportion and thickness, which is beneficial to modify surface chemical state and tune bandgap, layered double hydroxides(LDHs) have great promising potential for photocatalytic applications. In this study,we have successfully synthesized the ZnAl–LDH intercalated the single anion between ZnAl cationic interlayer without anionic impurities by using a facile calcining and reconstructing routes. The electron structure and surface chemical state of the prepared products have been investigated by combining the DFT calculation and experimental characterization methods. UV–vis DRS was used to certify the light absorption of the prepared products, and we performed the DFT calculation to demonstrate the density of state and activation of reactant. These results suggested that the ZnAl–LDH–CO3 possessed the more proper band structure and superior ability to activate NO and O2 for accelerating the photocatalytic NO oxidation activity. Moreover, the in situ DRIFTS with dynamically monitoring intermediates and products over the ZnAl–LDH–CO3 was adopted to declare the photocatalytic NO oxidized process during the photocatalytic reaction process. This work illustrated the influence of different interlayer anions to the electron structure and surface chemical state of ZnAl–LDH structure through the experimental verification combined DFT calculation and the photocatalytic NO oxidized process via in situ DRIFTS analyzing, which would provide a novel way to design and fabricate the efficient photocatalysis, and understand the reaction process.

Compulsive malposition of birnessite slab in 2D-Parallel birnessite on β-MnO_(2) networks for enhanced pseudocapacitance performances

High electrochemically active bimessite is always desirable pseudocapacitive material for supercapacitor.Here,two-dimensional(2D)compulsive malposition parallel bimessite standing on β-MnO_(2) interconnected networks have been designed.Due to the retrition of β-MnO_(2),compulsi ve malposition,slippage of MnO6 slab,occured in bimessite resulting in weaken bi nding force between bimessi te slab and interlayer cations,which enhanced their electrochemical performances.Additionally,the electrical conductivity of the structure was largely promoted by the 2D charge transfer route and double-exchange mechanism in bimessite,also leading to desirable electro-chemical properties.Based on the fraction of as-prepared nanostructure,the par all bimessite exhibited good pseudocapacitance performance(660 F g^(-1))with high rate capability.In addition,the asymmetrice supercapacitor assembled by reduced graphene oxide(RGO)and as-prepared nanostructure,which respectively served as the negative and positive eletrode,delivered an energy density of 33.1 Wh kg^(-1) and a mad mum power density of 64.0 kW kg^(-1) with excellent cyeling stability(95.8% after 10000 cycles).Finally,the study opens new avenwes for synthesizing high eletrochemically actiwe bimessite structure for high-performance energy storage devices.

The pseudocapacitance mechanism of graphene/CoAl LDH and its derivatives:Are all the modifications beneficial?

Cobalt-Aluminum layered double hydroxide(CoAl LDH) is a hopeful electrode material due to the advantage of easy modifiability for preparing LDH-based derivatives.However,there is short of modification methods to prepare the Co-based derivatives from CoAl LDH and also short of an intuitive perspective to analyze the pseudocapacitance mechanism of CoAl LDH and its derivatives.Herein,Graphene/CoAl LDH and its derivatives including Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP were prepared by reasonably using alkali etching treatment,sulfofication and phosphorization.The specific capacitance of Graphene/CoAl LDH,Graphene/CoS,Graphene/CoS-1,Graphene/CoOOH,Graphene/CoP at1 A g^(-1) are 260.7,371.3,440.8,61.4 and 122.2 F g^(-1),especially.The pseudocapacitance mechanism of Graphene/CoAl LDH and its derivatives was analyzed.Due to the positive effect of sulfofication on the electrical conductivity of GO and cobalt sulfide,the Graphene/CoS and Graphene/CoS-1 exhibit the optimal electrochemical performance and superior rate capability.In addition,due to the repulsion effect between Graphene and OH-,the Graphene/CoAl LDH exhibits optimal cycling stability of 224.1% capacitance retention after 20000 cycles.Besides,the reason of terrible specific capacitance of Graphene/CoOOH is that the presence of H bond in interlayer of CoOOH inhibits the interaction between Co3+ and OHspecies.Hence,not all modifications will increase the specific capacitance of the electrode materials.Overall,this work provides us with a detailed analysis of the electrochemical mechanism and correlation of CoAl LDH and its derivatives from the perspective of crystal structure and composition.

Bi2O3晶体结构和氧缺陷协同作用:促进中间产物的吸附活化、转化途径和光催化反应效率

在两种不同晶体结构的Bi2O3表面构造了人工氧缺陷,采用实验与模拟计算相结合的方法,从分子层面证实了特定晶体结构和氧缺陷的协同作用可以提高光催化效率,并有效调控光催化转化NO的反应路径,进而加快了整个反应历程.优化后的α-Bi2O3-X可见光净化NO去除率从7.3%增长至20.1%,而β-Bi2O3-X可见光光催化性能从25.2%提高至52.0%,活性增强的差异与不同的晶体结构、氧缺陷有关. DFT计算和实验结果证实,α-Bi2O3和β-Bi2O3表面氧缺陷作为活化中心,促进反应物和中间产物的吸附活化.同时,晶体结构和氧缺陷协同调控电子传递途径,原子排布呈隧道结构的氧缺陷β-Bi2O3对反应物活化以及电荷转移效率比Z型原子排布的氧缺陷α-Bi2O3更高效,这归因于在α-Bi2O3和β-Bi2O3表面构建的缺陷结构不同.原位FT-IR揭示了光催化氧化NO的反应机理,不同晶相的Bi2O3光催化NO转换途径可以由不同的表面缺陷结构进行有效调控.

Inhibition of the toxic byproduct during photocatalytic NO oxidation via La doping in ZnO

It is of a great challenge to develop semiconductor photocatalysts with potential possibilities to simultaneously enhance photocatalytic efficiency and inhibit generation of toxic intermediates.In this study,we developed a facile method to induce the La doping and cationic vacancie(V(Zn))on ZnO for the highly efficient complete NO oxidation.The photocatalytic NO removal efficiency increases from 36.2%to 53,6%.Most importantly,a significant suppressed NO2 production also has been realized.According to the DFT calculations,ESR spectra and in situ FTIR spectra,the introduction of La^3+induce the redistribution of charge carriers in La-ZnO,which promote the production of·O2^- and lead to the formation of V(Zn)for the formation of·OH,contributing to the complete oxidation of NO to nitrate.Besides,the conversion pathway of photocatalytic NO oxidation has been elaborated,This work paves a new way to simultaneously realize the photocatalytic pollutants removal and the inhibition of toxic intermediates generation for efficient and safe air purification.