Rate Law for Photoelectrochemical Water Splitting Over CuO

Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.

Signal intensity changes of dentate nucleus on plain MR T1WI innasopharyngeal carcinoma patients after radiotherapy andmultiple injections of gadolinium-base contrast agent

Objective To observe changes of plain MR T1WI signal intensity of dentate nucleus in nasopharyngeal carcinoma patients after radiotherapy and multiple times of intravenous injection of gadolinium-based contrast agent(GBCA).Methods Fifty patients with pathologically confirmed nasopharyngeal carcinoma and received intensity-modulated radiotherapy were retrospectively enrolled as the nasopharyngeal carcinoma group,and 50 patients with other malignant tumors and without history of brain radiotherapy were retrospectively enrolled as the control group.All patients received yearly GBCA enhanced MR examinations for the nasopharynx or the head.T1WI signal intensities of the dentate nucleus and the pons on same plane were measured based on images in the year of confirmed diagnosis(recorded as the first year)and in the second to the fifth years.T1WI signal intensity ratio of year i(ranging from 1 to 5)was calculated with values of dentate nucleus divided by values of the pons(ΔSI i),while the percentage of relative changes of year j(ranging from 2 to 5)was calculated withΔSI j compared toΔSI 1(Rchange j).The values of these two parameters were compared,and the correlation ofΔSI and GBCA injection year-time was evaluated within each group.Results No significant difference of gender,age norΔSI 1 was found between groups(all P>0.05).The second to the fifth yearΔSI and Rchange in nasopharyngeal carcinoma group were all higher than those in control group(all P<0.05).Within both groups,ΔSI was positively correlated with GBCA injection year-time(both P<0.05).Conclusion Patients with nasopharyngeal carcinoma who underwent radiotherapy and multiple times of intravenous injection of GBCA tended to be found with gradually worsening GBCA deposition in dentate nucleus,for which radiotherapy might be a risk factor.

How is a black hole created from nothing?

Using the synchronous coordinates,the creation of a Schwarzschild black hole immersed in a de Sitter spacetime can be viewed as a coherent creation of a collection of timelike geodesics.The previously supposed conical singularities do not exist at the horizons of the constrained instanton.Instead,the unavoidable irregularity is presented as a nonvanishing second fundamental form elsewhere at the quantum transition 3-surface.The same arguments can be applied to charged,topological,or higher dimensional black hole cases.

Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO_(2)electroreduction to CH4

Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2)reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N2-bidentate(note that N2-bidentate site=N^N-bidentate site;N2¹dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N2-bidentate site,a Cu SAC with isolated undercoordinated Cu-N2 sites(Cu1.0/N2-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N2-GDY exhibits the highest Faradaic efficiency(FE)of 80.6%for CH4 in electrocatalytic reduction of CO_(2)at-0.96 V vs.RHE,and the partial current density of CH4 is 160 mA cm^(-2).The selectivity for CH4 is maintained above 70%when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N2-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N2 sites are more favorable in generating key*COOH and*CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N2 sites toward efficient electrocatalysis.

Nonlinear Absorption and Low-threshold Two-photon Pumped Amplified Stimulated Emission from FAPbBr_(3) Nanocrystals

Formamidinium lead bromide(FAPbBr_(3))nanocrystals(NCs)have been considered to be a good optoelectronic material due to their pure green emission,excellent stability and superior carrier transport characteristics.However,two-photon pumped amplified spontaneous emission(ASE)and the corresponding nonlinear optical properties of FAPbBr_(3) NCs are scarcely revealed.Herein,we synthesized colloidal FAPbBr_(3) NCs with different sizes by changing the molar ratio of FABr/PbBr_(2) in the precursor solution,using ligand assisted precipitation(LARP)technology at room temperature.Photoluminescence(PL)and time resolved photoluminescence(TRPL)spectroscopy were measured to characterize their ASE properties.And their nonlinear optical properties were studied through the Zscan technique and the two-photon excited fluorescence method.The stimulated emission properties including oneand two-photon pumped ASE have been realized from FAPbBr_(3) NCs.With large two-photon absorption coefficient(0.27 cm/GW)and high non-linear absorption cross-section(7.52×10^(5) GM),ASE with threshold as low as 9.8μJ/cm^(2) and 487μJ/cm^(2) have been obtained from colloidal FAPbBr_(3) NCs using one-and two-photon excitations.These results indicate that as a new possible green-emitting frequency-upconversion material with low thresholds,FAPbBr_(3) NCs hold great potential in the development of high-performance two-photon pump lasers.

Structural design of mid-infrared waveguide detectors based on InAs/GaAsSb superlattice

In the realm of near-infrared spectroscopy,the detection of molecules has been achieved using on-chip waveguides and resonators.In the mid-infrared band,the integration and sensitivity of chemical sensing chips are often constrained by the reliance on off-chip light sources and detectors.In this study,we demonstrate an InAs/GaAsSb superlattice mid-infrared waveguide integrated detector.The GaAsSb waveguide layer and the InAs/GaAsSb superlattice absorbing layer are connected through evanescent coupling,facilitating efficient and highquality detection of mid-infrared light with minimal loss.We conducted a simulation to analyze the photoelectric characteristics of the device.Additionally,we investigated the factors that affect the integration of the InAs/GaAs⁃Sb superlattice photodetector and the GaAsSb waveguide.Optimal thicknesses and lengths for the absorption lay⁃er are determined.When the absorption layer has a thickness of 0.3μm and a length of 50μm,the noise equiva⁃lent power reaches its minimum value,and the quantum efficiency can achieve a value of 68.9%.The utilization of waveguide detectors constructed with Ⅲ-Ⅴ materials offers a more convenient means of integrating mid-infra⁃red light sources and achieving photoelectric detection chips.

An improved ASM-HEMT model for kink effect on GaN devices

With the analysis of experiment and theory on GaN HEMT devices under DC sweep,an improved model for kink effect based on advanced SPICE model for high electron mobility transistors(ASM-HEMT)is pro⁃posed,considering the relationship between the drain/gate-source voltage and kink effect.The improved model can not only accurately describe the trend of the drain-source current with the current collapse and kink effect,but also precisely fit different values of drain-source voltages at which the kink effect occurs under different gatesource voltages.Furthermore,it well characterizes the DC characteristics of GaN devices in the full operating range,with the fitting error less than 3%.To further verify the accuracy and convergence of the improved model,a load-pull system is built in ADS.The simulated result shows that although both the original ASM-HEMT and the improved model predict the output power for the maximum power matching of GaN devices well,the im⁃proved model predicts the power-added efficiency for the maximum efficiency matching more accurately,with 4%improved.

儿童血铅中毒事件损害赔偿和防治法律问题研究——专门立法的建议

环境污染导致的血铅中毒事件,大范围侵害儿童的健康权和发展权。儿童血铅中毒的损害有其特征,且危害巨大,必须重视这类事件的损害赔偿和预防控制。在赔偿待遇、救济方式和救济途径方面,需要拿出专门的法律方案。现行环境和职业病防治法律制度,难以有效地预防控制儿童血铅中毒事件的蔓延。建议制定《儿童铅中毒防治法》,就儿童铅中毒的损害赔偿所涉实体法和程序法问题,连同其预防控制问题,提出专门的法律解决方案;并且制定《公害疾病补偿法》,用于对重金属中毒、放射性损伤、食源性疾病等公害事件的系统补救,包括受理投诉、调查、认定、救治、康复、护理和特殊教育,解释和道歉,以及指定情况下的经济补偿和给付。

仅受第三人欺诈所签订担保合同的效力探析

仅受第三人欺诈所签订担保合同的效力,我国法律没有明确规定。从国内法学理论的阐述与部分发达国家的法律规定来看,并无统一的标准与定论。就我国目前民事法律的具体规定而言,仅受第三人欺诈所签订合同属于意思表示瑕疵,但又非无效的情况,应定性为可变更或可撤销的合同,适用可撤销或可变更的一般规定。

Stability of Cu-Mn bimetal catalysts based on different zeolites for NO_x removal from diesel engine exhaust

Cu–Mn bimetal catalysts were prepared to remove nitrogen oxides(NOx)from diesel engine exhaust at low temperatures.At a Cu/Mn ratio of 3:2,the NOx conversions at 200°C reached 65%and 90%on Cu–Mn/ZSM‐5 and Cu–Mn/SAPO‐34,respectively.After a hydrothermal treatment and reaction in the presence of C3H6,the activity of Cu–Mn/SAPO‐34 was more stable than that of Cu–Mn/ZSM‐5.No obvious variations in the crystal structure or dealumination were observed,whereas the physical structure was best maintained in Cu–Mn/SAPO‐34.The atomic concentration of Cu on the surface of Cu–Mn/SAPO‐34 was quite stable,and the consumption of octahedrally coordinated Cu2+could be recovered.Conversely,the proportion of octahedrally coordinated Cu2+on the surface of Cu–Mn/ZSM‐5 significantly decreased.Therefore,besides the structure,the redox cycle between Cu+and octahedrally coordinated Cu2+played an important role in the stability of the catalysts.

Acetylene hydrochlorination over supported ionic liquid phase(SILP)gold-based catalyst:Stabilization of cationic Au species via chemical activation of hydrogen chloride and corresponding mechanisms

The activation of HCl by cationic Au in the presence of C2H2 is important for the construction of active Au sites and in acetylene hydrochlorination.Here,we report a strategy for activating HCl by the Au-based supported ionic liquid phase(Au–SILP)technology with the[N(CN)2^–]anion.This strategy enables HCl to accept electrons from[N(CN)2^–]anions in Au–[N(CN)2^–]complexes rather than from pure[Bmim][N(CN)2],leading to notable improvement in both the reaction path and the stability of the catalyst without changing the reaction triggered by acetylene adsorption.Furthermore,the induction period of the Au–SILP catalyst was shown to be absent in the reaction process due to the high Au(III)content in the Au(Ⅲ)/Au(Ⅰ)site and the high substrate diffusion rate in the ionic liquid layer.This work provides a facile method to improve the stability of Au-based catalysts for acetylene hydrochlorination.

Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts

The structural complexity of supported metal catalysts,playing significant role in a wide range of chemical technologies,have prevented us from deeply understanding their catalytic mechanisms at atomic level.A fundamental understanding of the nature of active sites and structure–performance relationship of supported metal catalysts from a comprehensive view will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy conversion and environmental protection.This review surveys the effects of multiple factors,including the metal size,shape,support,alloy and ligand modifier,on the coordinated environment of active center and further their influence on the catalytic reactions,aiming to provide guidance for the design of industrialized heterogeneous catalysts with extraordinary performance.Subsequently,the key structure characterization techniques in determining the coordination structure of active metal sites,especially the dynamic coordination structure change under the reaction condition,are well summarized.A brief summary is finally provided together with personal perspectives on the further development in the field of heterogeneous metal catalysts.

Supercritical water syntheses of transition metal-doped CeO_2 nano-catalysts for selective catalytic reduction of NO by CO:An in situ diffuse reflectance Fourier transform infrared spectroscopy study

In the present study,we synthesized CeO2 catalysts doped with various transition metals(M=Co,Fe,or Cu)using a supercritical water hydrothermal route,which led to the incorporation of the metal ions in the CeO2 lattice,forming solid solutions.The catalysts were then used for the selective catalytic reduction(SCR)of NO by CO.The Cu‐doped catalyst exhibited the highest SCR activity;it had a T50(i.e.,50%NO conversion)of only 83°C and a T90(i.e.,90%NO conversion)of 126°C.Such an activity was also higher than in many state‐of‐the‐art catalysts.In situ diffuse reflectance Fourier transform infrared spectroscopy suggested that the MOx‐CeO2 catalysts(M=Co and Fe)mainly followed an Eley‐Rideal reaction mechanism for CO‐SCR.In contrast,a Langmuir‐Hinshelwood SCR reaction mechanism occurred in CuO‐CeO2 owing to the presence of Cu+species,which ensured effective adsorption of CO.This explains why CuO‐CeO2 exhibited the highest activity with regard to the SCR of NO by CO.

Selective oxidation of glycerol in a base-free aqueous solution: A short review

Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydroxyacetone, glyceric acid, glyceraldehydes, and tartronic acid is challenging both from the viewpoint of academic research and industrial application. Herein, we review the recent progresses in the selective oxidation of glycerol under base-free conditions. Those catalysts widely reported for the selective oxidation of the terminal hydroxyl and secondary hydroxyl groups in glycerol, such as monometallic Au, Pt, and Pd NPs, and bimetallic Au-Pt, Au-Pd, Pt-Bi, Pt-Sb, and Pt-Cu, were compared and discussed in detail. The reaction mechanism over Pt-based catalysts, possible catalyst deactivation, and the corresponding improvements are presented. Further, the recent progresses in the continuous oxidation of glycerol in fixed bed reactors and its excellent selectivity in the formation of dihydroxyacetone are highlighted.

Carbon-supported ruthenium catalysts prepared by a coordination strategy for acetylene hydrochlorination

The development of efficient and stable non-mercury catalysts for the chlor-alkali industry is desirable but remains a great challenge.Herein,we design a series of ruthenium catalysts for acetylene hydrochlorination by regulating the electronic structure of ruthenium ions through coordination with various ligands(thiourea,phenanthroline,and L-lactic).The turnover frequencies(TOFs)and apparent activation energies for the acetylene hydrochlorination have a linear relationship with the binding energy of Ru3+in the ruthenium catalysts.The synergetic effect of the ruthenium ion and ligands plays an important role in acetylene hydrochlorination.The Ru-Thi/AC catalyst with thiourea as the ligand shows the highest TOF and stability in acetylene hydrochlorination.The present study provides a rational method to regulate the electronic structure of supported metal catalysts with high catalytic performance exhibited by the carbon-supported heterogeneous catalysts.

Elimination of 1,2-dichloroethane over(Ce,Cr)_x O_2/Nb_2O_5 catalysts: synergistic performance between oxidizing ability and acidity

A series of(Ce,Cr)xO2/Nb2O5 catalysts with different(Ce,Cr)xO2 to Nb2O5 mass ratios were synthesized by the deposition-precipitation method for use in deep catalytic oxidation of 1,2-dichloroethane(DCE), which is one of the typical chlorinated volatile organic compound pollutants. The textural properties were characterized by X-ray diffraction, N2 adsorption/desorption isotherms, UV-Raman spectroscopy, and scanning electron microscopy. The surface acidity and the redox properties were characterized by ammonia temperature-programmed desorption and H2 temperature-programmed reduction, respectively. The results show that the addition of a proper amount of(Ce,Cr)xO2 over Nb2O5 significantly improves the intrinsic catalytic activity towards the deep oxidation of DCE, and only a very small amount of C2H3Cl is detected as the byproduct of the oxidation process. Further study reveals the existence of an obvious synergistic effect between Nb2O5, with abundant strong acid sites, and(Ce,Cr)xO2, with strong oxidation sites, as the strong acid sites of Nb2O5 promote the adsorption and dehydrochlorination of DCE, while the strong oxidation sites of(Ce,Cr)xO2 contribute to the deep oxidation of the reactant, intermediates, and byproducts.

Synergetic effect between non-thermal plasma and photocatalytic oxidation on the degradation of gas-phase toluene: Role of ozone

In this study, a hybrid process using non‐thermal plasma (NTP) and photocatalytic oxidation (PCO) was adopted for the degradation of gas‐phase toluene using TiO2 as the photocatalyst. To discover the synergetic effect between NTP and PCO, the performances of both sole (O3, UV, NTP, and PCO) and combined (O3 + TiO2, O3 + UV, NTP + UV, O3 + PCO, and NTP + PCO) processes were investigated from different perspectives, such as the toluene removal efficiency, selectivity of COx, mineralization rate, ozone utilization, and the generation of by‐products. The toluene removal efficiency of the combined NTP + PCO process was 80.2%, which was much higher than that of a sole degradation process such as NTP (18.8%) and PCO (13.4%). The selectivity of CO2 and the ozone utilization efficiency also significantly improved. The amount of by‐products in the gas phase and the carbon‐ based intermediates adsorbed on the catalyst surface dramatically reduced. The improvement in the overall performances of the combined NTP + PCO process was mainly ascribed to the efficient utilization of ozone in the photocatalytic oxidation, and the ozone further acting as an electron acceptor and scavenger, generating more hydroxyl radicals and reducing the recombination of electron‐ hole pairs.

Rational design of hydrogenation catalysts using nitrogen-doped porous carbon

1. Introduction Hydrogenation is one of the most important reactions in the chemical and petroleum refining industries. Since Sabatier [1] first studied the hydrogenation of unsaturated organic compounds in the presence of nickel in 1897, different catalysts have been tested for the hydrogenation of a wide range of substances to produce useful chemicals or intermediates. Compared with homogeneous catalysts, heterogeneous catalysts have attracted greater attention due to their easier separation and better handling properties [2]. Among the various heterogeneous catalysts, metal-supported catalysts are widely used in various hydrogenation reactions. Particularly, metal oxides are generally used as supports in consecutive hydrogenation reactions due to their high mechanical strength, whereas carbon supports are often utilized to produce fine medicals owing to their large surface area and acid-alkali resistance.

Visible light promoted difunctionalization reactions of alkynes

Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.

Wheat flour-derived N-doped mesoporous carbon extrudes as an efficient support for Au catalyst in acetylene hydrochlorination

We recently reported an N‐doped mesoporous carbon(N‐MC)extrudate,with major quaternary N species,prepared by a cheap and convenient method through direct carbonization of wheat flour with silica,which has excellent catalytic performance in acetylene hydrochlorination.Herein,we examined the activity of Au supported on N‐MC(Au/N‐MC)and compared it with that of Au supported on nitrogen‐free mesoporous carbon(Au/MC).The acetylene conversion of Au/N‐MC was 50%at 180°C with an acetylene space velocity of 600 h–1 and VHCl/VC2H2 of 1.1,which was double the activity of Au/MC(25%).The introduced nitrogen atoms acted as anchor sites that stabilized the Au3+species and inhibited the reduction of Au3+to Au0 during the preparation of Au/N‐MC catalysts.