Palladium single atoms from melting nanoparticles on WO_(3-x) for boosted hydrogen evolution reaction

Surface-supported isolated atoms in single-atom catalysts(SACs)grant maximum utilization of metals in heterogeneous catalysis.Herein,we report a feasible pyrolysis strategy to synthesize Pd single atoms by thermally melting Pd nanoparticles on an oxygen-vacancy-rich tungsten-oxide matrix at reduction atmosphere.Near ambient pressure X-ray photoelectron spectroscopy was used to monitor the formation of zero-valence Pd single atoms and the increased metallic feature of WO_(3-x)substrate.Accordingly,the as-obtained zero-valence Pd single-atom catalyst exhibits a markedly boosted HER activity with a low overpotential(η_(10)=70 mV)at the current density of 10 mA/cm2and a small Tafel slope(b=68 mV/dec),nearly 150 mV and a 3,0-fold enhancement than those of Pd nanoparticles(η_(10)=220 mV,b=133 mV/dec)under the same conditions.In addition,quasi in situ XPS results suggest the hydrogen spillover effect is more likely to occur on Pd single atoms during the electrochemical process.Our work may pave an interesting route for the rational design of highly-efficient single-atom catalysts,and the elucidation of corresponding enhanced reaction mechanisms by the utilization of advanced characterization techniques.

基于logistic模型的农户意愿对宅基地退出的影响——以无锡市为例

研究目的:在对无锡市锡山区东港镇三联村、港东村和惠山区堰桥街道村前村的96户农户问卷调查的基础上,通过构建logistic模型分析农户意愿对宅基地退出的影响。研究方法:问卷调查法、logistic模型。研究结果:农民受教育程度、家中老人小孩数量、宅基地面积对农民宅基地退出意愿有正向影响;年龄、房屋建造成本、现居住满意度对农民宅基地退出意愿有负向影响;性别、是否从事非农工作、家庭人口、家庭年收入、外出务工人数、房屋面积、房屋年限、是否购买商品房等因素对农民宅基地退出意愿没有显著影响;三联村宅基地退出意愿明显低于港东村和村前村。研究结论:农户宅基地退出意愿受农户个体、农户家庭和居住条件等多个方面的影响。

刘书楷先生学术思想初步研究

刘书楷先生是中国农业资源经济学和现代土地经济学的创始人之一,他毕生致力于学术研究,在农业资源及区划、土地经济与制度等领域成果卓著。本文主要基于刘书楷先生在农业区划理论与方法、农业资源经济理论探索及其应用、土地经济学的理论体系构建、农村土地制度研究等方面的代表性研究论著,分析了其主要学术思想和理论贡献。刘书楷先生的研究为农业区划学科发展及实践提供了理论和方法支撑,构建和发展了农业资源经济学和土地经济学的理论体系,也为中国农村土地制度的完善提出了富有远见的政策建议,值得后人整理凝练和学习研究。

公共用地配给对城市经济产出的影响研究

本文旨在探讨公共用地配给(投入)对城市经济产出的具体影响。论文在探究公共用地配给对城市经济产出影响机理的基础上,通过构建生产函数模型,并利用2000—2014年中国273个地级及地级以上市的统计数据,实证检验公共用地投入对城市经济产出的影响。研究结果显示,公共用地投入对城市经济产出有着显著的促进作用。其中,道路交通用地投入对城市经济产出的影响呈正'U'形变化规律,市政设施用地投入对于城市经济产出的影响表现为倒'U'形变化趋势,此外不同规模城市的人均公共用地配给对城市经济产出的影响存在明显差异。论文最后指出,政府有必要优化城市公共用地的供给结构,尤其是根据不同规模类型的城市,适时调控公共用地的供给,严格管控道路交通和市政设施用地的标准,以更好地发挥公共用地配给对城市经济增长的促进作用。

构筑Z型MnO_(2)/BiOBr异质结用于光催化环丙沙星去除和CO_(2)还原

日益严峻的能源短缺以及生态环境污染问题已成为引发全球持续关注的焦点问题,这严重影响了人类自身健康和社会可持续发展。多种技术被开发出来用于实现新能源开发和污染物控制,其中,光催化因其具有低耗能、无二次污染、操作流程简单、温和的反应条件等优点成为环境治理与能源催化领域的研究重点。不过值得注意的是,光催化技术尽管在抗生素的高效去除和CO_(2)还原领域的应用方兴未艾,但其工业化应用和大规模推广始终受限于光催化剂的光吸收效率、氧化还原能力和光生电子分离或迁移效率等诸多因素。基于当前光催化剂的组成/结构调控及其催化性能研究,探索高效实用的改性策略构筑性能更加优化的复合结构光催化剂,使光催化剂发挥出更高的光吸收/利用以及光催化表/界面反应性能是亟待解决的关键问题。在常见的改性策略中,Z型异质结构构筑不仅明显可以提高光吸收能力和显著降低光生电子空穴复合率,更重要的是,还可以保持光生电子/空穴的强还原/氧化能力来实现环境污染物去除和清洁能源转化。在本文中,采用机械辅助球磨法构建了MnO_(2)/BiOBr (MO/BiOBr) Z型异质结复合材料。在黑暗和光照条件下进行的原位X射线光电子能谱(XPS)测试可以证实MnO_(2)中的光生电子可以通过Mn3+/Mn4+氧化还原电对实现向BiOBr的定向迁移,以构建Z型载流子转移路径。通过电子自旋共振谱(ESR)和能带结构分析也可以推导出类似的结论。基于MnO_(2)中存在的Mn^(3+)/Mn^(4+)氧化还原电对以及MnO_(2)与BiOBr材料交错的能带位置,MnO_(2)和BiOBr材料可以构筑Z型异质结以实现氧化中心和还原中心的空间分离。此外,通过紫外可见光吸收光谱(UV-Vis DRS)和稳态荧光光谱(PL)分析相比较于BiOBr,MO/BiOBr复合材料具有增强的光吸收和显著降低的光生电子-空穴复合率。因此,MO/BiOBr复合材料表现出优异的光催化环丙沙星(CIP)氧化和CO释放性能。MO/BiOBr复合材料的CIP去除率在60min时可达77.3%,是BiOBr(60.2%)的1.28倍。同时,MO/BiOBr复合材料(20.02μmol·g^(-1)·h^(-1))的光催化CO生成性能是BiOBr (9.08μmol·g^(-1)·h^(-1))的2.2倍。光电流和电化学阻抗分析表明,相比于MnO_(2)和BiOBr单体,构筑的MnO_(2)/BiOBr Z型异质结具有更高的界面电子转移效率。此外,选用液相质谱联用光谱(LC-MS)和原位傅里叶变换红外光谱(in situ FTIR)对光催化CIP去除和CO_(2)还原过程的中间体生成路径进行分析。并通过毒性评估软件(T.E.S.T.)计算CIP和在MO/BiOBr复合材料光催化降解CIP过程中产生的中间体对应的大型溞的48 h半数致死浓度、黑头软口鲦的96 h半数致死量、致突变性和生物累积因子来评估CIP和相应中间体的实际生理毒性。因此,本研究提供了一种简便方法来构筑Z型异质结以实现太阳能驱动的高效抗生素去除和燃料合成。

Pt nanoparticles encapsulated on V_(2)O_(5)nanosheets carriers as efficient catalysts for promoted aerobic oxidative desulfurization performance

Platinum group metals(PGMs)usually exhibit promising aerobic catalytic abilities,providing a green and feasible oxidative desulfurization method.However,often,the PGM nanoparticles(NPs)get leached,and the catalysts are deactivated.In this work,Pt NPs with particle sizes of approximately 4–5 nm were encapsulated effectively and uniformly on the surface of vanadium pentoxide(V2O5)nanosheets(with thicknesses of approximately six atomic layers)through strong metal-support interactions.The synthesized catalysts promote catalytic aerobic oxidation reactions,realizing deep desulfurization(99.1%,<5μg g^(–1))under atmospheric pressure and 110℃reaction temperature.Remarkable degrees of sulfur removal could be achieved for oils with different initial S-concentrations and substrates.Additionally,the as-prepared catalysts could be recycled for reuse at least seven times.

Scalable and facile synthesis of V_(2)O_(5) nanoparticles via ball milling for improved aerobic oxidative desulfurization

In recent years, transition-metal oxides(TMOs) have been long employed for aerobic oxidative desulfurization. However, the inherent bottlenecks, such as the low explosion of active sites, limit the application of bulk TMOs catalyst. In this study, V_(2)O_(5) nanoparticles with oxygen vacancies were prepared in large-scale via facile ball milling strategy with adding oxalic acid as a reducing agent. The as-prepared catalysts exhibit remarkable sulfur removal for oils with different initial S-concentrations and different substrates. Sulfur removal could reach up to 99.7%(< 2 ppm) under the optimized reaction conditions. This work provides a feasible desulfurization strategy for fuel oils.

Gold/monolayer graphitic carbon nitride plasmonic photocatalyst for ultrafast electron transfer in solar-to-hydrogen energy conversion

Gold(Au)plasmonic nanoparticles were grown evenly on monolayer graphitic carbon nitride(g‐C3N4)nanosheets via a facile oil‐bath method.The photocatalytic activity of the Au/monolayer g‐C3N4 composites under visible light was evaluated by photocatalytic hydrogen evolution and environmental treatment.All of the Au/monolayer g‐C3N4 composites showed better photocatalytic performance than that of monolayer g‐C3N4 and the 1%Au/monolayer g‐C3N4 composite displayed the highest photocatalytic hydrogen evolution rate of the samples.The remarkable photocatalytic activity was attributed largely to the successful introduction of Au plasmonic nanoparticles,which led to the surface plasmon resonance(SPR)effect.The SPR effect enhanced the efficiency of light harvesting and induced an efficient hot electron transfer process.The hot electrons were injected from the Au plasmonic nanoparticles into the conduction band of monolayer g‐C3N4.Thus,the Au/monolayer g‐C3N4 composites possessed higher migration and separation efficiencies and lower recombination probability of photogenerated electron‐hole pairs than those of monolayer g‐C3N4.A photocatalytic mechanism for the composites was also proposed.

Facile microwave-assisted ionic liquid synthesis of sphere-like BiOBr hollow and porous nanostructures with enhanced photocatalytic performance

In this work, two kinds of self-assembled hierarchical BiOBr microcrystals were rapidly synthesized through a simple microwave-assisted route in the presence of reactable ionic liquid 1-hexadecyl-3-methylimidazolium bromide([C_(16)mim]Br). These porous and hollow BiOBr microspheres were obtained via a facile solvothermal method with or without polyvinyl pyrrolidone(PVP), respectively. During the synthetic process, ionic liquid [C_(16)mim]Br played as solvent, reactant and template at the same time. Moreover, the BiOBr hollow and porous microspheres exhibited outstanding photocatalytic activities for the degradation of rhodamine B(RhB) under visible light irradiation. A possible photocatalytic mechanism was also discussed in detail. It can be assumed that the higher photocatalytic activities of BiOBr porous microspheres materials could be ascribed to the novel structure, larger specific surface area, narrower band gap structure and smaller particle size.

Improved visible light photocatalytic activity of mesoporous FeVO_4 nanorods synthesized using a reactable ionic liquid

Mesoporous FeVO4 nanorods were successfully synthesized by calcining the precursor Fe- VO4·1.1H2O nanorods, which were obtained via a simple hydrothermal method in the presence of a reactable metal-ion-containing ionic liquid, 1-octyl-3-methylimidazolium tetrachloride ferrate(III)([Omim]FeCl4). The structure and morphology of the prepared samples were examined using various characterization techniques. During the synthetic process,[Omim]FeCl4 acted as the solvent, reactant, and capping agent simultaneously. Moreover, the porous FeVO4 nanorods as the heterogeneous photo-Fenton-like semiconductor catalyst for the degradation of tetracycline and rhodamine B under visible light irradiation exhibited excellent photocatalytic activity. This excellent photocatalytic activity of the porous FeVO4 nanorods can be attributed to the synergistic effect of their high electron-hole pair separation rate, suitable band gap structure, and large specific surface area. The possible photocatalytic degradation mechanism of FeVO4/H2O2 photocatalytic systems was also discussed in detail.

Designing all-solid-state Z-Scheme 2D g-C_3N_4/Bi_2WO_6 for improved photocatalysis and photocatalytic mechanism insight

Bi_2WO_6 was modified by two-dimensional g-C_3N_4(2D g-C_3N_4)via a hydrothermal method.The structure,morphology,optical and electronic properties were investigated by multiple techniques,including X-ray diffraction(XRD),X-ray photoelectron spectroscopy spectra(XPS),Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),transmission electron microscopy(TEM),Ultravioletvisible diffuse reflection spectroscopy(DRS),photocurrent and electrochemical impedance spectroscopy(EIS),electron spin resonance(ESR),respectively.Rhodamine B(Rh B)was used as the target organic pollutant to research the photocatalytic performance of as-prepared composites.The Bi_2WO_6/2D g-C_3N_4exhibited a remarkable improvement compared with the pure Bi_2WO_6.The enhanced photocatalytic activity was because the photogenerated electrons and holes can quickly separate by Z-Scheme passageway in composites.The photocatalytic mechanism was also researched in detail through ESR analysis.

Characterization and adsorption behaviors of a novel synthesized mesoporous silica coated carbon composite

A novel mesoporous silica coated carbon composite(denoted SEG) with hierarchical pore structure has been successfully prepared in an aqueous solution that contains triblock copolymer template, aluminum chloride, siliceous source and expanded graphite. Textural property and morphology of the SEG composite were characterized by the combination of X-ray diffraction, N_2 adsorption–desorption, scanning electron microscopy,transmission electron microscopy and Fourier transform infrared measurements. Results show that mesoporous silica is steadily and uniformly grown on the surface of the graphite slices and the thickness of the silica layer can be finely tuned according to the silica/C molar ratio in the initial reaction solution. This newly synthesized SEG composite shows greatly increased adsorption capacity to methylene blue than the pristine expanded graphite in the batch tests. Both Langmuir and Frendlich models were further used to evaluate the adsorption isotherms of methylene blue over expanded graphite and SEG samples with different silica contents. Finally, pseudosecond-order model was used to describe the kinetics of methylene blue over expanded graphite and the silica-carbon composites.

重复囚徒博弈在无标度网络中的演化

在P2P和移动P2P网络中,自主节点都需要在有限资源(带宽,电源等)下进行通信和数据共享。如何提高系统的合作水平而减少背叛(搭便车),是个值得深入研究的问题。重复囚徒博弈在生物学、社会学、经济学、信息学等领域正在被广泛的研究,在个体自私的情况下整体涌现合作行为是人们感兴趣的焦点。本文利用遗传算法研究重复囚徒困境博弈在无标度网络中的演化,揭示网络中节点产生合作的相关机制。网络中的节点记忆以前多次和相邻节点的博弈情况,按照一定的编码方法转换成遗传算法中的基因,本文研究了不同记忆长度对合作水平的影响,特征基因的显现分布和基因使用频率,合作节点的度分布情况等。这些研究结论对于设计一个自组织的具有合作机制的系统提供了理论上的支持。

Interfacial Bonding Strength of TiN Film Coated on Si_3N_4 Ceramic Substrate

The fraction of TiN/Si3N4 in the cross section was observed with scanning electric microscope （SEM）, and residual stresses of TiN coated on the surface of Si3N4 ceramic were measured with X-ray diffraction （XRD）.The hardness of TiN film was measured, and bonding strength of TiN film coated on Si3N4 substrate was measured by scratching method. The formed mechanism of residual stress and the failure mechanism of the bonding interface in the film were analyzed, and the adhesion mechanism of TiN film was investigated preliminarily. The results show that residual stresses of TiN film are all behaved as compressive stress, and TiN film is represented smoothly with brittle fracture, which is closely bonded with Si3N4 substrate. TiN film has high hardness and bonding strength of about 500 MPa, which could satisfy usage requests of the surface of cutting Si3N4 ceramic.

Comparative Study on Electromagnetic and Electrome-chanical Transient Model for Grid-connected Photovoltaic Power System

With the development of new energy technology, there are increasing applications of grid-connected photovoltaic power generation system. However, there is little research on development of electromechanical model of large scale photovoltaic power station. The computational speed will be very slow if electromagnetic transient model is used for stability study because of its complexity. Therefore, study on electromechanical transient model of grid-connected photovoltaic power generation system is of great meaning. In this paper, electromagnetic transient model of photovoltaic power generation system is introduced first, and then a general electromechanical transient model is proposed. These two kinds of simulation model are set up in PSCAD. By comparing the simulation results of two models, the correctness and validity of the electromechanical transient model is verified. It provides reference model for efficient simulation and modeling of grid-connected photovoltaic power station in large-scale power systems.

Partial Feedback Based Orthogonal Space-Time Block Coding With Flexible Feedback Bits

The conventional orthogonal space-time block code (OSTBC) with limited feedback has fixed p-1?feedback bits for the specific ntp?transmit antennas. A new partial feedback based OSTBC which provides flexible feedback bits is proposed in this paper. The proposed scheme inherits the properties of having a simple decoder and the full diversity of OSTBC, moreover, preserves full data rate. Simulation results show that for?ntp transmit antennas, the proposed scheme has the similar performance with the conventional one by using p-1?feedback bits, whereas has the better performance with more feedback bits.

A Novel Cooperative Multicast Scheme Based on Fountain Code

Multicast is an efficient way to support emerging multimedia services over wireless network. Fountain codes are used in multicast systems to enable a robust transmission without CSI feedback and ARQ. We propose a cooperative multicast scheme based on fountain code to improve the performance of multicast. The users are coordinated with each other to decode the message at different time slots within the data transmission of a multicast session. Speci?cally, we take the local channel state information (CSI) and the local residual energy information (REI) into consideration, and apply a relay-selection and power-allocation strategy in our cooperative multicast scheme to prolong the network lifetime, while keeping the transmission delay as low as possible. The simulation results show that the proposed scheme can achieve a good tradeoff between transmission delay and network lifetime.

Adaptive Rate Control for Multi-Antenna Multicast in OFDM Systems

We propose two rate control schemes for multi-antenna multicast in OFDM systems, which aim to maximize the minimum average rate over all users in a multicast group. In our system, we do not require all multicast users to successfully recover the signals received on each subcarrier. In contrast, we allow certain loss for multicast users, such that the multicast transmission rate can be increased. We assume that the loss-repairing can be completed at upper protocol layers via advanced fountain codes. Following this principle, we formulate the rate control problem via beamforming in multi-antenna multicast to optimize the minimum achievable rate for all multicast users. While the computation complexity to solve for the optimal beamformer is prohibitively high, we propose a suboptimal iterative rate control scheme. Moreover, we modify the above optimization problem by selecting a ?xed proportion of users on each subcarrier. The beamformer searching process will then be performed only based on the selected users on each subcarrier, such that the complexity can be further reduced. We also solve this new problem with a low complexity approach. Theoretical analyses and simulation results show that our proposed two rate control schemes can have higher minimum average rate than the baseline scheme without rate control, while achieving low complexity.

Simple and Selective Colorimetric Detection of Oxytetracycline Based on Fe(III) Ion-3,3’,5,5’-Tetramethylbenzidine

Oxytetracycline (OTC) is a common antibacterial agent used for the control of animal diseases. OTC abuse can seriously affect human health. Herein, based on the Fe(III)-3,3’,5,5’-tetramethylbenzidine (Fe(III)-TMB) system, a facile and rapid colorimetricassay for oxytetracycline (OTC) was successfully developed. The addition of OTC could remarkably enhance the Fe(III)-oxidized TMB reaction and the absorbance increase of Fe(III)-TMB solution is proportional to the added OTC. The linear range of proposed sensor for OTC was from 20 nM to 1000 nM with the detection limit of 7.97 nM. The high sensitivity for OTC detection was successfully achieved under optimal conditions. For real sample analysis, recoveries of 89.93% to 100.02% was obtained. This is the first report for detecting OTC based on the nonenzymatic colorimetric reaction using the intrinsic oxidized activity of OTC/Fe3+ complex. The present simple, low-cost and visualized sensor has great potential for OTC detection in food.

用于收集低品位热的热电化学电池研究进展

低品位热(<150℃)是一种丰富且广泛存在的可持续能源,但也存在分布弥散、利用率低的特点.因此,开发高效且经济的低品位热回收技术对于能源的利用有着重要的意义.近年来,一种新型的低成本低品位热富集体系——热电化学电池逐渐兴起,并引起研究者极大的兴趣.基于此,本综述详细总结了近十年来关于热电化学电池这一新兴能源富集体系的研究进展.本文首先介绍了热电化学电池的组成及工作原理,然后探讨了现有电池装置的主要设计类型;接着,针对如何提升电池体系的温度系数(Se)和功率密度(P),详细讨论了电解液和电极材料的研究进展;最后,介绍了电池体系在面向实际应用时的组装及设备集成方法,并展望了该研究领域未来所面临的机遇和挑战.