An infinite chain, {[Ni(tn)2]3[Fe(CN)4(μ-CN)2]2}n,a new catalyst for electrochemical-driven water splitting and photochemical-driven hydrogen evolution from water under blue light

A new catalyst for both water reduction and oxidation, based on an infinite chain, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n, is formed by the reaction of NiCl₂, 1,3-propanediamine (tn) and K₃ [Fe(CN)₆]. {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can electro-catalyze hydrogen evolution from a neutral aqueous buffer (pH 7.0) with a turnover frequency (TOF) of 1561 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) at an overpotential (OP) of 837 mV {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n also can electro-catalyze O₂ production from water with a TOF of ～45 mol O₂ (mol cat)^?1s^?1 at an OP of 591 mV. Under blue light (λ = 469 nm), together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H₂A) as a sacrificial electron donor, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can photo-catalyze hydrogen generation from an aqueous buffer (pH 4.0) with a turnover number (TON) of 11,450 mol H₂ per mole of catalyst (mol of H₂ (mol of cat)^?1) during 10 h irradiation. The average of apparent quantum yield (AQY) is as high as 40.96% during 10 h irradiation. Studies indicate that {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n exists in two forms: a cyano-bridged chain ({[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n) in solid, and a salt ([Ni(tn)₂]₃ [Fe(CN)₆]₂) in aqueous media; Catalytic reaction occurs on the nickel center of [Ni(tn)₂]²⁺, and the introduction of [Fe(CN)₆]^3- can improve the catalytic efficiency of [Ni(tn)₂]²⁺ for H₂ or O₂ generation. We hope these findings can afford a new method for the design of catalysts for both water reduction and oxidation.     

Modeling unaccounted-for gas among residential natural gas consumers using a comprehensive fuzzy cognitive map

Residential natural gas consumption depends on several factors. Available tools and methods to identify, categorize, and validate effective factors have some limitations, making consumption modeling more complex. Once a comprehensive model of effective consumption factors is developed for residential gas consumers, it can predict consumption. In addition, such a model could be used to verify the accuracy of measuring devices in order to reduce unaccounted for gas (UFG). The key factors affecting residential gas consumption were identified based on previous studies and their mutual effects were analyzed using a fuzzy cognitive mapping (FCM) method. The most significant factors and their effects on natural gas consumption in the residential sector were determined. In this study, for the first time, the expected consumption for each consumer was estimated using a consumption index. Generally, if the estimated consumption is significantly different from the amount recorded by the meter, it could suggest a potential source of UFG. The proposed method was applied to the data collected from the residential gas consumers of a small region in Iran (Dasht-e Arjan region, Fars province), and the results demonstrate the effectiveness of the proposed method.     

Nanoarchitectonics of CdS/ZnSnO3 heterostructures for Z-Scheme mediated directional transfer of photo-generated charges with enhanced photocatalytic performance

The construction of heterostructure is an effective strategy to synergetically couple wide-band-gap with the narrow-band-gap semiconductor with a mediate optical property and charge transfer capability. Herein, the Z-Scheme CdS/ZnSnO₃ (CdS/ZSO) heterostructures were constructed by anchoring CdS nanoparticles on the surface of double-shell hollow cubic ZnSnO₃ via the hydrothermal method. The direct recombination of excited electrons in the conduction band (CB) of ZSO and holes in the valence band (VB) of CdS via d-p conjugation at the interface greatly accelerated the internal electric field (IEF). The transfer mode follows the Z-Scheme mechanism, where CdS/ZSO synergistically facilitates the efficient charges transfer from CdS to ZnSnO₃ through the intimate interface. Here, ZnSnO₃ and CdS serve as an oxidation photocatalyst (OP) and reduction photocatalyst (RP), respectively. Thus, it can promote synergistically the oxidation half-reaction and reduction half-reaction of H₂ evolution. The density-functional theory (DFT) calculation further confirms the charges transfer from CdS to ZnSnO₃. The hydrogen evolution of 5% CdS/ZSO heterostructure reached 1167.3 μmol g^?1, which was about 8 and 3 folds high compared to pristine ZSO (141.9 μmol g^?1) and CdS (315.5 μmol g^?1), during 3 h of reaction respectively. Furthermore, the CdS/ZSO heterostructures could suppress the photo corrosion of CdS, resulting in its high stability. This work is expected to enlighten the rational design of heterostructure for OP and RP to promote the hybrid heterostructures photocatalytic H₂ evolution.     

Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

Evaluation of Scale and Corrosion Inhibition of Modified Polyaspartic Acid

Amino acid modified polyaspartic acids were evaluated as calcium-scale inhibitors. Feasibility of scale inhibition experiments was analyzed by molecular dynamics simulation and Gaussian optimization, and the scale inhibition mechanism was theoretically analyzed. Scale inhibition performance was studied by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, static scale inhibition experiments, and electrochemical performance testing, which provided an experimental basis for the molecular dynamics simulation. The experimental results showed that Arg-SA-PASP has better scale inhibition and corrosion inhibition performance than His-SA-PASP. The scale inhibition effect increased with increasing concentration. Electrochemical tests indicated that Arg-SA-PASP is an excellent scale and corrosion inhibitor.     

论携号转网行为的私法规制

以电信用户入网协议为切入点,电信用户的携号转网行为应受到《合同法》《消费者权益保护法》等私法规范的保护与限制。该行为引起的格式条款解释、合同终止、违约责任、损失赔偿等问题,不能仅靠《电信条例》等公法规范来调整。应当积极引导广大消费者用户以私法领域相关规定为依据,转变争议解决思维,拓宽纠纷处理途径,合理选择维权手段,以保护自身合法民事权益,与行业监管部门共同推动电信行业有序发展。     

Semantically enriched Massive Open Online Courses (MOOCs) platform

Massive Open Online Courses (MOOCs) are becoming an essential source of information for both students and teachers. Noticeably, MOOCs have to adapt to the fast development of new technologies; they also have to satisfy the current generation of online students. The current MOOCs’ Management Systems, such as Coursera, Udacity, edX, etc., use content management platforms where content are organized in a hierarchical structure. We envision a new generation of MOOCs that support interpretability with formal semantics by using the SemanticWeb and the online social networks. Semantic technologies support more flexible information management than that offered by the current MOOCs’ platforms. Annotated information about courses, video lectures, assignments, students, teachers, etc., can be composed from heterogeneous sources, including contributions from the communities in the forum space. These annotations, combined with legacy data, build foundations for more efficient information discovery in MOOCs’ platforms. In this article we review various Collaborative Semantic Filtering technologies for building Semantic MOOCs’ management system, then, we present a prototype of a semantic middle-sized platform implemented at Western Kentucky University that answers these aforementioned requirements.     

高温氢工质热物理性质计算分析

氢工质在新能源与动力、航天推进、化工材料等领域有着广泛应用。通过开展高温氢工质热力学与输运性质研究，建立了原子态氢、分子态氢、热解平衡态氢的热物理性质计算模型，开发了热物性计算程序Prop_H_H2，适用范围为温度100~3 500 K、压力104~5×107 Pa 。验证表明，Prop_H_H2在适用范围内计算氢工质的物性参数合理可靠，在温度200~3 000 K、压力104~107 Pa范围内，程序预测值更加准确，相对偏差在±5%左右。本研究可为氢工质相关的航天推进、应用物理学、能源动力等行业的科研和应用提供支持借鉴。     

The concept of smartness in cyber–physical systems and connection to urban environment

The next-generation systems are expected to be largely cyber–physical systems (CPSs) that autonomously control physical processes, through sensors and actuators typically in real-time feedback and cooperative control loops distributed among physical and cyber environments. The rapid technological advancements enhance the smartness of these CPSs, pushing their boundaries of performance and efficiency by embedding new information and communication technologies. However, to what extent CPSs should be smarter so that they do not compromise safety and security of safety critical systems? is an open research question. Towards this goal, the purpose of this study is to establish a grounded theory to analyse what makes these systems smart? and eventually, how to find a balance between smartness and safety risks? In this precinct, this article aims to develop a conceptual framework, define the dimensions and derive the characteristics that make CPSs smart. The proposed approach combines an automated informetric and systematic analysis of literature pertinent to the topic of smartness across anthropology, science, engineering and technology. The analysis of a case study building and the discussions presented herein support the connection between the existing understanding of CPSs and smartness offered by the building design approach in urban environment.