Coordinatively unsaturated sites in zeolite matrix: Construction and catalysis

Zeolites with ordered porous structure of molecular size are widely employed as commercial adsorbents and catalysts.On the other hand,the zeolite matrix is regarded as an ideal scaffold for hosting coordinatively unsaturated sites.Remarkable achievements have been made dealing with the construction,characterization and catalytic applications of coordinatively unsaturated sites in zeolite matrix.Herein,a literature overview of recent progresses on this important topic is presented from the specific view of coordination chemistry.Different strategies to construction coordinatively unsaturated sites in zeolite matrix,in zeolite framework or extraframework positions,are first introduced and their characteristics are compared.Then,spectroscopic techniques to determine the existing states of cation sites and their transformations in zeolite matrix are discussed.In the last section,the catalytic applications of coordinatively unsaturated sites in zeolite matrix for various important chemical transformations are summarized.

Asymmetric Zn-N_4 atomic sites embedded hollow fibers as stable Zn anode for high-performance Zn-ion hybrid capacitor

Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of Zn metal anodes(ZMAs)severely restrict their applications.To address these issues,we design the asymmetric Zn-N_(4) atomic sites embedded hollow fibers(AS-IHF)as the flexible host for stable ZMAs.Through introducing different nitrogen resources in the synthesis,two kinds of coordination,i,e.Zn-N(pyridinic)and Zn-N(pyrrolic),are introduced in the Zn-N_(4) atomic module synchronously.The asymmetric Zn-N_(4) module with regulated micro-environment facilitates the superior zincophilic features and promotes the Zn adsorption.Meanwhile,the highly porous structure of the hollow fiber effectively reduces local current density,homogenize Zn ion flux,and alleviate structure stress.All the advantages endow the high efficiency and good stability for Zn plating/stripping.Both theoretical and experimental results demonstrate the high reversibility,low nucleation overpotential,and dendritefree behavior of the AS-IHF@Zn anode,which afford the high stability in high-rate and long-term cycling.Moreover,the solid-state Zn-ion hybrid capacitor(ZIHC)based on AS-IHF@Zn anode shows the high flexibility,reliability,and superior long-term cycling capability in a wide-range of temperatures(-20-25℃).Therefore,the present work not only gives a new strategy for modulating local environments of single atomic sites,but also propels the development of flexible power sources for diverse electronics.

Regulating the coordination microenvironment of atomic bismuth sites in nitrogen-rich carbon nanosheets as anode for superior potassium-ion batteries

Carbon-based materials are recognized as anodes fulling of promise for potassium ion batteries(PIBs)due to advantages of affordable cost and high conductivity.However,they still face challenges including structural unstability and slow kinetics.It is difficult to achieve efficient potassium storage with unmodified carbonaceous anode.Herein,atomic bismuth(Bi)sites with different atom coordinations anchored on carbon nanosheets(CNSs)have been synthesized through a template method.The properties of prepared multi-doping carbon anodes Bi-N_(3)S_(1)/CNSs,Bi-N_(3)P_(1)/CNSs and Bi-N_(4)/CNSs were probed in PIBs.The configuration Bi-N_(3)S_(1) with stronger charge asymmetry exhibits superior potassium storage performance compared to Bi-N_(3)P_(1) and Bi-N_(4) configurations.The Bi-N_(3)S_(1)/CNSs display a rate capacity of 129.2 mAh g^(-1)even at 10 A g^(-1)and an impressive cyclability characterized by over 5000 cycles at 5 A g^(-1),on account of its optimal coordination environment with more active Bi centers and K^(+)adsorption sites.Notably,assembled potassium-ion full cell Mg-KVO//Bi-N_(3)S_(1)/CNSs also shows an outstanding cycling stability,enduring 3000 cycles at 2 A g^(-1).Therefore,it can be demonstrated that regulating the electronic structure of metallic centre M-N_(4) via changing the type of ligating atom is a feasible strategy for modifying carbon anodes,on the base of co-doping metal and non-metal.

Facile synthesis of metal-organic frameworks embedded in interconnected macroporous polymer as a dual acid-base bifunctional catalyst for efficient conversion of cellulose to 5-hydroxymethylfurfural

5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.

Tuning the atomic configuration environment of MnN_(4) sites by Co cooperation for efficient oxygen reduction

Carbon-based N-coordinated Mn(Mn-N_(x)/C)single-atom electrocatalysts are considered as one of the most desirable non-precious oxygen reduction reaction(ORR)candidates due to their insignificant Fenton reactivity,high abundance,and intriguing electrocatalytic performance.However,current MnN_(x)/C single-atom electrocatalysts suffer from high overpotentials because of their low intrinsic activity and unsatisfactory chemical stability.Herein,through an in-situ polymerization-assisted pyrolysis,the Co as a second metal is introduced into the Mn-N_(x)/C system to construct Co,Mn-N_(x)dual-metallic sites,which atomically disperse in N-doped 1D carbon nanorods,denoted as Co,Mn-N/CNR and hereafter.Using electron microscopy and X-ray absorption spectroscopy(XAS)techniques,we verify the uniform dispersion of CoN4and MnN4atomic sites and confirm the effect of Co doping on the MnN_(4) electronic structure.Density functional theory(DFT)calculations further elucidate that the energy barrier of ratedetermining step(^(*)OH desorption)decreases over the 2 N-bridged MnCoN_(6) moieties related to the pure MnN_(4).This work provides an effective strategy to modulate the local coordination environment and electronic structure of MnN_(4) active sites for improving their ORR activity and stability.

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.

Regulating Lewis Acid-Base Sites over Fenton System for Enhancing Degradation of Pollutants in Saline and Buffered Wastewater

The saline and buffered environment in actual wastewater imposes higher demands on Fenton and Fenton-like catalytic systems.This study developed a MoS_(2)co-catalytic Fe_(2)O_(3)Fenton-like system with controllable Lewis acid-base sites,achieving efficient treatment of various model pollutants and actual industrial wastewater under neutral buffered environment.The acidic microenvironment structured by the edge S sites(Lewis basic sites)in the MoS_(2)/Fe_(2)O_(3)catalyst is susceptible to the influence of Lewis acidic sites constructed by Mo and Fe element,affecting catalytic performance.Optimizing the ratio of precursor amounts ensures the stable presence of the acidic microenvironment on the surface of catalyst,enabling the beneficial co-catalytic effect of Mo sites to be realized.Furthermore,it transcends the rigid constraints imposed by the Fenton reaction on reaction environments,thereby expanding the applicability of commonplace oxides such as Fe_(2)O_(3)in actual industrial water remediation.

Regulation of Coordinating Anions around Single Co(Ⅱ)Sites in a Covalent Organic Framework for Boosting CO_(2)Photoreduction

While photocatalytic CO_(2)reduction has been intensively investigated,reports on the influence of anions coordinated to catalytic metal sites on CO_(2)photoreduction remain limited.Herein,different coordinated anions(F^(−),Cl^(−),OAc^(−),and NO_(3)^(−))around single Co sites installed on bipyridine-based three-component covalent organic frameworks(COFs)were synthesized,affording TBD-COF-Co-X(X=F,Cl,OAc,and NO3),for photocatalytic CO_(2)reduction.Notably,the presence of these coordinated anions on the Co sites significantly influences the photocatalytic performance,where TBD-COF-Co-F exhibits superior activity to its counterparts.Combined experimental and theoretical results indicate that the enhanced activity in TBD-COF-Co-F is attributed to its efficient charge transfer,high CO_(2)adsorption capacity,and low energy barrier for CO_(2)activation.This study provides a new strategy for boosting COF photocatalysis through coordinated anion regulation around catalytic metal sites.

Atom-level interfacial synergy of single-atom site catalysts for electrocatalysis

Single-atom site catalysts(SACs)have made great achievements due to their nearly 100%atomic utilization and uniform active sites.Regulating the surrounding environment of active sites,including electron structure and coordination environment via atom-level interface regulation,to design and construct an advanced SACs is of great significance for boosting electrocatalytic reactions.In this review,we systemically summarized the fundamental understandings and intrinsic mechanisms of SACs for electrocatalytic applications based on the interface site regulations.We elaborated the several different regulation strategies of SACs to demonstrate their ascendancy in electrocatalytic applications.Firstly,the interfacial electronic interaction was presented to reveal the electron transfer behavior of active sites.Secondly,the different coordination structures of metal active center coordinated with two or three non-metal elements were also summarized.In addition,other atom-level interfaces of SACs,including metal atom–atom interface,metal atom-X-atom interface(X:non-metal element),metal atom-particle interface,were highlighted and the corresponding promoting effect towards electrocatalysis was disclosed.Finally,we outlooked the limitations,perspectives and challenges of SACs based on atomic interface regulation.

Synergistic Lewis acid-base sites of ultrathin porous Co_(3)O_(4)nanosheets with enhanced peroxidase-like activity

Surface Lewis acid-base sites in crystal structure may influence the physicochemical properties and the catalytic performances in nanozymes.Understanding the synergistic effect mechanism of Co_(3)O_(4)nanozymes towards substances(3,3’,5,5’-tetramethylbenzidine(TMB)and hydrogen peroxide(H2O2))induced by surface Lewis acid-base sites is important to enhance the efficiency for peroxidase-like reaction.Herein,ultrathin porous Co_(3)O_(4)nanosheets with abundant Lewis acid-base sites were prepared by sodium borohydride(NaBH4)reduction treatment,which exhibited high-efficiency peroxidase-like activity compared with original Co_(3)O_(4)nanosheets.The Lewis acid-base sites for ultrathin porous Co_(3)O_(4)nanosheets nanozyme were owing to the coordination unsaturation of Co ions and the formation of defect structure.Ultrathin porous Co_(3)O_(4)nanosheets had 18.26-fold higher catalytic efficiency(1.27×10^(-2)s^(-1)·mM^(-1))than that of original Co_(3)O_(4)(6.95×10^(-4)s^(-1)·mM^(-1))in oxidizing TMB substrate.The synergistic effect of surface acid and base sites can enhance the interfacial electron transfer process of Co_(3)O_(4)nanosheets,which can be a favor of absorption substrates and the generation of reactive intermediates such as radicals.Furthermore,the limit of detection of hydroquinol was 0.58μM for ultrathin porous Co_(3)O_(4)nanosheets,965-fold lower than original Co_(3)O_(4)(560μM).Besides,the linear range of ultrathin porous Co_(3)O_(4)nanosheets was widely with the concentration of 5.0-1,000μM.Colorimetric detection of hydroquinol by agarose-based hydrogel membrane was provided based on excellent peroxidase-like properties.This study provided insights into designing high-performance nanozymes for peroxidase-like catalysis via a strategy of solid surface acid-base sites engineering.

Coordination cage with structural “defects” and open metal sites catalyzes selective oxidation of primary alcohols

Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions.We present herein a viable strategy to conveniently construct multimetallic active sites into a coordination cage via self-assembly of a pre-formed sulfonylcalix[4]arene-based tetranuclear copper(II)precursor and an amino-functionalized dicarboxylate linker.The cage exhibits a“defective”,partially open cylindrical structure and features coordinatively labile dimetallic Cu(II)sites.Modulated by this unique inner cavity environment,promising catalytic activity toward selective oxidation of primary alcohols to carboxylic acids at room temperature is achieved.Mechanistic studies reveal that the coordinatively labile dimetallic Cu(II)sites can efficiently capture and activate the substrate and oxidant to catalyze the reaction,while the confined nano-cavity environment modulates substrate binding and enhances the catalytic turnover.This study provides a new approach to designing biomimetic multifunctional coordination cages and environmentally friendly supramolecular catalysts.

Acid-base Vapor Sensing Enabled by ESIPT-attributed Cd(II) Coordination Polymer with Switchable Luminescence

Fluorescence materials based on excited state intramolecular proton transfer(ESIPT)have attracted great attentiori due to the unique four-level energy states.Herein,we report the assembly of a Cd-LF coordination polymer from purposely designed LF(H2hpi2cf)ligand,which can present switchable luminescence behavior by gain or loss protons originated in uncoordinated ESIPT sites and serve as acid-base vapor sensors.Fabricated into in-situ grown film or transparent ink by simple methods,Cd-LF presents facile and portable amine sensor for food spoilage detection and fluorescent anti-counterfeiting ink applications.

Research on Wireless Monitoring Technology of the Well Site Environment

Based on the characteristics of wireless communication technology and Wireless Sensor Network, this paper studies the well site environmental monitoring system. The relevant hardware and software of the system are designed to monitor the well site environment, thus preventing downhole accidents. The system uses the wireless ZigBee technology as the transmission mode, and combines the virtual instrument technology to design the upper machine interface. The test results show that the system can monitor the outdoor environment in real time. When the environmental parameters exceed the set value, the corresponding location of the LabVIEW interface will send an alarm.

Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction

With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

基于PID控制技术的电力系统运行自动化控制系统

为保证电力系统的调度效果,实现电力系统智能化管控,设计基于PID控制技术的电力系统运行自动化控制系统。系统的基础层通过数据采集设备采集电力系统运行状态数据,通过通信接口将其传送至数据层;数据层依据数据分层传输结构和数字签名机制,存储以及调度接收的数据;控制层调用数据层中的数据,利用模糊级联PID控制器完成电力系统运行自动化控制,并向基础层的现场控制器下达协调控制指令,实现电力系统现场控制,并回传控制结果。测试结果显示,该系统的数据调度能力较好,RPS系数结果均在0.942以上,电力系统运行的失效率和修复率均在92.7%以上,绝对误差积分结果均在0.025以下,控制响应能力较好。

计及静态电压稳定性的风光电站选址定容协同规划方法

为了降低风光电站并网给电力系统电压稳定性带来的负面影响,提出了计及静态电压稳定性的风光电站选址定容协同规划方法。分析了风光电站的发电特性,并对其建立数学模型;考虑并网等值阻抗和静态电压稳定性的内在制约关系,进一步综合风光电站及其汇集站选址定容、并网点位置等优化目标,建立了风光电站选址定容协同规划模型;基于地图栅格化和分段线性化方法,将所提规划模型转换为混合整数线性规划模型;在此基础上,利用K-means算法提取典型场景,并给出了所提模型的求解流程。基于西南某地区的实际数据进行算例验证,结果表明所提规划方法能够充分发挥规划区域内自然资源的禀赋特性和风光发电互补性,有效提高了风光电站并网后的静态电压稳定性。

多层级协同的地铁应急救援基地选址优化

地铁系统面对灾害、事故时具有天然的脆弱性,随着各大城市的地铁进入网络化运营时代,我国地铁应急救援基地存在选址不合理、救援效率低等问题,而现有研究缺少层级性和协同救援的考虑。为此,以时间惩罚值最小、平均救援距离最短、选址个数最少为目标,以救援时间为约束,建立了多层级协同的地铁应急救援基地选址多目标优化模型,设计了遗传算法进行求解,并以南昌地铁为例进行了案例分析。研究结果表明:相比于单道路救援和单地铁救援的选址方案,采用协同救援的区域级地铁应急救援基地在时间惩罚函数值上分别降低了71.54%和73.82%,在平均救援时间上分别降低了14.71%和20.58%,在选址个数上分别降低了20.83%和9.52%。

基于TOPSIS和耦合协调度的高标准农田改造提升项目遴选

科学确定高标准农田改造提升的重点区域是切实发挥高标准农田建设成效、提升粮食生产能力的关键。该研究以山东省乐陵市为研究区,运用层次分析法和优劣解距离法(technique for order preference by similarity to ideal solution,TOPSIS)构建考虑农田基础设施、耕地地力质量和水资源利用状况的高标准农田改造提升迫切性评价体系,并基于维度间的耦合协调度及其空间特征划定改造提升项目区。结果表明:1)乐陵市已建高标准农田占耕地面积的87.93%,西南和东部地区建设基础较好,南部和中部薄弱;高等地力农田面积较少,分布于中南地区和东北地区;水资源利用状况总体呈现“中部高、北部和南部低”的特征。2)农田基础设施、耕地地力质量和水资源利用状况3个维度间的耦合协调度指数为0.41~0.85,高值聚集分布于西南部、东部和东北部,低值聚集分布于南部和西北部,中值交叉分布于中西部和中南部地区。3)基于耦合协调度指数及其空间特征遴选出12个高标准农田改造提升项目区,根据指数分级结果从低到高确立为近期(8633.23 hm^(2))、中期(11004.64 hm^(2))、远期(9102.62 hm^(2))建设项目。结合各项目区立地条件和高障碍度、高频率障碍因子,建议围绕资金整合、水源保障、设施配套、地力提升、结构改良等方面分类推进。该方法对于高标准农田改造提升区域选择以及重点建设方向确定具有一定借鉴价值。

Catalysis stability enhancement of Fe/Co dual-atom site via phosphorus coordination for proton exchange membrane fuel cell

Non-precious metal catalysts(NPMCs)are promising low-cost alternatives of Pt/C for oxygen reduction reaction(ORR),which however suffer from serious stability challenge in the devices of proton-exchange-membrane fuel cells(PEMFC).Different from the traditional strategies of increasing the degree of graphitization of carbon substrates and using less Fenton-reactive metals,we prove here that proper regulation of coordination anions is also an effective way to improve the stability of NPMC.N/P cocoordinated Fe-Co dual-atomic-sites are constructed on ZIF-8 derived carbon support using a molecular precursor of C_(34)H_(28)Cl_(2)CoFeP_(2)and a“precursor-preselected”method.A composition of FeCoN_(5)P1 is infered for the dual-atom active site by microscopy and spectroscopy analysis.By comparing with N-coordinated references,we investigate the effect of P-coodination on the ORR catalysis of Fe-Co dual-atom catalysts in PEMFC.The metals in FeCoN_(5)P1 have the lower formation energy than those in the solo N-coordinated active sites of FeCoN6 and FeN_(4),and exhibits a much better fuel cell stability.This anion approach provides a new way to improve the stability of dual-atom catalysts.

基于面需求法的充电设施分区选址优化

为解决充电设施激增、充电桩容量不匹配等问题,平衡区域充电负荷,提升用户充电满意度,合理布局充电设施至关重要。为此,提出一种基于面需求法的电动汽车充电设施选址方法。首先,根据慢充桩和快充桩的现有分布情况,对配电网区域进行分区建模。其次,结合电动汽车用户的分布和各区域的车流量,确定最佳充电设施布局区域。考虑到分布式电源和储能设施较多,为减少弃风弃光情况,分区选址过程需综合考虑分布式能源设施的位置。最后,运用粒子群优化算法对案例进行仿真分析。结果表明,基于面需求法的充电设施分区选址优化方法可降低充电过载风险99.7%,提升充电设施功率稳定性63.2%,提高用户充电满意度3.2%,体现了分区选址策略的有效性。