Self-supporting and hierarchically porous Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure as a bifunctional electrocatalyst for fluctuating overall water splitting

Stable non-noble metal bifunctional electrocatalysts are one of the challenges to the fluctuating overall water splitting driven by re-newable energy.Herein,a novel self-supporting hierarchically porous Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure as bifunctional electrocatalyst was constructed based on porous Ni-Fe electrodeposition on three-dimensional(3D)carbon fiber cloth,in situ oxidation,and chemical sulfuration.Results showed that the Ni_(x)Fe-S/NiFe_(2)O_(4) heterostructure with a large specific surface area exhibits good bifunctional activity and stability for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)because of the abundance of active sites,synergistic effect of the heterostructure,superhydrophilic surface,and stable,self-supporting structure.The results further confirmed that the Ni_(x)Fe-S phase in the heterostructure is transformed into metal oxides/hydroxides and Ni_(3)S_(2) during OER.Compared with the commercial 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer,the self-supporting Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) electrolyzer exhibits better stability and lower cell voltage in the fluctu-ating current density range of 10-500 mA/cm^(2).Particularly,the cell voltage of Ni1/5Fe-S/NiFe_(2)O_(4)||Ni1/2Fe-S/NiFe_(2)O_(4) is only approximately 3.91 V at an industrial current density of 500 mA/cm^(2),which is lower than that of the 20wt%Pt/C||IrO_(2)-Ta_(2)O_(5) electrolyzer(i.e.,approximately 4.79 V).This work provides a promising strategy to develop excellent bifunctional electrocatalysts for fluctuating overall water splitting.

Optimizing band structure of CoP nanoparticles via rich-defect carbon shell toward bifunctional electrocatalysts for overall water splitting

Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of TMPs.Herein,a novel method for synthesizing CoP nanoparticles encapsu-lated in a rich-defect carbon shell(CoP/DCS)is developed through the self-assembly of modified polycyclic aromatic molecules.The graft and removal of high-activity C-N bonds of aromatic molecules render the controllable design of crystallite defects of carbon shell.The density functional theory calculation indicates that the carbon defects with unpaired electrons could effectively tailor the band structure of CoP.Benefiting from the improved activity and corrosion resistance,the CoP/DCS delivers outstanding difunctional hydrogen evolution reaction(88 mV)and oxygen evolution reaction(251 mV)performances at 10 mA cm^(−2)current density.Furthermore,the coupled water electrolyzer with CoP/DCS as both the cathode and anode presents ultralow cell voltages of 1.49 V to achieve 10 mA cm^(−2)with long-time stability.This strategy to improve TMPs electrocatalyst with rich-DCS and heterogeneous structure will inspire the design of other transition metal compound electrocatalysts for water splitting.

The Quaternion Structure of Space-Time and Arrow of Time

In fundamental theories of physics, the dynamical equations all have time inversion invariance. Except for the evolution of some simple system which has realistic inverse processes, but for a slightly more complicated system, the evolution processes are irreversible. This is the problem of arrow of time, which is always warmly debated. In different point of view, we find there may have some conceptual misunderstanding in the controversy: 1) The realization of an inverse process does not mean the time of the system goes backward. 2) The principles of relativity and covariance are the constraints to physical laws, but not constraints to specific solutions. The equations must be covariant, but the solutions are not definitely symmetric. 3) Time is a global property of the universe, which is a measurement of the evolution process of the universe. The internal time of a matter system reflecting its internal evolution speed also takes this cosmic time as a unified background and standard of measurement. 4) The universe has a unified cosmic time T and a cosmic space related to this cosmic time. They are objective and absolute. 5) The eigensolution of a spinor is a critical state losing time concept, which responses the interaction of environment with some uncertainty, then the evolution process of the world is not uniquely determined. 6) The non-uniqueness of the evolution process means that the inverse process is absent. So for a world including spinors, the evolution is essentially irreversible. In this paper, according to the widely accepted principles and direct calculations of transformation, we reveal the misunderstandings in the usual controversy, and then give more natural and reasonable explanations for structure of space-time and arrow of time.

Change of Space-Time Structure under Lorentz Transformation

When we study Lorentz transformation in the framework of quantum gauge theory of gravity, we will find that the vacuum gravitational gauge field will be changed under gravitational gauge transformation, which will change the structure of the physical space-time and cause clock dilation effect. The study in this paper provides us with new insights to understand the essential and intrinsic relation between special relativity and general relativity. It provides us with a new way to unify special relativity and general relativity.

Rational modulation of electronic structure in PtAuCuNi alloys boosts efficient electrocatalytic ethanol oxidation assisted with energy-saving hydrogen evolution

Compared to conventional electrocatalytic water splitting,electrocatalytic ethanol oxidation reaction(EOR)along with hydrogen production is considered a more energy-efficient strategy.Herein,we prepared a type of novel quaternary alloy catalyst(PtAuCuNi@NF)that exhibits excellent activity for EOR(0.215 V at 10 mA cm^(-2))and hydrogen evolution reaction(HER)(7 mV at 10 mA cm^(-2)).Experimental results demonstrated that both Cu and Ni modulated the electronic environment around Pt and Au.The electron-rich active center facilitates the rapid adsorption and dissociation of reactants and intermediates for both EOR and HER.Impressively,in the ethanol-assisted overall water splitting(E-OWS),a current density of 10 mA cm^(-2)was achieved at 0.28 V.Moreover,an advanced acid-base self-powered system(A-Bsps)that can achieve a self-powered voltage of 0.59 V was assembled.Accordingly,the self-driven hydrogen production with zero external power supply was realized by integrating A-Bsps with the E-OWS equipment.The interesting results can provide a feasible strategy for designing and developing advanced nanoalloy-based materials for clean energy integration and use in various fields.

MOF-Derived Iron-Cobalt Phosphide Nanoframe as Bifunctional Electrocatalysts for Overall Water Splitting

Transition metal phosphides(TMPs)have emerged as an alternative to precious metals as efficient and low-cost catalysts for water electrolysis.Elemental doping and morphology control are effective approaches to further improve the performance of TMPs.Herein,Fe-doped CoP nanoframes(Fe-CoP NFs)with specific open cage configuration were designed and synthesized.The unique nano-framework structured Fe-CoP material shows overpotentials of only 255 and 122 mV at 10 mA cm^(−2)for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER),respectively,overwhelming most transition metal phosphides.For overall water splitting,the cell voltage is 1.65 V for Fe-CoP NFs at a current density of 10 mA cm^(−2),much superior to what is observed for the classical nanocubic structures.Fe-CoP NFs show no activity degradation up to 100 h which contrasts sharply with the rapidly decaying performance of noble metal catalyst reference.The superior electrocatalytic performance of Fe-CoP NFs due to abundant accessible active sites,reduced kinetic energy barrier,and preferable*O-containing intermediate adsorption is demonstrated through experimental observations and theoretical calculations.Our findings could provide a potential method for the preparation of multifunctional material with hollow structures and offer more hopeful prospects for obtaining efficient earth-abundant catalysts for water splitting.

In-situ building of multiscale porous NiFeZn/NiZn-Ni heterojunction for superior overall water splitting

The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).A self-supporting,multiscale porous NiFeZn/NiZn-Ni catalyst with a triple interface heterojunction on nickel foam(NF)(NiFeZn/NiZn-Ni/NF)was in-situ fabricated using an electroplating-annealing-etching strategy.The unique multiinterface engineering and three-dimensional porous scaffold significantly modify the mass transport and electron interaction,resulting in superior bifunctional electrocatalytic performance for water splitting.The NiFeZn/NiZn-Ni/NF catalyst demonstrates low overpotentials of 187 m V for HER and 320 mV for OER at a current density of 600 mA/cm^(2),along with high durability over 150 h in alkaline solution.Furthermore,an electrolytic cell assembled with NiFeZn/NiZn-Ni/NF as both the cathode and anode achieves the current densities of 600 and 1000 m A/cm^(2) at cell voltages of 1.796 and 1.901 V,respectively,maintaining the high stability at 50 mA/cm^(2) for over 100 h.These findings highlight the potential of NiFeZn/NiZn-Ni/NF as a cost-effective and highly efficient bifunctional electrocatalyst for overall water splitting.

Efficient electrocatalytic overall water splitting and structural evolution of cobalt iron selenide by one-step electrodeposition

Developing bifunctional electrocatalysts with both high catalytic activity and high stability is crucial for efficient water splitting in alkaline media.Herein,a Fe-incorporated dual-metal selenide on nickel foam(Co_(0.9)Fe_(0.1)-Se/NF) is synthesized via a facile one-step electrodeposition method.As-synthesized materials could serve as self-supported bifunctional electrocatalysts with excellent catalytic activity towards oxygen evolution reaction(OER) and hydrogen evolution reaction(HER) in alkaline media.Experimental results show that delivering a 10 mA cm^(-2) water splitting current density only requires a cell voltage of 1.55 V.In addition,a very stable performance could be kept for about 36 hours,indicating their excellent working stability.Moreover,by means of phase analysis,we have identified that the evolution of the synthesized Co_(0.9)Fe_(0.1)-Se/NF experiences two entirely different processes in HER and OER,which hydroxide and oxyhydroxide are regarded as the real active sites,respectively.This work may pave the way to further understanding the relationships between the reactivity and stability of chalcogenide-based electrocatalysts and facilitating the rational design of efficient electrocatalysts for future renewable energy system applications.

Design of p-n homojunctions in metal-free carbon nitride photocatalyst for overall water splitting

Two-dimensional(2D)carbon nitride(CN)photocatalysts are attracting extensive attention owing to their excellent photocatalytic properties.In this study,we successfully prepared CN materials with heterogeneous structures via hydrothermal treatment,high-temperature roasting,ball milling,sintering,and other processes.Benefitting from interface interactions in hybrid architectures,the CN photocatalysts exhibited high photocatalytic activity.The rate of hydrogen production using these CN photocatalysts reached 17028.82μmol h^(−1)g^(−1),and the apparent quantum efficiency was 11.2%at 420 nm.The ns-level time-resolved photoluminescence(PL)spectra provided information about the time-averaged lifetime of fluorescence charge carriers;the lifetime of the charge carriers causing the fluorescence of CN reached 9.99 ns.Significantly,the CN photocatalysts displayed satisfactory results in overall water splitting without the addition of sacrificial agents.The average hydrogen and oxygen production rates were 270.95μmol h^(−1)g^(−1)and 115.21μmol h^(−1)g^(−1)in 7 h,respectively,which were promising results for the applications of the catalysts in overall water splitting processes.We investigated the high efficiency of the prepared CN photocatalysts via a series of tests(UV-vis diffuse reflectance spectroscopy,photocurrent response measurements,PL emission spectroscopy,time-resolved PL spectroscopy,and Brunauer-Emmett-Teller analysis).Furthermore,the Mott-Schottky plot and current-voltage curve were acquired via electrochemical tests.The fabricated CN photocatalyst had a small p-n junction in its heterogeneous structure,which further enhanced its photocatalytic efficiency.Therefore,this work can promote the development of CN photocatalysts.

A new layered space-time detection algorithm for frequency selective fading multiple-input multiple-output channels based on particle filter

In this paper, a new observation equation of non-Gaussian frequency selective fading Bell Labs layered space time （BLAST） architecture system is proposed, which is used for frequency selective fading channels and non-Gaussian noise in an application environment of BLAST system. With othogonal matrix triangularization （QR decomposition） of the channel matrix, the static observation equation of frequency selective fading BLAST system is transformed into a dynamic state space model, and then the particle filter is used for space-time layered detection. Making the full use of the finite alphabet of the digital modulation communication signal, the optimal proposal distribution can be chosen to produce particle and update the weight. Incorporated with current method of reducing error propagation, a new space-time layered detection algorithm is proposed. Simulation result shows the validity of the proposed algorithm.

Two-dimensional bifunctional electrocatalyst(Mo-NiFe-LDH)with multilevel structure for highly efficient overall water splitting

To effectively address energy challenges,it is crucial to explore efficient and stable bifunctional nonprecious metal catalysts.In this study,a Mo-doped nickeliron layered double hydroxide with flower-cluster architecture was successfully prepared by a one-step hydrothermal method,which demonstrated a good water splitting performance.After an appropriate amount of Mo doping,some lattice distortions in the material provided reactive sites for the adsorption and conversion of intermediates,thus optimising the charge distribution of the material.Moreover,the multidimensional void structures formed after doping had a larger specific surface area and accelerated the penetration of the electrolyte,which significantly improved the activity of the catalyst in alkaline media.At 10 mA·cm^(-2),the hydrogen and oxygen evolution overpotentials of Mo-doped nickel-iron double hydroxides(Mo-NiFe LDH/NF-0.2)were 167 and 220 mV,respectively,with an excellent durability up to 24 h.When the Mo-NiFe LDH/NF-0,2 catalyst was used as the cathode and anode of an electrolytic cell,the catalyst achieved a current density of 10 mA·cm^(-2)at an applied voltage of 1.643 V.This study provides a novel approach for designing excellent bifunctional electrocatalysts containing nonprecious metals.

Laser-induced periodic surface structured electrodes with 45% energy saving in electrochemical fuel generation through field localization

Electrochemical oxidation/reduction of radicals is a green and environmentally friendly approach to generating fuels.These reactions,however,suffer from sluggish kinetics due to a low local concentration of radicals around the electrocatalyst.A large applied electrode potential can enhance the fuel generation efficiency via enhancing the radical concentration around the electrocatalyst sites,but this comes at the cost of electricity.Here,we report about a~45%saving in energy to achieve an electrochemical hydrogen generation rate of 3×10^(16) molecules cm^(–2)s^(–1)(current density:10 mA/cm^(2))through localized electric field-induced enhancement in the reagent concentration(LEFIRC)at laser-induced periodic surface structured(LIPSS)electrodes.The finite element model is used to simulate the spatial distribution of the electric field to understand the effects of LIPSS geometric parameters in field localization.When the LIPSS patterned electrodes are used as substrates to support Pt/C and RuO_(2) electrocatalysts,the η_(10) overpotentials for HER and OER are decreased by 40.4 and 25%,respectively.Moreover,the capability of the LIPSS-patterned electrodes to operate at significantly reduced energy is also demonstrated in a range of electrolytes,including alkaline,acidic,neutral,and seawater.Importantly,when two LIPSS patterned electrodes were assembled as the anode and cathode into a cell,it requires 330 mVs of lower electric potential with enhanced stability over a similar cell made of pristine electrodes to drive a current density of 10 mA/cm^(2).This work demonstrates a physical and versatile approach of electrode surface patterning to boost electrocatalytic fuel generation performance and can be applied to any metal and semiconductor catalysts for a range of electrochemical reactions.

In situ growth of NiSe@Co_(0.85)Se heterointerface structure with electronic modulation on nickel foam for overall water splitting

Constructing heterointerface engineering has becoming an effective and general strategy for developing highly efficient and durable nonnoble electrocatalysts for catalyzing both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In this work,we synthesized a self-supporting heterogeneous NiSe@Co_(0.85)Se/NF electrocatalyst using a facile in situ selenization of transition metal precursors that coated on the nickel foam(NF)in polyol solution.The NF was used as both conductive substrate and nickel source,ensuring superior electronic conductivity for catalyzing.The NiSe@-Co_(0.85)Se/NF exhibited remarkable bifunctional electrocatalytic activities with HER overpotential of 168 mV and OER overpotential of 258 mV to achieve 10 mA·cm-2.The water splitting system using NiSe@Co_(0.85)Se/NF as both anode and cathode electrodes achieved a current density of 10 mA·cm^(-2) at 1.61 V with nearly 100% faradaic efficiency and impressively long-term stability.The efficient bifunctional catalytic performance of NiSe@-Co_(0.85)Se/NF should be attributed to the electronic modulation and synergistic effect between NiSe and Co_(0.85)Se,the intrinsic metallic conductivity and the enlarged active sites exposure.This work provides a facile method for developing heterogeneous bifunctional catalysts for advanced electrochemical energy conversion technologies.

Structural design for electrocatalytic water splitting to realize industrial-scale deployment: Strategies, advances, and perspectives

The green hydrogen generation powered by renewable electricity promises the potential decarbonization of the hard-to-abate sector and is essential for the fulfillment of the Paris Agreement that attempts to limit the global average temperature rise in the range of 1.5–2.0 ℃ above the pre-industrial level by the end of this century. Tremendous efforts have been devoted to the optimization of the electrocatalytic performance of the catalysts under industrial-relevant current densities via rational structure design,which induces a preferential electron distribution that favors the adsorption/desorption behavior of the key intermediates, thus accelerating the reaction kinetics. In this review, a brief introduction of the current energy status will be first presented to necessitate the importance of green hydrogen.Followed by the basic concepts and fundamental understanding of the reaction mechanisms, we present efficient strategies for the enhancement of the electrocatalytic performance of the catalysts to meet the rigorous requirement under industrial conditions and the in-depth understanding behind the reinforcement will be briefly discussed next. Then the recent advances regarding the rational design of electrocatalysts operating at an industrial scale will be summarized. Finally, the challenges and perspectives in this thriving field will be proposed from our point of view.

Inhomogeneous space-time structure and two-pion interferometry in NEXSPHERIO model

We examine the space-time structure of particle-emitting source and two-pion interferometry in a smoothed hydrodynamic model with fluctuating initial conditions. An equation of state with a crossover transition between quark-gluon plasma and hadronic gas is adopted in the description of the system evolution. We find that the fluctuating initial conditions lead to inhomogeneous particle-emitting sources. The interferometry results of Rs and Ro indicate that both the source size and the duration of pion emission decrease when the freeze-out temperature increases. The values of Ro/Rs obtained by our simulated two-pion interferometry are consistent with the previous results of smoothed particle hydrodynamics, and smaller than those calculated in usual hydrodynamic models.

On the Planning of Chinese Marine High-tech Industry Demonstration Zones:From the Perspective of Supply-side Structural Reform

China’s national agricultural high-tech industry demonstration zones focus on supply-side structural reform in their overall plan of development.This paper selected the China’s marine industry as its research subject and analyzes its current situation and major problems.After summarizing the current researches of China’s marine industry parks,from the perspective of supply-side structural reform,this paper specifies the tasks and objectives of the construction of the marine hi-tech industry demonstration zones.The overall planning of the demonstration zones must set distinctive developmen as its orientation,and we should emphasize innovation-driven and green development,devise a functional zoning that embraces marine-land and allround integration,and seek mechanism innovations that could invigorate the inner drive of development.The paper also puts forward the major principles that the planning of marine hi-tech industry demonstration zones should obey in the context of supply-side structural reform.

异形单层网壳结构的整体稳定性研究及关键节点分析

单层网壳结构属于缺陷敏感结构,整体稳定问题是结构设计的关键.单层网壳结构可以采用空间相贯节点,有必要对节点进行三维实体有限元分析,在此基础上研究节点的力学性能.本文总结了单层网壳结构整体稳定分析的方法,归纳了空间相贯节点三维实体有限元分析方法;针对异形单层网壳结构,研究了结构的静力性能、结构网格与建筑形状对结构承载能力的影响,确定了结构的弹性稳定承载力和弹塑性稳定承载力;对空间相贯节点进行了有限元分析,得到节点处应力的分布情况,并研究了节点隐蔽部位有无焊缝对节点力学性能的影响.结果表明:异形单层网壳的曲率变化和结构网格对关键部位处杆件受力影响较大;稳定承载力对单层网壳结构起控制作用,对此异形单层网壳进行弹塑性稳定分析,结构安全系数达到24;隐蔽部位焊缝对节点承载力的影响较大,设置隐蔽部位焊缝后,节点处各杆件的最大应力可减小20%以上.

制浆造纸电磁感应加热压光机结构设计研究

压光整饰是制浆造纸过程中的重要工序,压光机作为制浆造纸工业中必不可少的纸张表面压光加工装置,其压光效果直接影响纸张的质量、应用和性能。对此,简述了传统制浆造纸压光机的弊端,介绍了电磁感应加热原理和电磁感应加热压光机的应用优势,设计了一种采用电磁感应加热方式的制浆造纸压光机,确定了压光机的总体结构和加热方案,并对压光机的加热线圈、加热辊筒、电机、轴承等关键部件进行设计与分析。以期开发节能高效的新型制浆造纸压光设备,使其应用领域更加广泛。

中国高等教育政策网络演进:从资源获取到功能实现的跃迁

通过对1980—2024年607份高等教育领域相关政策文件中的多个政策主体协同所形成的政策网络进行社会网络分析,重点研究整体网络和个体网络并进行可视化,以期更全面地理解不同政策主体在高等教育发展过程中的相互关系,为高等教育政策的制定和调整提供科学依据。研究表明:高等教育政策网络现处于第二层次向第三层次转型时期,即从资源获取阶段逐步过渡到功能实现阶段;高等教育政策网络规模呈现跨越式增长,结构呈现动态复杂变化特征;高等教育政策网络主体呈现“主副核心”共存,核心间构成紧密“铁三角”关系;教育部核心职能尚未完全发挥,相关产业部门参与度与协同作用有待加强。未来,在保持教育部作为“主核心”部门的引领地位的基调上,教育部可与相关产业部门建立定期对话机制,或鼓励教育部与产业部门之间的人员交流,积极培育位于政策网络边缘的创新型机构或组织,构建“核心-边缘”的创新网络,并加强与国际组织和其他国家的政策交流与合作,以此加快高等教育政策网络转型为功能实现层次,促进我国高等教育发展。

基于地下结构整体损伤表征的复合地震动参数构造及其性能验证

在地下结构抗震设计中,不同的输入地震动引起的地下结构响应有显著差异,因此,合理通过地震动参数选择输入地震动是正确开展地下结构抗震设计的重要前提。针对单一地震动参数难以表征地下结构地震动潜在破坏势问题,文章构造了能更好表征地下结构损伤破坏的复合地震动参数。具体开展了以下工作:提出基于变形与滞回耗能的地下结构整体损伤指标作为结构需求参数,以定量化评估地下结构的整体破坏状态。选取64条真实地震动记录作为输入地震动,开展四层三跨地铁车站地震弹塑性动力时程分析。基于分析结果提供的数据样本,采用偏最小二乘法从统计角度构造复合地震动参数。最后,选用100条真实地震动记录开展两层三跨地铁车站弹塑性动力时程分析,对文章所构造的复合地震动参数进行验证。对比分析复合地震动参数、12个常用地震动参数与地下结构整体损伤指数的回归统计特征。结果表明:复合地震动参数与结构需求数之间具有更好拟合优度值,其Pearson相关性、有效性也优于单一地震动参数。