Strategic comparison of membrane-assisted and membrane-less water electrolyzers and their potential application in direct seawater splitting(DSS)

Electrocatalytic splitting of water by means of renewable energy as the electricity supply is one of the most promising methods for storing green renewable energy as hydrogen. Although two-thirds of the earth’s surface is covered with water, there is inadequacy of freshwater in most parts of the world. Hence, splitting seawater instead of freshwater could be a truly sustainable alternative. However, direct seawater splitting faces challenges because of the complex composition of seawater. The composition, and hence, the local chemistry of seawater may vary depending on its origin, and in most cases, tracking of the side reactions and standardizing and customizing the catalytic process will be an extra challenge. The corrosion of catalysts and competitive side reactions due to the presence of various inorganic and organic pollutants create challenges for developing stable electro-catalysts. Hence, seawater splitting generally involves a two-step process, i.e., purification of seawater using reverse osmosis and then subsequent fresh water splitting. However, this demands two separate chambers and larger space, and increases complexity of the reactor design. Recently, there have been efforts to directly split seawater without the reverse osmosis step. Herein, we represent the most recent innovative approaches to avoid the two-step process, and compare the potential application of membrane-assisted and membrane-less electrolyzers in direct seawater splitting(DSS). We particularly discuss the device engineering, and propose a novel electrolyzer design strategies for concentration gradient based membrane-less microfluidic electrolyzer.

Electronically modulated d-band centers of MOF-derived carbon-supported Ru/HfO_(2) for oxygen reduction and aqueous/flexible zinc-air batteries

The construction of oxide/metal composite catalysts is a competent means of exploiting the electronic interactions between oxide/metal to enhance catalytic activity.In this work,we construct a novel heterogeneous composite(Ru/HfO_(2)-NC)with Ru/HfO2nanoparticles nested in nitrogen-doped porous carbon via a zeolitic imidazole frameworks-assisted(ZIF)co-precipitation and calcination approach.In particular,ZIF guides an in-situ construction of nested configuration and confines the scattered nanoparticles.Strikingly,Ru/HfO_(2)-NC exhibits unusual ORR activity,superb durability,and methanol tolerance in0.1 M KOH solution with high half-wave potential(E1/2)of 0.83 V and follows a near-4e-reaction pathway.Additionally,the ZAB assembled with cathodic Ru/HfO_(2)-NC outputs a power density of 157.3 m W cm^(-2),a specific capacity of 775 mA h g-1Zn,and a prolonged lifespan of 258 h at 5 mA cm^(-2).Meanwhile,the catalyst has demonstrated potential applicability in flexible ZAB.As suggested by experimental results and density functional theory(DFT)analysis,the remarkable property possibly originated from the optimization of the adsorption and desorption of reactive intermediates caused by the reconfiguration of the electronic structure between Ru and HfO_(2).

Mechanical and hydraulic properties of carbonate rock:The critical role of porosity

Carbonate rocks are extensively used in civil infrastructure and play a critical role in geoenergy geoengineering,either as hydrocarbon reservoirs or potential repositories for CO_(2)geological storage.Carbonate genesis and diagenetic overprint determine the properties of carbonate rocks.This study combines recent data gathered from Madison Limestone and an extensive dataset compiled from published sources to analyze the hydraulic and mechanical properties of limestone carbonate rocks.Physical models and data analyses recognize the inherently granular genesis of carbonate rocks and explain the strong dependency of physical properties on porosity.The asymptotically-correct power model in terms of(1-Ф/Ф*)a is a good approximation to global trends of unconfined stiffness E and unconfined compressive strength UCS,cohesive intercept in Mohr-Coulomb failure envelopes,and the brittle-toductile transition stress.This power model is the analytical solution for the mechanical properties of percolating granular structures.We adopted a limiting granular porosityФ*=0.5 for all models,which was consistent with the loosest packing of monosize spheres.The fitted power model has exponent(α=2)in agreement with percolation theory and highlights the sensitivity of mechanical properties to porosity.Data and models confirm a porosity-independent ratio between unconfined stiffness and strength,and the ratio follows a log-normal distribution with mean(E/UCS)≈300.The high angle of internal shear strength measured for carbonate rocks reflects delayed contact failure with increased confinement,and it is not sensitive to porosity.Permeability spans more than six orders of magnitude.Grain size controls pore size and determines the reference permeability k^(*)at the limiting porosityФ*=0.5.For a given grain size from fine to coarse-grained dominant carbonates,permeability is very sensitive to changes in porosity,suggesting preferential changes in the internal pore network during compaction.

Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution

Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.

Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Boosting Fischer-Tropsch Synthesis via Tuning of N Dopants in TiO_(2)@CN-Supported Ru Catalysts

Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.

Resolving co- and early post-seismic slip variations of the 2021 MW 7.4 Madoi earthquake in east Bayan Har block with a block-wide distributed deformation mode from satellite synthetic aperture radar data

On 21 May 2021(UTC),an MW 7.4 earthquake jolted the east Bayan Har block in the Tibetan Plateau.The earthquake received widespread attention as it is the largest event in the Tibetan Plateau and its surroundings since the 2008 Wenchuan earthquake,and especially in proximity to the seismic gaps on the east Kunlun fault.Here we use satellite interferometric synthetic aperture radar data and subpixel offset observations along the range directions to characterize the coseismic deformation of the earthquake.Range offset displacements depict clear surface ruptures with a total length of~170 km involving two possible activated fault segments in the earthquake.Coseismic modeling results indicate that the earthquake was dominated by left-lateral strike-slip motions of up to 7 m within the top 12 km of the crust.The well-resolved slip variations are characterized by five major slip patches along strike and 64%of shallow slip deficit,suggesting a young seismogenic structure.Spatial-temporal changes of the postseismic deformation are mapped from early 6-day and 24-day InSAR observations,and are well explained by time-dependent afterslip models.Analysis of Global Navigation Satellite System(GNSS)velocity profiles and strain rates suggests that the eastward extrusion of plateau is diffusely distributed across the east Bayan Har block,but exhibits significant lateral heterogeneities,as evidenced by magnetotelluric observations.The block-wide distributed deformation of the east Bayan Har block along with the significant co-and post-seismic stress loadings from the Madoi earthquake imply high seismic risks along regional faults,especially the Tuosuo Lake and Maqên-Maqu segments of the Kunlun fault that are known as seismic gaps.

Growth behavior and electronic properties of Ge_(n+1) and AsGe_n(n = 1–20) clusters: a DFT study

We present a systematic computational study based on the density functional theory(DFT) aiming to high light the possible effects of one As doping atom on the structural, energetic, and electronic properties of different isomers of Ge_(n+1) clusters with n = 1–20 atoms. By considering a large number of structures for each cluster size, the lowest-energy isomers are determined. The lowest-energy isomers reveal three-dimensional structures starting from n = 5. Their relative stability versus atomic size is examined based on the calculated binding energy, fragmentation energy, and second-order difference of energy. Doping Ge_(n+1) clusters with one As atom does not improve their stability. The electronic properties as a function of the atomic size are also discussed from the calculated HOMO–LUMO energy gap, vertical ionization potential, vertical electron affinity, and chemical hardness. The obtained results are significantly affected by the inclusion of one As atom into a Gen cluster.

A techno-economic and life cycle assessment for the production of green methanol from CO_(2): catalyst and process bottlenecks

The success of catalytic schemes for the large-scale valorization of CO_(2) does not only depend on the development of active,selective and stable catalytic materials but also on the overall process design.Here we present a multidisciplinary study(from catalyst to plant and techno-economic/lifecycle analysis)for the production of green methanol from renewable H2 and CO_(2).We combine an in-depth kinetic analysis of one of the most promising recently reported methanol-synthesis catalysts(InCo)with a thorough process simulation and techno-economic assessment.We then perform a life cycle assessment of the simulated process to gauge the real environmental impact of green methanol production from CO_(2).Our results indicate that up to 1.75 ton of CO_(2) can be abated per ton of produced methanol only if renewable energy is used to run the process,while the sensitivity analysis suggest that either rock-bottom H2 prices(1.5$kg1)or severe CO_(2) taxation(300$per ton)are needed for a profitable methanol plant.Besides,we herein highlight and analyze some critical bottlenecks of the process.Especial attention has been paid to the contribution of H2 to the overall plant costs,CH4 trace formation,and purity and costs of raw gases.In addition to providing important information for policy makers and industrialists,directions for catalyst(and therefore process)improvements are outlined.

Phase control of 2D binary hydroxides nanosheets via controlling-release strategy for enhanced oxygen evolution reaction and supercapacitor performances

An OH^--slow-release strategy was established to controllably tune the( α-and β-) phase of nickel cobalt binary hydroxide in the presence of ammonium chloride. Ammonium chloride is added to the ionic solution to regulate the p H of the solution and slow down the release of OH^-, effectively regulating the phase, nanostructure, interlayer spacing, surface area, thickness, and the performance of binary Ni –Co hydroxide. The ion-slow-release mechanism is conducive to the formation of α-phase with larger interlayer spacing and thinner flakes rather than β-phase. Attributed to the enlarged interlayer spacing, thinner nanosheets, and more exposed active sites, the resultant α-phase hydroxides(NCNS-5.2), displayed much lower over potential of 285 mV with respect to the dense-stacked β-phase hydroxides(362 mV) for OER at 10 mA/cm^2. It also exhibited high specific capacitance of 1474.2 F/g, when tested at 0.5 A/g within a voltage range of 0–0.45 Vvs. Hg/Hg O. This composite was also stable for water oxidation reaction and supercapacitor. The proof-of-concept of using controlled-release agent may provide suggestive insights for the material innovation and a variety of applications.

Deep-ultraviolet integrated photonic and optoelectronic devices:A prospect of the hybridization of group Ⅲ–nitrides, Ⅲ–oxides,and two-dimensional materials

Progress in the design and fabrication of ultraviolet and deep-ultraviolet groupⅢ–nitride optoelectronic devices,based on aluminum gallium nitride and boron nitride and their alloys,and the heterogeneous integration with two-dimensional and oxide-based materials is reviewed.We emphasize wide-bandgap nitride compound semiconductors(i.e.,(B,Al,Ga)N)as the deep-ultraviolet materials of interest,and two-dimensional materials,namely graphene,two-dimensional boron nitride,and two-dimensional transition metal dichalcogenides,along with gallium oxide,as the hybrid integrated materials.We examine their crystallographic properties and elaborate on the challenges that hinder the realization of efficient and reliable ultraviolet and deep-ultraviolet devices.In this article we provide an overview of aluminum nitride,sapphire,and gallium oxide as platforms for deep-ultraviolet optoelectronic devices,in which we criticize the status of sapphire as a platform for efficient deep-ultraviolet devices and detail advancements in device growth and fabrication on aluminum nitride and gallium oxide substrates.A critical review of the current status of deep-ultraviolet light emission and detection materials and devices is provided.

Fabrication and Applications of Micro/Nanostructured Devices for Tissue Engineering

Nanotechnology allows the realization of new materials and devices with basic structural unit in the range of1–100 nm and characterized by gaining control at the atomic, molecular, and supramolecular level. Reducing the dimensions of a material into the nanoscale range usually results in the change of its physiochemical properties such as reactivity,crystallinity, and solubility. This review treats the convergence of last research news at the interface of nanostructured biomaterials and tissue engineering for emerging biomedical technologies such as scaffolding and tissue regeneration. The present review is organized into three main sections. The introduction concerns an overview of the increasing utility of nanostructured materials in the field of tissue engineering. It elucidates how nanotechnology, by working in the submicron length scale, assures the realization of a biocompatible interface that is able to reproduce the physiological cell–matrix interaction. The second, more technical section, concerns the design and fabrication of biocompatible surface characterized by micro- and submicroscale features, using microfabrication, nanolithography, and miscellaneous nanolithographic techniques.In the last part, we review the ongoing tissue engineering application of nanostructured materials and scaffolds in different fields such as neurology, cardiology, orthopedics, and skin tissue regeneration.

Multi-Panel Extra-Large Scale MIMO Based Joint Activity Detection and Channel Estimation for Near-Field Massive IoT Access

The extra-large scale multiple-input multiple-output(XL-MIMO)for the beyond fifth/sixth generation mobile communications is a promising technology to provide Tbps data transmission and stable access service.However,the extremely large antenna array aperture arouses the channel near-field effect,resulting in the deteriorated data rate and other challenges in the practice communication systems.Meanwhile,multi-panel MIMO technology has attracted extensive attention due to its flexible configuration,low hardware cost,and wider coverage.By combining the XL-MIMO and multi-panel array structure,we construct multi-panel XL-MIMO and apply it to massive Internet of Things(IoT)access.First,we model the multi-panel XL-MIMO-based near-field channels for massive IoT access scenarios,where the electromagnetic waves corresponding to different panels have different angles of arrival/departure(AoAs/AoDs).Then,by exploiting the sparsity of the near-field massive IoT access channels,we formulate a compressed sensing based joint active user detection(AUD)and channel estimation(CE)problem which is solved by AMP-EM-MMV algorithm.The simulation results exhibit the superiority of the AMP-EM-MMV based joint AUD and CE scheme over the baseline algorithms.

A Hybrid Local/Nonlocal Continuum Mechanics Modeling and Simulation of Fracture in Brittle Materials

Classical continuum mechanics which leads to a local continuum model,encounters challenges when the discontinuity appears,while peridynamics that falls into the category of nonlocal continuum mechanics suffers from a high computational cost.A hybrid model coupling classical continuum mechanics with peridynamics can avoid both disadvantages.This paper describes the hybrid model and its adaptive coupling approach which dynamically updates the coupling domains according to crack propagations for brittle materials.Then this hybrid local/nonlocal continuum model is applied to fracture simulation.Some numerical examples like a plate with a hole,Brazilian disk,notched plate and beam,are performed for verification and validation.In addition,a peridynamic software is introduced,which was recently developed for the simulation of the hybrid local/nonlocal continuum model.

Synthesis and Immobilization of Polystyrene-b-Polyvinyltriethoxysilane Micelles

Diblock copolymers polystyrene-block-polyvinyltriethoxysilane(PS-b-PVTES) were synthesized via atom transfer radical polymerization(ATRP), which self-assembled into spherical micelles in solvent of THF-methanol mixtures. The self-assembled micelles were immobilized by cross-linking reaction of VTES in a shell layer of micelles. The chemical structures of block copolymers and morphology of micelles were characterized in detail. It was found that the size of immobilized micelles was strongly affected by the copolymer concentration, composition of mixture solvent, and block ratios.

Delicate surface vacancies engineering of Ru doped MOF-derived Ni-NiO@C hollow microsphere superstructure to achieve outstanding hydrogen oxidation performance

Surface vacancy defects,as the bridge between theoretical structural study and the design of heterogenous catalysts,have captured much attention.This work develops a metal-organic framework-engaged replacement-pyrolysis approach to obtain highly dispersed Ru nanoparticles immobilized on the vacancy-rich Ni-NiO@C hollow microsphere(Ru/Ni-NiO@C).Fine annealing at 400°C introduces nickel and oxygen vacancies on Ru/Ni-NiO@C surface,resulting in an improved electrical conductivity and rapid mass-charge transfer efficiency.Ru/Ni-NiO@C with a hollow micro/nanostructure and interconnected meso-porosity favors the maximal exposure of abundant active sites and elevation of hydrogen oxidation reaction(HOR)activity.Experimental results and density functional theory(DFT)calculations reveal that an electronic effect between Ru and Ni-NiO@C,in conjunction with nickel/oxygen vacancies in the NiO species could synergistically optimize hydrogen binding energy(HBE)and hydroxide binding energy(OHBE).The HBE and OHBE optimizations thus created confer Ru/Ni-NiO@C with a mass activity over 7.75 times higher than commercial Pt/C.Our work may provide a constructive route to make a breakthrough in elevating the hydrogen electrocatalytic performance.

Interface engineering of porous Fe^(2)P-WO_(2.92) catalyst with oxygen vacancies for highly active and stable large-current oxygen evolution and overall water splitting

Constructing a low cost,and high-efficiency oxygen evolution reaction(OER)electrocatalyst is of great significance for improving the performance of alkaline electrolyzer,which is still suffering from highenergy consumption.Herein,we created a porous iron phosphide and tungsten oxide self-supporting electrocatalyst with oxygen-containing vacancies on foam nickel(Fe_(2)P-WO_(2.92)/NF)through a facile insitu growth,etching and phosphating strategies.The sequence-controllable strategy will not only generate oxygen vacancies and improve the charge transfer between Fe_(2)P and WO_(2.92) components,but also improve the catalyst porosity and expose more active sites.Electrochemical studies illustrate that the Fe_(2)P-WO_(2.92)/NF catalyst presents good OER activity with a low overpotential of 267 mV at 100 mA cm^(-2),a small Tafel slope of 46.3 mV dec^(-1),high electrical conductivity,and reliable stability at high current density(100 mA cm^(-2) for over 60 h in 1.0 M KOH solution).Most significantly,the operating cell voltage of Fe_(2)P-WO_(2.92)/NF‖Pt/C is as low as 1.90 V at 400 mA cm^(-2) in alkaline condition,which is one of the lowest reported in the literature.The electrocatalytic mechanism shows that the oxygen vacancies and the synergy between Fe_(2)P and WO_(2.92) can adjust the electronic structure and provide more reaction sites,thereby synergistically increasing OER activity.This work provides a feasible strategy to fabricate high-efficiency and stable non-noble metal OER electrocatalysts on the engineering interface.

Quantitative heterogeneity and subgroup classification based on motility of breast cancer cells

Cancer cell motility and its heterogeneity play an important role in metastasis, which is responsible for death of 90% of cancer patients. Here, in combination with a microfluidic technique, single-cell tracking, and systematic motility analysis,we present a rapid and quantitative approach to judge the motility heterogeneity of breast cancer cells MDA-MB-231 and MCF-7 in a well-defined three-dimensional(3D) microenvironment with controllable conditions. Following this approach,identification of highly mobile active cells in a medium with epithelial growth factor will provide a practical tool for cell invasion and metastasis investigation of multiple cancer cell types, including primary cells. Further, this approach could potentially become a speedy(~ hours) and efficient tool for basic and clinical diagnosis.

Statistical prediction of waterflooding performance by K-means clustering and empirical modeling

Statistical prediction is often required in reservoir simulation to quantify production uncertainty or assess potential risks.Most existing uncertainty quantification procedures aim to decompose the input random field to independent random variables,and may suffer from the curse of dimensionality if the correlation scale is small compared to the domain size.In this work,we develop and test a new approach,K-means clustering assisted empirical modeling,for efficiently estimating waterflooding performance for multiple geological realizations.This method performs single-phase flow simulations in a large number of realizations,and uses K-means clustering to select only a few representatives,on which the two-phase flow simulations are implemented.The empirical models are then adopted to describe the relation between the single-phase solutions and the two-phase solutions using these representatives.Finally,the two-phase solutions in all realizations can be predicted using the empirical models readily.The method is applied to both 2D and 3D synthetic models and is shown to perform well in the P10,P50 and P90 of production rates,as well as the probability distributions as illustrated by cumulative density functions.It is able to capture the ensemble statistics of the Monte Carlo simulation results with a large number of realizations,and the computational cost is significantly reduced.

Pt-confinement catalyst with dendritic hierarchical pores on excellent sulfur-resistance for hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

Metal confinement catalyst Mo S_(2)/Pt@TD-6%Ti(TD,TS-1/Dendritic mesoporous silica nanoparticles composite) in dendritic hierarchical pore structures was synthesized and showed excellent sulfur-resistance performance and stabilities in catalytic hydrodesulfurization reactions of probe sulfide molecules.The Mo S_(2)/Pt@TD-6%Ti catalyst combines the concepts of Pt-confinement effect and hydrogen spillover of Pt noble metal.The modified micropores of Mo/Pt@TD-6%Ti only allow the migration and dissociation of small H_(2) molecules(0.289 nm),and effectively keep the sulfur-containing compounds(e.g.H_(2)S,0.362 nm) outside.Thus,the Mo S_(2)/Pt@TD-6%Ti catalyst exhibits higher DBT and 4,6-DMDBT HDS activities because of the synergistic effect of the strong H_(2) dissociation ability of Pt and desulfurization ability of Mo S_(2) with a lower catalyst cost.This new concept combining H2dissociation performance of noble metal catalyst with the desulfurization ability of transition metal sulfide Mo S_(2) can protect the noble metal catalyst avoiding deactivation and poison,and finally guarantee the higher activities for DBT and 4,6-DMDBT HDS.