Recent advances and key perspectives of in-situ studies for oxygen evolution reaction in water electrolysis

Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.

Water-induced physicochemical and pore changes in limestone for surrounding rock across pressure aquifers

Osmotic water alters the physicochemical properties and internal structures of limestone.This issue is particularly critical in tunnel construction across mountainous regions with aquifers,where pressurized groundwater can destabilize the limestone-based surrounding rock.Thus,systematic research into the physicochemical properties and pore structure changes in the limestone under pressurized water is essential.Additionally,it is essential to develop an interpretable mathematical model to accurately depict how pressurized osmotic water weakens limestone.In this research,a specialized device was designed to simulate the process of osmotic laminar flow within limestone.Then,four main tests were conducted:mass loss,acoustic emission(AE),mercury intrusion porosimetry(MIP),and fluorescence analysis.Experimental results gained from tests led to the development of a“Particle-pore throat-water film”model.Proposed model explains water-induced physicochemical and pore changes in limestone under osmotic pressure and reveals evolutionary mechanisms as pressure increases.Based on experimental results and model,we found that osmotic pressure not only alters limestone composition but also affects pore throats larger than 0.1μm.Furthermore,osmotic pressure expands pore throats,enhancing pore structure uniformity,interconnectivity,and permeability.These effects are observed at a threshold of 7.5 MPa,where cohesive forces within the mineral lattice are surpassed,leading to the breakdown of erosion-resistant layer and a significant increase in hydrochemical erosion.

Effect of high-multiple water injection on rock pore structure and oil displacement efficiency

Experimental methods,including mercury pressure,nuclear magnetic resonance(NMR)and core(wateroil)displacement,are used to examine the effects of high-multiple water injection(i.e.water injection with high injected pore volume)on rock properties,pore structure and oil displacement efficiency of an oilfield in the western South China Sea.The results show an increase in the permeability of rocks along with particle migration,an increase in the pore volume and the average pore throat radius,and enhanced heterogeneity after high-multiple water injection.Compared with normal water injection methods,a high-multiple water injection is more effective in improving the oil displacement efficiency.The degree of recovery increases faster in the early stage due to the expansion of the swept area,and the transition from oil-wet to water-wet.The degree of recovery increases less in the late stage due to various factors,including the enhancement of heterogeneity in the rocks.Considering both the economic aspect and the production limit of water flooding,it is recommended to adopt other technologies to further enhance oil recovery after 300 PV water injection.

Experimental analysis of the pore structure, relative permeability, and water flooding characteristics of the Yan'an Formation sandstone, southwestern Ordos Basin

The oil and gas potential of the Yan'an Formation in the Ordos Basin has yet to be fully tapped. In this study, the pore structure, mobile fluid saturation, and water flooding micro-mechanism of the Yan'an Formation sandstone are systematically studied through the application of a series of rock physics and fluid experiments. The results show that there is a good positive correlation between porosity and permeability, and the reservoirs are divided into types Ⅰ, Ⅱ, and Ⅲ. Mercury injection tests show that the average pore throat radius of the oil-bearing reservoir ranges from 1 to 7 μm. The displacement pressure of the Yan'an Formation is also relatively low, and it decreases from 0.1 MPa to 0.01 MPa as the rock porosity increases from 11% to 18%. NMR tests show that small (diameter <0.5 μm) and medium pores (diameter ranging from 0.5 to 2.5 μm) are predominant in the reservoir. Different types of reservoirs have different characteristics of relative permeability curve. In addition, when the average oil recovery rate is less than 1 ml/min, the oil displacement efficiency increases faster. However, when the average oil recovery rate is between 1–3.5 ml/min, the oil displacement efficiency is maintained at around 27%–30%. Physical properties of the reservoir, pore-throat structure, experimental pressure difference, and pore volume injected — all have significant effects on oil displacement efficiency. For Type Ⅰ and Type Ⅱ reservoirs, the increase of the pore volume injected has a significant effect on oil displacement efficiency. However, for Type Ⅲ reservoirs, the change of pore volume injected has insignificant effect on oil displacement efficiency. This study provides a reference for the formulation of estimated ultimate recovery (EUR) measures for similar sandstone reservoirs.

Numerical analysis on mechanical difference of sandstone under in-situ stress,pore pressure preserved environment at depth

Deep in-situ rock mechanics considers the influence of the in-situ environment on mechanical properties,differentiating it from traditional rock mechanics.To investigate the effect of in-situ stress,pore pressure preserved environment on the mechanical difference of sandstone,four tests are numerically modeled by COMSOL:conventional triaxial test,conventional pore pressure test,in-situ stress restoration and reconstruction test,and in-situ pore pressure-preserved test(not yet realized in the laboratory).The in-situ stress restoration parameter is introduced to characterize the recovery effect of in-situ stress on elastic modulus and heterogeneous distribution of sandstone at different depths.A random function and nonuniform pore pressure coefficient are employed to describe the non-uniform distribution of pore pressure in the in-situ environment.Numerical results are compared with existing experimental data to validate the models and calibrate the numerical parameters.By extracting mechanical parameters from numerical cores,the stress-strain curves of the four tests under different depths,in-situ stress and pore pressure are compared.The influence of non-uniform pore pressure coefficient and depth on the peak strength of sandstone is analyzed.The results show a strong linear relationship between the in-situ stress restoration parameter and depth,effectively characterizing the enhanced effect of stress restoration and reconstruction methods on the elastic modulus of conventional cores at different depths.The in-situ pore pressurepreserved test exhibits lower peak stress and peak strain compared to the other three tests,and sandstone subjected to non-uniform pore pressure is more prone to plastic damage and failure.Moreover,the influence of non-uniform pore pressure on peak strength gradually diminished with increasing depth.

The fate of carbon resulting from pore water exchange in a mangrove and Spartina alterniflora ecozone

Mangrove and salt-marsh wetlands are important coastal carbon sinks.In order to quantify carbon export via pore water exchange and to evaluate subsequent fate of the exported carbon,we carried out continuous observations in a mangrove-Spartina alterniflora ecozone in the Zhangjiang River Estuary,China.The carbon fluxes via pore water exchange were estimated using^(222)Rn and^(228)Ra as tracers to be(2.15±0.63)mol/(m^(2)∙d)for dissolved inorganic carbon(DIC)and(-0.008±0.07)mol/(m^(2)∙d)for dissolved organic carbon(DOC)in the wet season and(3.02±0.65)mol/(m^(2)∙d)for DIC and(-0.15±0.007)mol/(m^(2)∙d)for DOC in the dry season in the mangrove-dominated creek(M-creek),while(2.52±0.82)mol/(m^(2)∙d)for DIC and(0.02±0.09)mol/(m^(2)∙d)for DOC in the dry season in the S.alterniflora-dominated creek(SA-creek).The negative value means that pore water was a sink of DOC in the creek.The total carbon via pore water exchange in the tidal creeks in the mangroves accounted for 41%-55%of the net carbon fixed by mangrove vegetation and was 3-4 times as much as the soil carbon accretion in the mangroves.The exported carbon in the form of DIC contributed all of the carbon outwelling from the M-creek and 79%of the carbon outwelling from the SA-creek,implying effective fixation of carbon by the wetland ecosystem.Moreover,it resulted in 54%in the dry season,75%in the wet season of the carbon dioxide released from the M-creek to the atmosphere,and 84%of the release from the SA-creek.Therefore,quantification of pore water exchange and related soil carbon loss is essential to trace the fate of carbon fixed in intertidal wetlands.

In situ Hydrothermal Oxidation of Ternary FeCoNi Alloy Electrode for Overall Water Splitting

Exploring noble metal-free catalyst materials for high efficient electrochemical water splitting to produce hydrogen is strongly desired for renewable energy development.In this article,a novel bifunctional catalytic electrode of insitu-grown type for alkaline water splitting based on FeCoNi alloy substrate has been successfully prepared via a facile one-step hydrothermal oxidation route in an alkaline hydrogen peroxide medium.It shows that the matrix alloy with the atom ratio 4∶3∶3 of Fe∶Co∶Ni can obtain the best catalytic performance when hydrothermally treated at 180℃for 18 h in the solution containing 1.8 M hydrogen peroxide and 3.6 M sodium hydroxide.The as-prepared Fe_(0.4)Co_(0.3)Ni_(0.3)-1.8 electrode exhibits small overpotentials of only 184 and 175 mV at electrolysis current density of 10 mA cm^(-2)for alkaline OER and HER processes,respectively.The overall water splitting at electrolysis current density of 10 mA cm^(-2)can be stably delivered at a low cell voltage of 1.62 V.These characteristics including the large specific surface area,the high surface nickel content,the abundant catalyst species,the balanced distribution between bivalent and trivalent metal ions,and the strong binding of in-situ naturally growed catalytic layer to matrix are responsible for the prominent catalytic performance of the Fe_(0.4)Co_(0.3)Ni_(0.3)-1.8 electrode,which can act as a possible replacement for expensive noble metal-based materials.

Wave-induced pore water pressure in marine cohesive soils

Cyclic triaxial tests and numerical analyses were undertaken, in order to evaluate the wave-induced pore water pressure in seabed sediments in the Hangzhou Bay. The cyclic triaxial tests indicate that the rate of pore water pressure generation in cohesive soils decreases with time, and the development of the pore water pressure can be represented by a hyperbolic curve. Numerical analyses, taking into account the generation and dissipation of pore water pressure simultaneously, suggest that the pore water pressure buildup in cohesive soils may increase with time continuously until the pore water pressure ratio approaches to 1, or it may decrease after a certain time, which is controlled by drain conditions. These phenomena are different from those in sands. For waves with a retum period of 100 a in the Hangzhou Bay, if the wave duration is more than 60 h, then the pore water pressure ratio will be close to 1 and soil fabric failure will take place.

Influences of material dilatancy and pore water pressure on stability factor of shallow tunnels

Explicit finite difference code was used to calculate the stability factors of shallow tunnels without internal support in limit state. The proposed method was formulated within the nonassociative plasticity. For the shallow tunnels in soft clay, without considering the influences of pore water pressure and dilatancy, numerical results were compared with the previously published solutions. From the comparisons, it is found that the present solutions agree well with the previous solutions. The accuracy of the strength reduction technique was demonstrated through the comparisons. The influence of the pore water pressure was discussed. For the shallow tunnels in dilatant cohesive-frictional soils, the dilatant analysis was carried out.

Study of pores produced in underwater wet welding

This paper deals with the effect of water depth in the range of 10 m to 80 m upon the formation of pores produced during underwater wet welding. The results show that it is easy for the inner pores to occur owing to the particularity of the molten metal solidification that the outer pores begin to appear when the water depth increases to about 60 m, that the porosity increases and pore grows up as the water depth increases, and that pores are all hydrogen-containing ones through the examination of the variation of number of pores with the residual hydrogen and oxygen content in the weld metal.

Influence of subsequent curing on water sorptivity and pore structure of steam-cured concrete

Steam-cured condition is found to cause larger porosity and worse properties of concrete compared with normal curing condition. For the sake of seeking effective measurements to eliminate this bad effect of steam-cured condition on concrete, the water sorptivity and pore structure of steam-cured concretes exposed to different subsequent curing conditions were investigated after steam-curing treatment. The capillary absorption coefficient and porosity of the corresponding concretes were analyzed, and their mechanisms were also discussed. The results indicate that water sorptivity and pore structure of steam-cured concrete are greatly influenced by the curing condition used in subsequent ages. Exposure steam-cured concrete to air condition has an obviously bad effect on its properties and microstructures. Adopting subsequent curing of immersing steam-cured concrete into about 20℃ water after steam curing period can significantly decrease its capillary absorption coefficient and porosity. Steam-cured concrete with 7 d water curing has minimum capillary absorption coefficient and total porosity. Its water sorptivity is decreased by 23% compared with standard curing concrete and the porosity is 9.6% lower. Moreover, the corresponding gradient of water sorptivity and porosity of steam-cured concrete both decrease, thus mictostructure of concrete becomes more homogeneous.

The numerical study of wave-induced pore water pressure response in highly permeable seabed

The coupling numerical model of wave interaction with porous medium is used to study wave- induced pore water pressure in high permeability seabed. In the model, the wave field solver is based on the two dimensional Reynolds-averaged Navier-Stokes （RANS） equations with a k-s closure, and Forchheimer equations are adopted for flow within the porous media. By introducing a Velocity-Pressure Correction equation for the wave flow and porous flow, a highly efficient coupling between the two flows is implemented. The numerical tests are conducted to study the effects of seabed thickness, porosity, particle size and intrinsic permeability coefficient on regular wave and solitary wave-induced pore water pressure response. The results indicate that, as compared with regular wave-induced, solitary wave-induced pore water pressure has larger values and stronger action on seabed with different parameters. The results also clearly show the flow characteristics of pore water flow within seabed and water wave flow on seabed. The maximum pore water flow velocities within seabed under solitary wave action are higher than those under regular wave action.

Influence of pore water pressure on upper bound analysis of collapse shape for square tunnel in Hoek-Brown media

To investigate the effective shape of collapsing block in square tunnel subjected to pore water pressure,the analytical solution of detaching curve was derived using upper bound theorem of limit analysis with Hoek-Brown failure criterion. The work rate of pore water pressure,which was regarded as an external rate of work,was taken into account in the framework of limit analysis. Taking advantages of variational calculation,the objective function with respect to detaching curve was optimized to obtain the effective shape of collapsing block for square tunnel. According to the numerical results,it is found that the varying pore water pressure coefficient only affects the height and width of the collapsing block,whereas the shape of collapsing block remains unchanged.

Water sorption on coal:effects of oxygen-containing function groups and pore structure

Coal-water interactions have profound influences on gas extraction from coal and coal utilization.Experimental measurements on three coals using X-ray photoelectron spectroscopy(XPS),low-temperature nitrogen adsorption and dynamic water vapor sorption(DVS)were conducted.A mechanism-based isotherm model was proposed to estimate the water vapor uptake at various relative humidities,which is well validated with the DVS data.The validated isotherm model of sorption was further used to derive the isosteric heat of water vapor sorption.The specific surface area of coal pores is not the determining parameter that controls water vapor sorption at least during the primary adsorption stage.Oxidation degree dominates the primary adsorption,and which togethering with the cumulative pore volume determine the secondary adsorption.Higher temperature has limited effects on primary adsorption process.The isosteric heat of water adsorption decreases as water vapor uptake increases,which is found to be close to the latent heat of bulk water condensation at higher relative humidity.The results confirmed that the primary adsorption is controlled by the stronger bonding energy while the interaction energy between water molecules during secondary adsorption stage is relatively weak.However,the thermodynamics of coal-water interactions are complicated since the internal bonding interactions within the coal are disrupted at the same time as new bonding interactions take place within water molecules.Coal has a shrinkage/swelling colloidal structure with moisture loss/gain and it may exhibit collapse behavior with some collapses irreversible as a function of relative humidity,which further plays a significant role in determining moisture retention.

Relative roles of resuspended particles and pore water in release of contaminants from sediment

Sediment layers containing contaminants play a significant role in environmental hydrodynamics. Experiments were conducted in order to characterize the relative roles of resuspended particles and pore water under different flow and sediment conditions. A conservative tracer （NaC1） and a reactive tracer （phosphate） were used as contaminants in the bottom sediment in a laboratory flume. The mixing between the overlying water and pore water occurred over a short time while the desorption of contaminants from fine-grained resuspended particles lasted a relatively long time. The effects of resuspended particles and pore water on the variations of release flux and concentration of contaminants in water with time under different hydrodynamic conditions were quantified. The results show that pore water dominated the initial release flux, which could be several orders of magnitude greater than the flux due to molecular diffusion. Flux contribution of desorption from sediment particles in the latter release could be equal to what was seen from pore water in the initial stage.

Developing new understanding of photoelectrochemical water splitting via in-situ techniques:A review on recent progress

Photoelectrochemical(PEC) water splitting is a promising technology for solar hydrogen production to build a sustainable, renewable and clean energy economy. Given the complexity of the PEC water splitting processes, it is important to note that developing in-situ techniques for studying PEC water splitting presents a formidable challenge. This review is aimed at highlighting advantages and disadvantages of each technique, while offering a pathway of potentially combining several techniques to address different aspects of interfacial processes in PEC water splitting. We reviewed recent progress in various techniques and approaches utilized to study PEC water splitting, focusing on spectroscopic and scanning-probe methods.

Geochemical Characteristics of Heavy Metals in Riparian Sediment Pore Water of Songhua River, Northeast China

This study reports the geochemical characteristics of zinc (Zn), copper (Cu), lead (Pb), nickel (Ni), mercury (Hg), iron (Fe), and manganese (Mn) in the riparian sediment pore water of the Songhua River, Northeast China. In total, 36 pore water samples and 18 surface water samples from three typical sections were collected and analyzed in June 2009. Cluster analysis of heavy metals was performed to analyze the pollution sources of the metals. Results showed that Hg concentrations in the pore water were greater than those in the surface water, indicating a potential ability of Hg release from riparian sediment system to river water. However, concentrations of Fe and Mn in the surface water were greater than those in the pore water, demonstrating that the microenvironments of riparian and riverbed sediment systems were quite different. Variations of Zn, Cu, Pb and Ni between the surface and the pore water were different in each section. Most metals had similar horizontal and profile distribution characteristics in the three sections except for Zn and Ni. Hg, Fe and Mn concentrations in the pore water increased gradually with the increase in horizontal distance from water body, in contrast to this, Cu decreased, and Pb presented a fluctuating trend. With the increase in depth, Pb and Fe, Cu and Mn showed the same trends, and Hg showed a variable trend. The above distribution characteristics could mainly be attributed to the properties and the interactions of metals, pH and oxidation-reduction conditions, and the complex pollution sources and hydrologic regime in history. The probable sources of metals include the historical and ongoing discharge of industrial wastewater, mining activities, sewage irrigation for agricultural production, and atmospheric deposition from coal-fired plants.

Initial excess pore water pressures induced by tunnelling in soft ground

Tunnelling-induced long-term consolidation settlement attracts a great interest of engineering practice. The distribution and magnitude of tunnelling-induced initial excess pore water pressure have significant effects on the long-term consolidation settlement. A simple and reliable method for predicting the tunnel-induced initial excess pore water pressure calculation in soft clay is proposed. This method is based on the theory of elasticity and SKEMPTON's excess pore water pressure theory. Compared with the previously published field measurements and the finite-element modelling results, it is found that the suggested initial excess pore water pressure theory is in a good agreement with the measurements and the FE results. A series of parametric analyses are also carried out to investigate the influences of different factors on the distribution and magnitude of the initial excess pore water pressure in soft ground.

Experimental Study of Pore Water Pressure and Bed Profile Change Under Regular Breaking Waves

There lies a close relationship between the seabed destruction and the distribution of pore water pressure under the action of breaking wave. The experiments were carried out in a wave flume with a 1：30 sloping sandy seabed to study regular breaking wave induced pore water pressure. A wide range of measurements from the regular wave runs were reported, including time series of wave heights, pore pressures. The video records were analysed to measure the time development of the seabed form and the characteristics of the orbital motion of the sand in the wave breaking region. The pore water pressure in the breaker zone showed the time variation depending on the wave phases including wave breaking and bore propagation. The time-averaged pore water pressure was higher near the seabed surface. The peak values of pore water pressure increase significantly at the breaking point. The direction of pore water pressure difference forces in the breaker zone is of fundamental importance for a correct description of the sediment dynamics. The upwards- directed pressure differences may increase sand transport by reducing the effective weight of the sediment, thereby increasing the bed form evolution. The seabed configuration changed greatly at the wave breaking zone and a sand bar was generated remarkably. The amplitude of the pore water pressure changed with the seabed surface. The results are to improve the understanding of sand transport mechanisms and seabed responses due to breaking regular waves over a sloping sandy bed.

Influence of Superplasticizer Type and Dosage on Early-age Drying Shrinkage of Cement Paste with Consideration of Pore Size Distribution and Water Loss

We introduced a parameter r_s(the radius of the pores where the meniscus forms),which is composed of two factors,i e,water loss and cumulative pore size distribution(PSD),to provide a better explanation of the influence of superplasticizers(SPs)on early-age drying shrinkage.In our experiments,it is found that the addition of three types of SPs leads to a significant increase in the early-age drying shrinkage of cement paste,and drying shrinkage increases with the dosage of SPs.Based on the results above,we further studied the mechanism of the effects of SPs on the early-age drying shrinkage of cement paste by PSD and water loss,which are two components of r_s.The experimental results indicate that r_s can be a better index for the early-age drying shrinkage of cement-based materials with SPs than a single factor.In addition,the effects of SPs on other factors such as hydration degree and elastic modulus were also investigated and discussed.