Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferou...Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.展开更多
The effects of relative humidity (RH) on a printed circuit board finished with electroless nickel immersion gold (PCB-ENIG) under an adsorbed thin electrolyte layer (ATEL) were investigated in situ via the measurement...The effects of relative humidity (RH) on a printed circuit board finished with electroless nickel immersion gold (PCB-ENIG) under an adsorbed thin electrolyte layer (ATEL) were investigated in situ via the measurement of cathodic polarization curves, electrochemical impedance spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy to clearly elaborate the corrosion behavior of PCB-ENIG in the atmospheric environment. Results indicated that the cathodic process of PCB-ENIG under ATEL was dominated by the reduction of dissolved oxygen, corrosion products, and H2O. The cathodic current density of PCB-ENIG increased progressively with increasing RH. Moreover, its cathodic current density in the solution was greater than that under ATEL. This result demonstrated that the diffusion process was not the controlling step during the limiting reduction of cathodic oxygen. When the polarization potentials were located in a more negative region, the cathodic polarization current density gradually decreased under 75% and 85% RH. Notably, the anodic process became the controlling step in the extremely thin liquid film during the remainder of the experiment.展开更多
This article summarized systematically the previous investigations on t he dielectric relaxation of wood, the main substances and extractives in wood at oven-dry state, and the dielectric relaxation based on the adso...This article summarized systematically the previous investigations on t he dielectric relaxation of wood, the main substances and extractives in wood at oven-dry state, and the dielectric relaxation based on the adsorbed water in w o od cell wall under equilibrium and non-equilibrium state. Moreover, some expect a tions for future research were proposed on this basis. The purpose of this artic le is to provide other researchers an overall understanding about the research i n this region, and further to promote the research onto a new and higher level.展开更多
Elastic behaviors of protein-like chains are investigated by Pruned-Enriched-Rosenbluth method and modified orientation-dependent monomer-monomer interactions model. The protein-like chain is pulled away from the attr...Elastic behaviors of protein-like chains are investigated by Pruned-Enriched-Rosenbluth method and modified orientation-dependent monomer-monomer interactions model. The protein-like chain is pulled away from the attractive surface slowly with elastic force acting on it. Strong adsorption interaction and no adsorption interaction are both considered. We calculate the characteristic ratio and shape factor of protein-like chains in the process of elongation. The conformation change of the protein-like chain is well depicted. The shape of chain changes from “rod” to “sphere” at the beginning of elongation. Then, the shape changes from “sphere” to “rod”. In the end, the shape becomes a “sphere” as the chain leaves away from the surface. In the meantime, we discuss average Helmoholtz free energy per bond, average energy per bond, average adsorbed energy per bond, average α-helical energy per bond, average β-sheet energy per bond and average contact energy per bond. On the other hand, elastic force is also studied. It is found that elastic force has a long plateau during the tensile elongation when there exists adsorption interaction. This result is consistent with SMFS experiment of general polymers. Energy contribution to elastic force and contact energy contribution to elastic force are both discussed. These investigations can provide some insights into the elastic behaviors of adsorbed protein chains.展开更多
In this paper,the content and density of adsorbed water in fine-grained soil are determined.According to the test results,the calculation method of compaction degree of the solid-phase and void ration of soil is impro...In this paper,the content and density of adsorbed water in fine-grained soil are determined.According to the test results,the calculation method of compaction degree of the solid-phase and void ration of soil is improved.Four kinds of fine-grained soils from different regions in China were selected,and the adsorbed water content and density of four kinds of fine-grained soils were determined by thermogravimetry and volumetric flask method.Furthermore,SEM and XRD experiments were used to analyze the differences in the ability of each soil sample to absorb water.In order to study the compression characteristics of adsorbed water,four saturated soil samples were tested by consolidation method.The results show that the desorption temperature range of the adsorbed water and its density were equal to 100−115℃and 1.30 g/cm^(3),respectively.Adsorbed water plays a positive role in keeping the compressibility of fine-grained soil at a low rate when it has high water content.Besides,adsorbed water can be a stable parameter and is difficult to discharge during the operation period of subgrade.The settlement of fine-grained soil embankment is predicted by engineering example,and compared with the result of conventional calculation method.The results show that it is more close to the field monitoring results by using the improved void ratio of soil as the parameter.展开更多
Exploration practice indicates that free gas is the key to the large-scale development of shale gas,while adsorbed gas is also of great significance to the sustainable development of shale gas,and thus systematic rese...Exploration practice indicates that free gas is the key to the large-scale development of shale gas,while adsorbed gas is also of great significance to the sustainable development of shale gas,and thus systematic researches on absorbed pores are needed.To date,researches on pore structure and multi-scale fractal characteristics of absorbed pores in marine shale are obviously insufficient,limited the understanding of gas production behavior from shale reservoir.In this study,total organic carbon(TOC),X-ray diffraction(XRD),CH_(4) adsorption,field emission electron microscopy(FE-SEM),and low temperature gas(i.e.,CO_(2)and N_(2))adsorption/desorption analyses were conducted on 10 continuously core samples from the Lower Silurian Longmaxi shale in the Fuling region of Sichuan Basin,China.The results indicate that the TOC content of marine shale samples changes from 0.95%to 4.55%with an average of 2.62%,showing an increasing trend with the increase of burial depth;moreover,quartz and clay are the dominated mineral compositions in marine shale,and they show a certain negative correlation.FE-SEM analysis indicates that almost all pore types in marine shale are related to organic matter(OM).Hysteresis loops of marine shale samples mainly belong to Type H2,further indicating that the pores in marine shale are mainly ink-bottle pores(i.e.,OM pores);moreover,adsorption isotherms obtained from CO_(2)adsorption data all belong to typeⅠ,indicating microporous properties for all shale samples.Comprehensive analysis indicates that pore volume and pore surface area of adsorbed pores(<300 nm)is mainly provided by the pores within the pore range of 0.6–0.7,0.80–0.85,and 1.7–5.0 nm.Based on the micropore filling model and the Frenkel-Halsey-Hill(FHH)model,multiscale fractal dimensions(D1,D2,and D3)are calculated from gas adsorption data(i.e.,CO_(2)and N_(2)),corresponding to part of micropore(0.6–1.1 nm),small-mesopore(1.7–5.0 nm),big-mespore and part of macropore(5.0–300 nm),respectively.Relationships between shale compositions,pore structure,and fractal dimensions(D1,D2,and D3)indicate that pore structure and multi-scale fractal characteristics of absorbed pores in marine shale are obviously influenced by the contents of TOC and quartz,while clay minerals have little effect on them.Comprehensive analysis indicates that the complexity of marine shale pores within the range of 0.6–1.1 and 1.7–5.0 nm has significant effects on CH_(4) adsorbability,while the larger pores(5.0–300 nm)almost have no effect.展开更多
Silk fibroin(SF)can be used to construct various stiff material interfaces to support bone formation.An essential preparatory step is to partially transform SF molecules from random coils toβ-sheets to render the mat...Silk fibroin(SF)can be used to construct various stiff material interfaces to support bone formation.An essential preparatory step is to partially transform SF molecules from random coils toβ-sheets to render the material water insoluble.However,the influence of the SF conformation on osteogenic cell behavior at the material interface remains unknown.Herein,three stiff SF substrates were prepared by varying theβ-sheet content(high,medium,and low).The substrates had a comparable chemical composition,surface topography,and wettability.When adsorbed fibronectin was used as a model cellular adhesive protein,the stability of the adsorbed protein-material interface,in terms of the surface stability of the SF substrates and the accompanying fibronectin detachment resistance,increased with the increasingβ-sheet content of the SF substrates.Furthermore,(i)larger areas of cytoskeleton-associated focal adhesions,(ii)higher orders of cytoskeletal organization and(iii)more elongated cell spreading were observed for bone marrow-derived mesenchymal stromal cells(BMSCs)cultured on SF substrates with high vs.lowβ-sheet contents,along with enhanced nuclear translocation and activation of YAP/TAZ and RUNX2.Consequently,osteogenic differentiation of BMSCs was stimulated on highβ-sheet substrates.These results indicated that theβ-sheet content influences osteogenic differentiation of BMSCs on SF materials in vitro by modulating the stability of the adsorbed protein-material interface,which proceeds via protein-focal adhesion-cytoskeleton links and subsequent intracellular mechanotransduction.Our findings emphasize the role of the stability of the adsorbed protein-material interface in cellular mechanotransduction and the perception of stiff SF substrates with differentβ-sheet contents,which should not be overlooked when engineering stiff biomaterials.展开更多
Exploiting efficient and low-cost cocatalyst with a facile grafting strategy is of critical importance for significantly boosting the photocatalytic H2-evolution activity.In this study,S2^--adsorbed MoSx nanoparticle ...Exploiting efficient and low-cost cocatalyst with a facile grafting strategy is of critical importance for significantly boosting the photocatalytic H2-evolution activity.In this study,S2^--adsorbed MoSx nanoparticle as a superior H2-evolutoin cocatalyst was successfully grafted on the TiO2 surface to greatly boost its photocatalytic activity via one-step lactic acid-induced synthesis strategy.Herein,the lactic acid can induce the homogeneous production of amorphous MoSx(a-MoSx)nanoparticles from MoS42-precursor,while the symbiotic S2^-ions can be easily and availably self-adsorbed on the a-Mo Sxsurface,resulting in the formation of S2^--adsorbed a-Mo Sxnanoparticles with a small size of 0.5-3 nm.Photocatalytic results manifested that the S2^--adsorbed Mo Sxnanoparticles could dramatically facilitate the H2-generation rate of TiO2 photocatalysts(3452μmol h^-1 g^-1,AQE=16.5%).In situ irradiated XPS in conjunction with transient-state PL and photoelectrochemical tests reveal that the improved H_(2)-generation activity can be ascribed to the synergistic effect of boosted interfacial charge transfer from TiO_(2) to S^(2-)adsorbed Mo Sx and the superior H_(2)-evolution reaction on self-adsorbed S_(2-)ions.In addition,the S^(2-)-adsorbed Mo Sx nanoparticles can also act as the general H_(2)-generation cocatalyst to obviously promote the activity of other typical host photocatalysts such as g-C_(3) N_(4) and Cd S.This work provides an innovative approach to develop high-efficiency Mo Sx-based cocatalyst with boosted interfacial charge transfer toward highly efficient photocatalytic materials.展开更多
CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catal...CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catalytic site.Here,we present a mechanistic study that overturns this understanding by using Rh-based single-atom catalysis centers as model catalysts.We precisely modulated the chelation structure of the Rh catalyst by coordinating Rh with C or N atoms,and probed the reaction mechanism by surface-enhanced Raman spectroscopy.Direct spectroscopic evidence for intermediates indicates that the reactivity of adsorbed OH^(*),rather than the adsorption strength of CO^(*),dictates the CO electrocatalytic oxidation behavior.The RhN_(4)sites,which adsorb the OH^(*)intermediate more weakly than RhC4 sites,showed prominent CO oxidation activity that not only far exceeded the traditional Pt/C but also the RhC4 sites with similar CO adsorption strength.From this study,it is clear that a paradigm shift in future research should be considered to rationally design high-performance CO electro-oxidation reaction catalysts by sufficiently considering the water-related reaction intermediate during catalysis.展开更多
In recent years, excessive use of chemical nitrogen （N） fertilizers has resulted in the accumulation of excess ammonium （NH4＋） in many agricultural soils. Though rice is known as an NH4＋-tolerant species and can...In recent years, excessive use of chemical nitrogen （N） fertilizers has resulted in the accumulation of excess ammonium （NH4＋） in many agricultural soils. Though rice is known as an NH4＋-tolerant species and can directly absorb soil intact amino acids, we still know considerably less about the role of high exogenous NH4＋ content on rice uptake of soil amino acids. This experiment examined the effects of the exogenous NH4＋ concentration on rice uptake of soil adsorbed glycine in two different soils under sterile culture. Our data showed that the sorption capacity of glycine was closely related to soils＇ physical and chemical properties, such as organic matter and cation exchange capacity. Rice biomass was significantly inhibited by the exogenous NH4＋ content at different glycine adsorption concentrations. A three-way analysis of variance demonstrated that rice glycine uptake and glycine nutritional contribution were not related to its sorption capacity, but significantly related to its glycine：NH4＋ concentration ratio. After 21-d sterile cultivation, the rice uptake of adsorbed glycine accounted for 8.8%-22.6% of rice total N uptake, which indicates that soil adsorbed amino acids theoretically can serve as an important N source for plant growth in spite of a high NH4＋ application rate. However, further studies are needed to investigate the extent to which this bioavailability is realized in the field using the 13C, 15N double labeling technology.展开更多
Single-layer MoSi_(2)N_(4),a high-quality two-dimensional material,has recently been fabricated by chemical vapor deposition.Motivated by this latest experimental work,herein,we apply first principles calculations to ...Single-layer MoSi_(2)N_(4),a high-quality two-dimensional material,has recently been fabricated by chemical vapor deposition.Motivated by this latest experimental work,herein,we apply first principles calculations to investigate the electronic,optical,and photocatalytic properties of alkali-metal(Li,Na,and K)-adsorbed MoSi_(2)N_(4) monolayer.The electronic structure analysis shows that pristine MoSi_(2)N_(4) monolayer exhibits an indirect bandgap(E_(g)=1.89 eV).By contrast,the bandgaps of one Li-,Na-,and K-adsorbed MoSi_(2)N_(4) monolayer are 1.73 eV,1.61 eV,and 1.75 eV,respectively.Moreover,the work function of MoSi_(2)N_(4) monolayer(4.80 eV)is significantly reduced after the adsorption of alkali metal atoms.The work functions of one Li-,Na-,and K-adsorbed MoSi_(2)N_(4) monolayer are 1.50 eV,1.43 eV,and 2.03 eV,respectively.Then,optical investigations indicate that alkali metal adsorption processes substantially increase the visible light absorption range and coefficient of MoSi_(2)N_(4) monolayer.Furthermore,based on redox potential variations after alkali metals are adsorbed,Li-and Na-adsorbed MoSi_(2)N_(4) monolayers are more suitable for the water splitting photocatalytic process,and the Li-adsorbed case shows the highest potential application for CO_(2) reduction.In conclusion,alkali-metal-adsorbed MoSi_(2)N_(4) monolayer exhibits promising applications as novel optoelectronic devices and photocatalytic materials due to its unique physical and chemical properties.展开更多
I.r.bands at 1559.0, 1441 .0, 1378 .9, 13603, 1031. 1,981 .4 and 947.3 cm -1 due tovarious types of dissociative adsorption of H2 over ZrO2 with changing temperatore wereobserved by in situ FT-IR spectroscopy.
Surface enhanced Raman scattering of water adsorbed at silver electrodes in very negative potential region was first observed and a simple model related to the adsorption configuration is proposed.
Based on the nanostructured surface model that the （platinum, Pt） nanocones grow out symmetrically from a plane substrate, the local electric field near the conical nanoparticle surface is computed and discussed. On...Based on the nanostructured surface model that the （platinum, Pt） nanocones grow out symmetrically from a plane substrate, the local electric field near the conical nanoparticle surface is computed and discussed. On the basis of these results, the adsorbed CO molecules are modelled as dipoles, and three kinds of interactions, i.e. interactions between dipoles and local electric field, between dipoles and dipoles, as well as between dipoles and nanostructured substrate, are taken into account. The spatial configuration of CO molecules adsorbed on the nanocone surface is then given by Monte-Carlo simulation. Our results show that the CO molecules adsorbed on the nanocone surface cause local agglomeration under the action of an external electric field, and this agglomeration becomes more compact with decreasing conical angle, which results in a stronger interaction among molecules. These results serve as a basis for explaining abnormal phenomena such as the abnormal infrared effect （AIRE）, which was found when CO molecules were adsorbed on the nanostructured transition-metal surface.展开更多
It was observed that the p-aminobenzoic acid(PABA)molecules adsorbed on A92CO3 colloids exhibited strong SERS effect,the enhancement factor is estimated at 10~7—10~8 The mechanism of SERS effect on PABA adsorbed on t...It was observed that the p-aminobenzoic acid(PABA)molecules adsorbed on A92CO3 colloids exhibited strong SERS effect,the enhancement factor is estimated at 10~7—10~8 The mechanism of SERS effect on PABA adsorbed on the colloids was discussed.展开更多
The paper presents ac impedance behaviours of phenyl iso-thiocyanate adsorbed on Pt electrode.Nyquist plots are analysed and simulated,and parameters of relative equivalent circuits are obtained.
A new reagent. trimethylammonium chlorochromate adsorbed on alumina, suitable for the oxidation of hydroxy compounds to the corresponding carbonyl compounds is described.
This paper shows that the local electric field distribution near the nanostructure metallic surface is obtained by solving the Laplace equation, and furthermore, the configuration of CO molecules adsorbed on a Pt nano...This paper shows that the local electric field distribution near the nanostructure metallic surface is obtained by solving the Laplace equation, and furthermore, the configuration of CO molecules adsorbed on a Pt nanoparticle surface is obtained by using Monte Carlo simulation. It is found that the uneven local electric field distribution induced by the nanostructure surface can influence the configuration of carbon monoxide （CO） molecules by a force, which drags the adsorbates to the poles of the nanoparticles. This result, together with our results obtained before, may explain the experimental results that the nanostructure metallic surface can lead to abnormal phenomena such as anti-absorption infrared effects.展开更多
The orientational ordering in adsorbed incommensurate monolayers is discussed in an anharmonic approach.A nonlinear relationship is predicted between the orientation of the monolayer relative to the substrate and the ...The orientational ordering in adsorbed incommensurate monolayers is discussed in an anharmonic approach.A nonlinear relationship is predicted between the orientation of the monolayer relative to the substrate and the monolayer lattice parameter.Calculated values of the rninimum energy crientation angle for Ar on graphite are in good agreement with the experimental reported measurements.展开更多
基金Youth Fund of National Natural Science Foundation of China(42302170)CNPC Scientific and Technological Innovation Fund(2022DQ02-0104)RIPED Open Project Fund(2024-KFKT-31).
文摘Taking deep coal-rock gas in the Yulin and Daning-Jixian areas of the Ordos Basin,NW China,as the research object,full-diameter coal rock samples with different cleat/fracture development degrees from the Carboniferous Benxi Formation were selected to conduct physical simulation and isotope monitoring experiments of the full-life-cycle depletion development of coal-rock gas.Based on the experimental results,a dual-medium carbon isotope fractionation(CIF)model coupling cleats/fractures and matrix pores was constructed,and an evaluation method for free gas production patterns was established to elucidate the carbon isotope fractionation mechanism and adsorbed/free gas production characteristics during deep coal-rock gas development.The results show that the deep coal-rock gas development process exhibits a three-stage carbon isotope fractionation pattern:“Stable(Ⅰ)→Decrease(Ⅱ)→Increase(Ⅲ)”.A rapid decline in boundary pressure in stageⅢleads to fluctuations in isotope value,characterized by a“rapid decrease followed by continued increase”,with free gas being produced first and long-term supply of adsorbed gas.The CIF model can effectively match measured gas pressure,cumulative gas production,and δ^(13)C_(1) value of produced gas.During the first two stages of isotope fractionation,free gas dominated cumulative production.During the mid-late stages of slow depletion production,the staged pressure control development method can effectively increase the gas recovery.The production of adsorbed gas is primarily controlled by the rock's adsorption capacity and the presence of secondary flow channels.Effectively enhancing the recovery of adsorbed gas during the late stage remains crucial for maintaining stable production and improving the ultimate recovery factor of deep coal-rock gas.
基金Project(51271032)supported by the National Natural Science Foundation of ChinaProject(2014CB643300)supported by the National Basic Research Program of ChinaProject supported by the National Environmental Corrosion Platform,China
文摘The effects of relative humidity (RH) on a printed circuit board finished with electroless nickel immersion gold (PCB-ENIG) under an adsorbed thin electrolyte layer (ATEL) were investigated in situ via the measurement of cathodic polarization curves, electrochemical impedance spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy to clearly elaborate the corrosion behavior of PCB-ENIG in the atmospheric environment. Results indicated that the cathodic process of PCB-ENIG under ATEL was dominated by the reduction of dissolved oxygen, corrosion products, and H2O. The cathodic current density of PCB-ENIG increased progressively with increasing RH. Moreover, its cathodic current density in the solution was greater than that under ATEL. This result demonstrated that the diffusion process was not the controlling step during the limiting reduction of cathodic oxygen. When the polarization potentials were located in a more negative region, the cathodic polarization current density gradually decreased under 75% and 85% RH. Notably, the anodic process became the controlling step in the extremely thin liquid film during the remainder of the experiment.
文摘This article summarized systematically the previous investigations on t he dielectric relaxation of wood, the main substances and extractives in wood at oven-dry state, and the dielectric relaxation based on the adsorbed water in w o od cell wall under equilibrium and non-equilibrium state. Moreover, some expect a tions for future research were proposed on this basis. The purpose of this artic le is to provide other researchers an overall understanding about the research i n this region, and further to promote the research onto a new and higher level.
基金ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.20904047）.
文摘Elastic behaviors of protein-like chains are investigated by Pruned-Enriched-Rosenbluth method and modified orientation-dependent monomer-monomer interactions model. The protein-like chain is pulled away from the attractive surface slowly with elastic force acting on it. Strong adsorption interaction and no adsorption interaction are both considered. We calculate the characteristic ratio and shape factor of protein-like chains in the process of elongation. The conformation change of the protein-like chain is well depicted. The shape of chain changes from “rod” to “sphere” at the beginning of elongation. Then, the shape changes from “sphere” to “rod”. In the end, the shape becomes a “sphere” as the chain leaves away from the surface. In the meantime, we discuss average Helmoholtz free energy per bond, average energy per bond, average adsorbed energy per bond, average α-helical energy per bond, average β-sheet energy per bond and average contact energy per bond. On the other hand, elastic force is also studied. It is found that elastic force has a long plateau during the tensile elongation when there exists adsorption interaction. This result is consistent with SMFS experiment of general polymers. Energy contribution to elastic force and contact energy contribution to elastic force are both discussed. These investigations can provide some insights into the elastic behaviors of adsorbed protein chains.
基金Project(51978085)supported by the National Natural Science Foundation of ChinaProject(K2019G045)supported by the Science and Technology Research and Development Plan of China National Railway Group Co.,Ltd.Project(201808430102)supported by the China Scholarship Council。
文摘In this paper,the content and density of adsorbed water in fine-grained soil are determined.According to the test results,the calculation method of compaction degree of the solid-phase and void ration of soil is improved.Four kinds of fine-grained soils from different regions in China were selected,and the adsorbed water content and density of four kinds of fine-grained soils were determined by thermogravimetry and volumetric flask method.Furthermore,SEM and XRD experiments were used to analyze the differences in the ability of each soil sample to absorb water.In order to study the compression characteristics of adsorbed water,four saturated soil samples were tested by consolidation method.The results show that the desorption temperature range of the adsorbed water and its density were equal to 100−115℃and 1.30 g/cm^(3),respectively.Adsorbed water plays a positive role in keeping the compressibility of fine-grained soil at a low rate when it has high water content.Besides,adsorbed water can be a stable parameter and is difficult to discharge during the operation period of subgrade.The settlement of fine-grained soil embankment is predicted by engineering example,and compared with the result of conventional calculation method.The results show that it is more close to the field monitoring results by using the improved void ratio of soil as the parameter.
基金financially supported by the PetroChina Innovation Foundation(No.2019D-5007-0107)the National Natural Science Foundation of China(No.42172192)+3 种基金the National Natural Science Foundation for Young Scholars of China(No.41902173)the Fundamental Research Funds for the Central Universities(No.CUG170678)the Natural Science Foundation of Hubei Province(No.2019CFA028)the Program of Introducing Talents of Discipline to Universities(No.B14031)。
文摘Exploration practice indicates that free gas is the key to the large-scale development of shale gas,while adsorbed gas is also of great significance to the sustainable development of shale gas,and thus systematic researches on absorbed pores are needed.To date,researches on pore structure and multi-scale fractal characteristics of absorbed pores in marine shale are obviously insufficient,limited the understanding of gas production behavior from shale reservoir.In this study,total organic carbon(TOC),X-ray diffraction(XRD),CH_(4) adsorption,field emission electron microscopy(FE-SEM),and low temperature gas(i.e.,CO_(2)and N_(2))adsorption/desorption analyses were conducted on 10 continuously core samples from the Lower Silurian Longmaxi shale in the Fuling region of Sichuan Basin,China.The results indicate that the TOC content of marine shale samples changes from 0.95%to 4.55%with an average of 2.62%,showing an increasing trend with the increase of burial depth;moreover,quartz and clay are the dominated mineral compositions in marine shale,and they show a certain negative correlation.FE-SEM analysis indicates that almost all pore types in marine shale are related to organic matter(OM).Hysteresis loops of marine shale samples mainly belong to Type H2,further indicating that the pores in marine shale are mainly ink-bottle pores(i.e.,OM pores);moreover,adsorption isotherms obtained from CO_(2)adsorption data all belong to typeⅠ,indicating microporous properties for all shale samples.Comprehensive analysis indicates that pore volume and pore surface area of adsorbed pores(<300 nm)is mainly provided by the pores within the pore range of 0.6–0.7,0.80–0.85,and 1.7–5.0 nm.Based on the micropore filling model and the Frenkel-Halsey-Hill(FHH)model,multiscale fractal dimensions(D1,D2,and D3)are calculated from gas adsorption data(i.e.,CO_(2)and N_(2)),corresponding to part of micropore(0.6–1.1 nm),small-mesopore(1.7–5.0 nm),big-mespore and part of macropore(5.0–300 nm),respectively.Relationships between shale compositions,pore structure,and fractal dimensions(D1,D2,and D3)indicate that pore structure and multi-scale fractal characteristics of absorbed pores in marine shale are obviously influenced by the contents of TOC and quartz,while clay minerals have little effect on them.Comprehensive analysis indicates that the complexity of marine shale pores within the range of 0.6–1.1 and 1.7–5.0 nm has significant effects on CH_(4) adsorbability,while the larger pores(5.0–300 nm)almost have no effect.
基金supported by the National Key R&D Program of China(2017YFC1104301,to L.C.)the National Natural Science Foundation of China for Distinguished Young Scholars(31725011,to L.C.)the China Scholarship Council(201606160095,to X.C.)。
文摘Silk fibroin(SF)can be used to construct various stiff material interfaces to support bone formation.An essential preparatory step is to partially transform SF molecules from random coils toβ-sheets to render the material water insoluble.However,the influence of the SF conformation on osteogenic cell behavior at the material interface remains unknown.Herein,three stiff SF substrates were prepared by varying theβ-sheet content(high,medium,and low).The substrates had a comparable chemical composition,surface topography,and wettability.When adsorbed fibronectin was used as a model cellular adhesive protein,the stability of the adsorbed protein-material interface,in terms of the surface stability of the SF substrates and the accompanying fibronectin detachment resistance,increased with the increasingβ-sheet content of the SF substrates.Furthermore,(i)larger areas of cytoskeleton-associated focal adhesions,(ii)higher orders of cytoskeletal organization and(iii)more elongated cell spreading were observed for bone marrow-derived mesenchymal stromal cells(BMSCs)cultured on SF substrates with high vs.lowβ-sheet contents,along with enhanced nuclear translocation and activation of YAP/TAZ and RUNX2.Consequently,osteogenic differentiation of BMSCs was stimulated on highβ-sheet substrates.These results indicated that theβ-sheet content influences osteogenic differentiation of BMSCs on SF materials in vitro by modulating the stability of the adsorbed protein-material interface,which proceeds via protein-focal adhesion-cytoskeleton links and subsequent intracellular mechanotransduction.Our findings emphasize the role of the stability of the adsorbed protein-material interface in cellular mechanotransduction and the perception of stiff SF substrates with differentβ-sheet contents,which should not be overlooked when engineering stiff biomaterials.
基金financially supported by the National Natural Science Foundation of China(Nos.51872221 and 21771142)the Fundamental Research Funds for the Central Universities(No.WUT 2019IB002)。
文摘Exploiting efficient and low-cost cocatalyst with a facile grafting strategy is of critical importance for significantly boosting the photocatalytic H2-evolution activity.In this study,S2^--adsorbed MoSx nanoparticle as a superior H2-evolutoin cocatalyst was successfully grafted on the TiO2 surface to greatly boost its photocatalytic activity via one-step lactic acid-induced synthesis strategy.Herein,the lactic acid can induce the homogeneous production of amorphous MoSx(a-MoSx)nanoparticles from MoS42-precursor,while the symbiotic S2^-ions can be easily and availably self-adsorbed on the a-Mo Sxsurface,resulting in the formation of S2^--adsorbed a-Mo Sxnanoparticles with a small size of 0.5-3 nm.Photocatalytic results manifested that the S2^--adsorbed Mo Sxnanoparticles could dramatically facilitate the H2-generation rate of TiO2 photocatalysts(3452μmol h^-1 g^-1,AQE=16.5%).In situ irradiated XPS in conjunction with transient-state PL and photoelectrochemical tests reveal that the improved H_(2)-generation activity can be ascribed to the synergistic effect of boosted interfacial charge transfer from TiO_(2) to S^(2-)adsorbed Mo Sx and the superior H_(2)-evolution reaction on self-adsorbed S_(2-)ions.In addition,the S^(2-)-adsorbed Mo Sx nanoparticles can also act as the general H_(2)-generation cocatalyst to obviously promote the activity of other typical host photocatalysts such as g-C_(3) N_(4) and Cd S.This work provides an innovative approach to develop high-efficiency Mo Sx-based cocatalyst with boosted interfacial charge transfer toward highly efficient photocatalytic materials.
基金Jilin Province Science and Technology Development Program,Grant/Award Numbers:20180101030JC,20190201270JC,20200201001JCNational Natural Science Foundation of China,Grant/Award Numbers:21633008,21673221,21875243,U1601211+1 种基金Research Innovation Fund,Grant/Award Number:DNL202010Special Funds for Guiding Local Scientific and Technological Development by the Central Government,Grant/Award Number:2020JH6/10500021。
文摘CO impurity-induced catalyst deactivation has long been one of the biggest challenges in proton-exchange membrane fuel cells,with the poisoning phenomenon mainly attributed to the overly strong adsorption on the catalytic site.Here,we present a mechanistic study that overturns this understanding by using Rh-based single-atom catalysis centers as model catalysts.We precisely modulated the chelation structure of the Rh catalyst by coordinating Rh with C or N atoms,and probed the reaction mechanism by surface-enhanced Raman spectroscopy.Direct spectroscopic evidence for intermediates indicates that the reactivity of adsorbed OH^(*),rather than the adsorption strength of CO^(*),dictates the CO electrocatalytic oxidation behavior.The RhN_(4)sites,which adsorb the OH^(*)intermediate more weakly than RhC4 sites,showed prominent CO oxidation activity that not only far exceeded the traditional Pt/C but also the RhC4 sites with similar CO adsorption strength.From this study,it is clear that a paradigm shift in future research should be considered to rationally design high-performance CO electro-oxidation reaction catalysts by sufficiently considering the water-related reaction intermediate during catalysis.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(No.LQ15C130004)the National Basic Research Program(973)of China(No.2015CB150502)the National Natural Science Foundation of China(Nos.31172032 and 31270035)
文摘In recent years, excessive use of chemical nitrogen （N） fertilizers has resulted in the accumulation of excess ammonium （NH4＋） in many agricultural soils. Though rice is known as an NH4＋-tolerant species and can directly absorb soil intact amino acids, we still know considerably less about the role of high exogenous NH4＋ content on rice uptake of soil amino acids. This experiment examined the effects of the exogenous NH4＋ concentration on rice uptake of soil adsorbed glycine in two different soils under sterile culture. Our data showed that the sorption capacity of glycine was closely related to soils＇ physical and chemical properties, such as organic matter and cation exchange capacity. Rice biomass was significantly inhibited by the exogenous NH4＋ content at different glycine adsorption concentrations. A three-way analysis of variance demonstrated that rice glycine uptake and glycine nutritional contribution were not related to its sorption capacity, but significantly related to its glycine：NH4＋ concentration ratio. After 21-d sterile cultivation, the rice uptake of adsorbed glycine accounted for 8.8%-22.6% of rice total N uptake, which indicates that soil adsorbed amino acids theoretically can serve as an important N source for plant growth in spite of a high NH4＋ application rate. However, further studies are needed to investigate the extent to which this bioavailability is realized in the field using the 13C, 15N double labeling technology.
基金This research was supported by the National Natural Science Foundation of China(Grant No.11774054,12075036)the talents and high-level paper cultivation plan from the School of Optoelectronic Engineering,Yangtze University.
文摘Single-layer MoSi_(2)N_(4),a high-quality two-dimensional material,has recently been fabricated by chemical vapor deposition.Motivated by this latest experimental work,herein,we apply first principles calculations to investigate the electronic,optical,and photocatalytic properties of alkali-metal(Li,Na,and K)-adsorbed MoSi_(2)N_(4) monolayer.The electronic structure analysis shows that pristine MoSi_(2)N_(4) monolayer exhibits an indirect bandgap(E_(g)=1.89 eV).By contrast,the bandgaps of one Li-,Na-,and K-adsorbed MoSi_(2)N_(4) monolayer are 1.73 eV,1.61 eV,and 1.75 eV,respectively.Moreover,the work function of MoSi_(2)N_(4) monolayer(4.80 eV)is significantly reduced after the adsorption of alkali metal atoms.The work functions of one Li-,Na-,and K-adsorbed MoSi_(2)N_(4) monolayer are 1.50 eV,1.43 eV,and 2.03 eV,respectively.Then,optical investigations indicate that alkali metal adsorption processes substantially increase the visible light absorption range and coefficient of MoSi_(2)N_(4) monolayer.Furthermore,based on redox potential variations after alkali metals are adsorbed,Li-and Na-adsorbed MoSi_(2)N_(4) monolayers are more suitable for the water splitting photocatalytic process,and the Li-adsorbed case shows the highest potential application for CO_(2) reduction.In conclusion,alkali-metal-adsorbed MoSi_(2)N_(4) monolayer exhibits promising applications as novel optoelectronic devices and photocatalytic materials due to its unique physical and chemical properties.
文摘I.r.bands at 1559.0, 1441 .0, 1378 .9, 13603, 1031. 1,981 .4 and 947.3 cm -1 due tovarious types of dissociative adsorption of H2 over ZrO2 with changing temperatore wereobserved by in situ FT-IR spectroscopy.
文摘Surface enhanced Raman scattering of water adsorbed at silver electrodes in very negative potential region was first observed and a simple model related to the adsorption configuration is proposed.
基金supported by the Natural Science Foundation of Fujian Province of China (Grant Nos C0710036 and T0750008)
文摘Based on the nanostructured surface model that the （platinum, Pt） nanocones grow out symmetrically from a plane substrate, the local electric field near the conical nanoparticle surface is computed and discussed. On the basis of these results, the adsorbed CO molecules are modelled as dipoles, and three kinds of interactions, i.e. interactions between dipoles and local electric field, between dipoles and dipoles, as well as between dipoles and nanostructured substrate, are taken into account. The spatial configuration of CO molecules adsorbed on the nanocone surface is then given by Monte-Carlo simulation. Our results show that the CO molecules adsorbed on the nanocone surface cause local agglomeration under the action of an external electric field, and this agglomeration becomes more compact with decreasing conical angle, which results in a stronger interaction among molecules. These results serve as a basis for explaining abnormal phenomena such as the abnormal infrared effect （AIRE）, which was found when CO molecules were adsorbed on the nanostructured transition-metal surface.
文摘It was observed that the p-aminobenzoic acid(PABA)molecules adsorbed on A92CO3 colloids exhibited strong SERS effect,the enhancement factor is estimated at 10~7—10~8 The mechanism of SERS effect on PABA adsorbed on the colloids was discussed.
文摘The paper presents ac impedance behaviours of phenyl iso-thiocyanate adsorbed on Pt electrode.Nyquist plots are analysed and simulated,and parameters of relative equivalent circuits are obtained.
文摘A new reagent. trimethylammonium chlorochromate adsorbed on alumina, suitable for the oxidation of hydroxy compounds to the corresponding carbonyl compounds is described.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 10225420, 90206039 and 20021002）.
文摘This paper shows that the local electric field distribution near the nanostructure metallic surface is obtained by solving the Laplace equation, and furthermore, the configuration of CO molecules adsorbed on a Pt nanoparticle surface is obtained by using Monte Carlo simulation. It is found that the uneven local electric field distribution induced by the nanostructure surface can influence the configuration of carbon monoxide （CO） molecules by a force, which drags the adsorbates to the poles of the nanoparticles. This result, together with our results obtained before, may explain the experimental results that the nanostructure metallic surface can lead to abnormal phenomena such as anti-absorption infrared effects.
基金the Science Fund of the Chinese Academy of Sciences。
文摘The orientational ordering in adsorbed incommensurate monolayers is discussed in an anharmonic approach.A nonlinear relationship is predicted between the orientation of the monolayer relative to the substrate and the monolayer lattice parameter.Calculated values of the rninimum energy crientation angle for Ar on graphite are in good agreement with the experimental reported measurements.
