Rapid analysis of metal ions and organic compounds in strong acidic solutions is of sustainable interest in multiple disciplines.However,complicated and time-consuming pretreatments are always required for MS analysis...Rapid analysis of metal ions and organic compounds in strong acidic solutions is of sustainable interest in multiple disciplines.However,complicated and time-consuming pretreatments are always required for MS analysis of the compounds in strong acidic solutions.Otherwise,it will result in a weak signal and cause serious damage to the mass spectrometer.Herein,a simple method inherited from nano-ESI MS was developed for rapid analysis of strong acidic solutions.Nanoliter(nL)strong acidic solution was first loaded in the nano-ESI emitter,followed by evaporation to remove the H+and leave the analytes on the wall of the nano-ESI emitter.The evaporation process can be completed within 1 min because of the extremely tiny volume(≤1 nL)of the loaded solution.Then,the dried analytes on the wall of the nano-ESI emitter were redissolved by loading a new solvent,followed by nano-ESI MS analysis.By using this method,metal ions and organic compounds in the strong acidic solution can be detected with low sample consumption(1 nL),high speed(<2 min/sample),high sensitivity(limit of detection=0.2µg/L),and high accuracy(>90%).Proof-of-concept applications of the present method have been successfully achieved for the analysis of gastric juice(pH of the sample=1),monitoring reaction catalyzed by strong acid(pH of the system=0),and micro-area analysis of ores(pH of the extraction solvent=0),showing great application potential in multiple fields.展开更多
Lithium(Li)is an important energy metal in the 21st century.However,the selective recovery of Li is still a big challenge,especially from acidic solutions with multiple metal ions existence.Herein we report a new ion ...Lithium(Li)is an important energy metal in the 21st century.However,the selective recovery of Li is still a big challenge,especially from acidic solutions with multiple metal ions existence.Herein we report a new ion pair induced mechanism for selectively extracting Li^(+)from acidic chloride solutions by tributyl phosphate(TBP).It is shown that the acidity and the chloride ions in the aqueous phase have great effects on the extraction of Li^(+).The FT-IR,UV-Vis and ESI-MS experiments provide solid evidence for the formation of ion-pair complex[Li(TBP)_n(H_(2)O)_(m)]^(+)[FeCl_(4)]^(-)(n-1,2,3;m-0,1)in the organic phase,which brings about the effective and efficient extraction of Li^(+).This mechanism can overcome the Hofmeister bias and allow for the selective extraction of Li^(+) from the extremely hydrophilic chlorides.It has also been proved that the loaded Li in TBP can be effectively stripped by concentrated HCl solution with a Li/Fe separation factor>500.The understanding of the ion-pair transport mechanism is helpful for optimizing the recovery process or further advancing more efficient recovery techniques for Li from acidic liquor.展开更多
Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the inte...Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the interface,further growth of hydrate due to the suction of water in the capillary system formed between the wall of the cuvette and the end boundary of the hydrate layer occurs.Most probably,substantial effects on the formation of this capillary system may be caused by variations in reactor wall properties,for example,hydrophobic-hydrophilic balance,roughness,etc.We found,that the rate of CO_(2) hydrate film growth on the surface of the humic acid aqueous solution is 4-fold to lower in comparison with the growth rate on the surface of pure water.We suppose that this is caused by the adsorption of humic acid associates on the surface of hydrate particles and,as a consequence,by the deceleration of the diffusion of dissolved carbon dioxide to the growing hydrate particle.展开更多
Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the o...Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.展开更多
In order to improve corrosion resistance of stainless steel 316L in warm acidic solution, Ni？Cu？P coatings with high copper and phosphorus contents were deposited onto stainless steel 316L substrates via electroless...In order to improve corrosion resistance of stainless steel 316L in warm acidic solution, Ni？Cu？P coatings with high copper and phosphorus contents were deposited onto stainless steel 316L substrates via electroless plating. The structure of the film and its resistance to corrosion in a warm acidic environment were investigated using scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS）, X-ray diffraction spectrometry （XRD）, polarization curves, electrochemical impedance spectroscopy （EIS）, and dipping corrosion tests, respectively. The results demonstrate that Ni？Cu？P coatings consist of two types of nodules, which are 19.98% Cu and 39.17% Cu （mass fraction） respectively. The corrosion resistance of the 316L substrate when subjected to a warm acidic solution is significantly improved by the addition of the new type of the Ni？Cu？P coating. The as-plated coatings demonstrate better corrosion resistance than annealed coatings. As-plated coatings and those annealed at 673 K are found to corrode selectively, while pitting is observed to be the main corrosion mechanism of coatings annealed at 773 and 873 K.展开更多
The adsorption behavior of ion exchange resin D301 in the extraction of hexavalent molybdenum from high acidic leach solution was investigated. SEM, EDS and Raman spectra analyses were applied to studying the adsorpti...The adsorption behavior of ion exchange resin D301 in the extraction of hexavalent molybdenum from high acidic leach solution was investigated. SEM, EDS and Raman spectra analyses were applied to studying the adsorption capacity, reaction kinetics and possible adsorption mechanism in detail. Results showed that the adsorption capacity of D301 resin for molybdenum from high acidic leach solution was up to 463.63 mg/g. Results of the kinetic analysis indicated that the adsorption process was controlled by the particle diffusion with the activation energy 25.47 k J/mol（0.9-1.2 mm） and 20.38 k J/mol（0.6-0.9 mm）. Furthermore, the molybdenum loaded on the resin could be eluted by using 2 mol/L ammonia hydroxide solution. Besides, dynamic continuous column experiments verified direct extraction of molybdenum from acidic leach solutions by ion exchange resin D301 and the upstream flow improved dynamic continuous absorption.展开更多
Electrochemical corrosion behavior of Nd-Fe-B sintered magnets in nitric acid, hydrochloric acid, sulfuric acid, phosphate acid and in oxalic acid was studied. Potentiodynamic polarization curves and immersion time de...Electrochemical corrosion behavior of Nd-Fe-B sintered magnets in nitric acid, hydrochloric acid, sulfuric acid, phosphate acid and in oxalic acid was studied. Potentiodynamic polarization curves and immersion time dependence of corrosion rates of Nd-Fe-B sintered magnets in different acid solutions were tested. Microstructures of corroded Nd-Fe-B sintered magnets were investigated by means of SEM and AFM. The results indicate that in strong acid solutions of similar hydrogen ion concentration, the corrosion current increases in the order of HCl 〉 H3SO4 〉 HNO3 solution and Nd-Fe-B sintered magnets are passivated in phosphate acid and oxalic acid. Within 25 min, the corrosion rates of Nd-Fe-B sintered magnets in H2SO4 and H3PO4 solutions show a declining trend with immersion time, while in HNO3 and HCl solutions the corrosion rates are rising. And in H2C2O4 solution, weight of the magnets increases. The brim of Nd-Fe-B sintered magnets is corroded rather seriously and the size of the magnets changed greatly in nitric acid. The surfaces of the corroded magnets in the above mentioned acid solutions are all coarse.展开更多
The reaction mechanisms of phenol with formaldehyde in the first and second addition at the ortho- and para-position in acid solution were theoretically investigated at the PW91/DNP level with solvent effects included...The reaction mechanisms of phenol with formaldehyde in the first and second addition at the ortho- and para-position in acid solution were theoretically investigated at the PW91/DNP level with solvent effects included. The reaction of phenol with protonated methanediol firstly forms an adduct intermediate, via a SN2 mechanism with a water molecule as the leaving group. From the adduct intermediate, there are two reaction channels involving a proton transfer to form the addition products. One is that a proton directly transfers via a four-membered ring transition state with a notable energy barrier （Four-member mechanism）. Another mechanism involving a water molecule as catalyst to mediate the proton transfer （WCP mechanism）, is a barrierless process, indicating that the formation of the adduct intermediate, the first reaction step, is rate-limiting. The reaction products are free hydroxymethyl phenols and/or hydroxybenzy carbocation （HOC6H4CH2＋） which plays an important role in the following formation of methylene and methylene ether linkages. The second addition reactions between formaldehyde and hydroxymethyl phenol at all possible reaction sites of the phenol ring in acid solution were also investigated and discussed.展开更多
The dissolution of carbon steel in 5% HCl in the temperature range of 30~90℃ was inhibited by two organic compounds having the general formula: ClR NH2(CH2)n NH2 RCl where R is a benzyl group. The behaviour of these ...The dissolution of carbon steel in 5% HCl in the temperature range of 30~90℃ was inhibited by two organic compounds having the general formula: ClR NH2(CH2)n NH2 RCl where R is a benzyl group. The behaviour of these inhibitors in acidic medium were investigated using weight loss method, open circuit potential and linear polarization technique. These inhibitors provided satisfactory corrosion inhibition for carbon steel in hydrochloric acid solutions even at higher temperature and acid concentration (10%). The electrochemical results showed that the polarization resistance (Rp) values increased with increasing inhibitor concentration, also the corrosion current decreased and a higher inhibition efficiency was obtained. The protective properties of these two organic inhibitors were attributed to the chemisorption mechanism展开更多
The oxygen evolution reaction(OER) is the basis of various sustainable energy conversion and storage techniques,especially hydrogen production by water electrolysis.To realize the practical application of hydrogen ene...The oxygen evolution reaction(OER) is the basis of various sustainable energy conversion and storage techniques,especially hydrogen production by water electrolysis.To realize the practical application of hydrogen energy and mass-scale hydrogen production via water electrolysis,several obstacles,such as the multi-electron transfer OER process with sluggish kinetics and overall high reaction barrier,should be overcome.Manganese oxide-based(MnOx) materials,especially MnO_(2),have emerged as promising non-noble electrocatalysts for water electro-oxidation under acidic conditions due to their wellbalanced properties between catalytic activity and stability.This review introduces the fundamental understanding of the catalytic OER process on MnOx-based materials,including the conventional adsorbate evolution mechanism(AEM) and emerging lattice oxygen oxidation mechanism(LOM).The rational screening and prediction of MnOx-based catalysts that can stably catalyze OER in acid are summarized based on Pourbaix diagram analysis and thermodynamic density functional theory(DFT) calculations.Then,the up-to-date progress of upgrading the OER catalytic performance of MnOx-based catalysts by composite construction is reviewed.Afterward,feasible strategies to improve the electrocatalytic activity and lifetime of MnOx-based catalysts are systemically discussed in terms of crystal structure control,reasonable setting of working potential and electrolyte environment,optimal selection of acid-stable conductive supports,and self-healing engineering.Finally,future scientific challenges and research directions are outlined to guide the construction of advanced MnOx-based electrocatalysts for OER in acid.展开更多
Potentiodynamic polarization tests and slow strain rate test（SSRT） in combination with fracture morphology observations were conducted to investigate the stress corrosion cracking（SCC） behavior of 7003 aluminum al...Potentiodynamic polarization tests and slow strain rate test（SSRT） in combination with fracture morphology observations were conducted to investigate the stress corrosion cracking（SCC） behavior of 7003 aluminum alloy（AA7003） in acid and alkaline chloride solutions under various applied potentials（Ea）. The results show that AA7003 is to a certain extent susceptible to SCC via anodic dissolution（AD） at open-circuit potential（OCP） and is highly susceptible to hydrogen embrittlement（HE） at high negative Ea in the solutions with p H levels of 4 and 11. The susceptibility increases with negative shift in the potential when Ea is less than-1000 m V vs. SCE. However, the susceptibility distinctly decreases because of the inhibition of AD when Ea is equal to-1000 m V vs. SCE. In addition, the SCC susceptibility of AA7003 in the acid chloride solution is higher than that in the alkaline solution at each potential. Moreover, the effect of hydrogen on SCC increases with increasing hydrogen ion concentration.展开更多
The acid gas absorption in four potassium based amino acid salt solutions was predicted using artificial neural network(ANN). Two hundred fifty-five experimental data points for CO_2 absorption in the four potassium b...The acid gas absorption in four potassium based amino acid salt solutions was predicted using artificial neural network(ANN). Two hundred fifty-five experimental data points for CO_2 absorption in the four potassium based amino acid salt solutions containing potassium lysinate, potassium prolinate, potassium glycinate, and potassium taurate were used in this modeling. Amine salt solution's type, temperature, equilibrium partial pressure of acid gas, the molar concentration of the solution, molecular weight, and the boiling point were considered as inputs to ANN to prognosticate the capacity of amino acid salt solution to absorb acid gas. Regression analysis was employed to assess the performance of the network. Levenberg–Marquardt back-propagation algorithm was used to train the optimal ANN with 5:12:1 architecture. The model findings indicated that the proposed ANN has the capability to predict precisely the absorption of acid gases in various amino acid salt solutions with Mean Square Error(MSE) value of 0.0011, the Average Absolute Relative Deviation(AARD) percent of 5.54%,and the correlation coefficient(R^2) of 0.9828.展开更多
The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were ...The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.展开更多
The existing form of molybdenum in acidic sulfate solution was studied by means of ion exchange, infrared （IR） spectra and X-ray photoelectron spectroscopy （XPS）. The results indicate that the anionic molybdenum s...The existing form of molybdenum in acidic sulfate solution was studied by means of ion exchange, infrared （IR） spectra and X-ray photoelectron spectroscopy （XPS）. The results indicate that the anionic molybdenum species are predominant in acidic sulfate solution, and Mo（VI） can combine with sulfate radical to form heteropoly acid anions [Mo205（804）2]2- and [MoO2（HSO4）4]2-. With the decrease in solution pH from 1.92 to 0.06, the existing form of Mo（VI） changes from MovO21（OH）3^3- to [Mo205（S04）2]2- and then becomes [MoOz（HSO4）4]2-, which results in the decrease in the resin adsorption capacity for molybdenum.展开更多
The corrosion-wear behavior of a nanocrystalline Fe_（88）Si_（12） alloy disc coupled with a Si_3N_4 ball was investigated in acid（pH 3） and alkaline（pH 9） aqueous solutions. The dry wear was also measured for re...The corrosion-wear behavior of a nanocrystalline Fe_（88）Si_（12） alloy disc coupled with a Si_3N_4 ball was investigated in acid（pH 3） and alkaline（pH 9） aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe_（88）Si_（12） alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe_（88）Si_（12） alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe_（88）Si_（12） alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si_3N_4 ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe_（88）Si_（12） alloy in the pH 9 aqueous solution.展开更多
Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what th...Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what the key factors are of CO2 RR kinetics and selectivity will be of great help in optimizing electrolysers for CO2 reduction.In this work,we report our results of hydrogen evolution and CO2 reduction on Pt(111)and Pt film electrodes in CO2 saturated acid solution by cyclic voltammetry and infrared spectroscopy.In solution with pH>2,the major process is HER and the interfacial pH increases abruptly during HER;COad is the only adsorbed intermediate detected in CO2 reduction by infrared spectroscopy;the rate for COad formation increases with the coverage of UPD-H and reaches maximum at the onset potential for HER;the decrease of COad formation under HER is attributed to the available limited sites and the limited residence time for the reduction intermediate(Had),which is necessary for CO2 adsorption and reduction.展开更多
Fluid-rock interaction plays a critical function in physical and chemical processes associated with the formation and evolution of oil and gas reservoir space.In the diagenetic stage of shallow burial,the dissolution ...Fluid-rock interaction plays a critical function in physical and chemical processes associated with the formation and evolution of oil and gas reservoir space.In the diagenetic stage of shallow burial,the dissolution of carbonate rocks by acidic fluids is conducive to the development of secondary pore space in reservoirs.In contrast,the free drift experiment based on water bath instrument can simulate the dissolution process of carbonate rocks in shallow burial environment effectively.In order to study the shallow burial dissolution mechanism of carbonate rocks in different acid solutions,14 samples of typical carbonate rocks of Sinian,Cambrian,Ordovician,Permian and Triassic ages in the Tarim and Sichuan basins,China were used.The dissolution experiments on carbonate rocks in sulfuric acid,acetic acid,hydrochloric acid,silicic acid and carbonic acid at shallow burial temperature(30℃≤T≤90℃)were carried out using a water bath instrument.The PHREEQC software was used to simulate the dissolution of carbonate minerals,in order to compare the results of constant temperature water bath experiment.The results show that acid solutions have significant dissolution effect on shallow burial carbonate rocks when T=50–60℃,which corresponds to the burial depth of 1500–2000 m in the Tarim Basin and 1110–1480 m in the Sichuan Basin.However,there were obvious differences in the dissolution and reformation of carbonate rocks in different acids.In particular,sulfuric acid solution produced by thermochemical sulfate reduction can significantly promote the dissolution of carbonate rocks,especially dolomitic limestone.Moreover,the dissolution of limestone reservoirs is stronger than that of dolomite reservoirs in shallow burial.The results will provide new insights into the study of dissolution laws and influencing factors of reservoir spaces and the evaluation and prediction of carbonate reservoirs in China.展开更多
This study investigates the effects of varying Sc content on phase composition,corrosion resistance and passive film characteristic of Al_(1.2)CoCrFeNiSc_(x)(x=0,0.1,0.2,0.3)high-entropy alloys in 0.5 mol/L H_(2)SO_(4...This study investigates the effects of varying Sc content on phase composition,corrosion resistance and passive film characteristic of Al_(1.2)CoCrFeNiSc_(x)(x=0,0.1,0.2,0.3)high-entropy alloys in 0.5 mol/L H_(2)SO_(4) solution.The addition of Sc causes the alloys to form a Laves phase which is a(Ni,Co)_(2)Sc intermetallic compound with face centred cubic(FCC)structure and lattice parameter of 0.695 nm.During the potentiodynamic polarization process,Laves phase is severely corroded due to its large grain orientation spread value and high electrochemical activity.Sc deteriorates the corrosion resistance of the alloy primarily by significantly accelerating the corrosion rate rather than altering the corrosion tendency.Al_(1.2)CoCrFeNiSc_(x) alloys exhibit poorer corrosion resistance in 0.5 mol/L H_(2)SO_(4) than in 3.5 wt.%NaCl solution,with severe intergranular corrosion observed on the alloy surface.The passive films on Sc-free alloys primarily composed of Al_(2)O_(3) and Cr_(2)O_(3),while for Sc-containing alloys,the film mainly contains Al_(2)O_(3),Cr_(2)O_(3) and Sc_(2)O_(3).In addition,the passive films on Sc-free alloys behave as an n-type semiconductor,while the passive films on Sc-containing alloys surface exhibit the electronic characteristics of p-n junctions.As the Sc content rises,the defect density in passive film increases from 10^(21) cm^(-3) to 10^(23) cm^(-3),which leads to a less compact and less protective passive film,ultimately decreasing the alloy’s corrosion resistance.This work holds significant guiding significance for the engineering application of high-entropy alloys in acidic environments and is conducive to the development of high-performance corrosion-resistant alloys.展开更多
The Hastelloy C22 coatings on Q235 steel substrate were produced by high power diode laser cladding technique. Their corrosion behaviors in static and cavitation hydrochloric, sulfuric and nitric acid solutions were i...The Hastelloy C22 coatings on Q235 steel substrate were produced by high power diode laser cladding technique. Their corrosion behaviors in static and cavitation hydrochloric, sulfuric and nitric acid solutions were investigated. The electrochemical results show that corrosion resistance of coatings in static acid solutions is higher than that in cavitation ones. In each case, coating corrosion resistance in descending order is in nitric, sulfuric and hydrochloric acid solutions. Obvious erosion-corrosion morphology and serious intercrystalline corrosion of coating are noticed in cavitation hydrochloric acid solution. This is mainly ascribed to the aggressive ions in hydrochloric acid solution and mechanical effect from cavitation bubbles collapse. While coating after corrosion test in cavitation nitric acid solution shows nearly unchanged surface morphology. The results indicate that the associated action of cavitation and property of acid solution determines the corrosion development of coating. Hastelloy C22 coating exhibits better corrosion resistance in oxidizing acid solution for the stable formation of dense oxide film on the surface.展开更多
Variation and degradation of P-110 casing steel mechanical properties, due to sulfide stress cracking (SSC) in sour environments, was investigated using tensile and impact tests. These tests were carried out on specim...Variation and degradation of P-110 casing steel mechanical properties, due to sulfide stress cracking (SSC) in sour environments, was investigated using tensile and impact tests. These tests were carried out on specimens, which were pretreated under the following conditions for 168 hours: temperature, 60 ℃; pressure, 10 MPa; H2S partial pressure, 1 MPa and CO_(2) partial pressure, 1 MPa; preload stress, 80% of the yield strength (os); medium, simulated formation water. The reduction in tensile and impact strengths for P-110 casing specimens in corrosive environments were 28% and 54%, respectively. The surface morphology analysis indicated that surface damage and uniform plastic deformation occurred as a result of strain aging. Impact toughness of the casing decreased significantly and intergranular cracking occurred when specimens were maintained at a high stress level of 85% %.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21864001,21727812 and 21765001)the Ph.D.Start-up Foundation of East China University of Technology(No.DHBK2020001).
文摘Rapid analysis of metal ions and organic compounds in strong acidic solutions is of sustainable interest in multiple disciplines.However,complicated and time-consuming pretreatments are always required for MS analysis of the compounds in strong acidic solutions.Otherwise,it will result in a weak signal and cause serious damage to the mass spectrometer.Herein,a simple method inherited from nano-ESI MS was developed for rapid analysis of strong acidic solutions.Nanoliter(nL)strong acidic solution was first loaded in the nano-ESI emitter,followed by evaporation to remove the H+and leave the analytes on the wall of the nano-ESI emitter.The evaporation process can be completed within 1 min because of the extremely tiny volume(≤1 nL)of the loaded solution.Then,the dried analytes on the wall of the nano-ESI emitter were redissolved by loading a new solvent,followed by nano-ESI MS analysis.By using this method,metal ions and organic compounds in the strong acidic solution can be detected with low sample consumption(1 nL),high speed(<2 min/sample),high sensitivity(limit of detection=0.2µg/L),and high accuracy(>90%).Proof-of-concept applications of the present method have been successfully achieved for the analysis of gastric juice(pH of the sample=1),monitoring reaction catalyzed by strong acid(pH of the system=0),and micro-area analysis of ores(pH of the extraction solvent=0),showing great application potential in multiple fields.
基金supported by the National Natural Science Foundation of China(21706257,21878180)the Shanxi Province Coal Based Low-carbon Technology Major Projects(MC2016-05)the Xiangyuan Key Technology Research Projects(2018XYSDYY-02)。
文摘Lithium(Li)is an important energy metal in the 21st century.However,the selective recovery of Li is still a big challenge,especially from acidic solutions with multiple metal ions existence.Herein we report a new ion pair induced mechanism for selectively extracting Li^(+)from acidic chloride solutions by tributyl phosphate(TBP).It is shown that the acidity and the chloride ions in the aqueous phase have great effects on the extraction of Li^(+).The FT-IR,UV-Vis and ESI-MS experiments provide solid evidence for the formation of ion-pair complex[Li(TBP)_n(H_(2)O)_(m)]^(+)[FeCl_(4)]^(-)(n-1,2,3;m-0,1)in the organic phase,which brings about the effective and efficient extraction of Li^(+).This mechanism can overcome the Hofmeister bias and allow for the selective extraction of Li^(+) from the extremely hydrophilic chlorides.It has also been proved that the loaded Li in TBP can be effectively stripped by concentrated HCl solution with a Li/Fe separation factor>500.The understanding of the ion-pair transport mechanism is helpful for optimizing the recovery process or further advancing more efficient recovery techniques for Li from acidic liquor.
基金supported by the Russian Science Foundation(23-29-00830).
文摘Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the interface,further growth of hydrate due to the suction of water in the capillary system formed between the wall of the cuvette and the end boundary of the hydrate layer occurs.Most probably,substantial effects on the formation of this capillary system may be caused by variations in reactor wall properties,for example,hydrophobic-hydrophilic balance,roughness,etc.We found,that the rate of CO_(2) hydrate film growth on the surface of the humic acid aqueous solution is 4-fold to lower in comparison with the growth rate on the surface of pure water.We suppose that this is caused by the adsorption of humic acid associates on the surface of hydrate particles and,as a consequence,by the deceleration of the diffusion of dissolved carbon dioxide to the growing hydrate particle.
基金partly supported by the National Natural Science Foundation of China(NSFCs,52202050,52122308,21905253,51973200)the China Postdoctoral Science Foundation(2022TQ0286)the Natural Science Foundation of Henan(202300410372)。
文摘Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.
基金Project(CKJA201202)supported by the Innovation Fund Key Project of Nanjing Institute of Technology,ChinaProject(51301088)supported by the National Natural Science Foundation of China
文摘In order to improve corrosion resistance of stainless steel 316L in warm acidic solution, Ni？Cu？P coatings with high copper and phosphorus contents were deposited onto stainless steel 316L substrates via electroless plating. The structure of the film and its resistance to corrosion in a warm acidic environment were investigated using scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS）, X-ray diffraction spectrometry （XRD）, polarization curves, electrochemical impedance spectroscopy （EIS）, and dipping corrosion tests, respectively. The results demonstrate that Ni？Cu？P coatings consist of two types of nodules, which are 19.98% Cu and 39.17% Cu （mass fraction） respectively. The corrosion resistance of the 316L substrate when subjected to a warm acidic solution is significantly improved by the addition of the new type of the Ni？Cu？P coating. The as-plated coatings demonstrate better corrosion resistance than annealed coatings. As-plated coatings and those annealed at 673 K are found to corrode selectively, while pitting is observed to be the main corrosion mechanism of coatings annealed at 773 and 873 K.
基金Projects(21376251,21406233) supported by the National Natural Science Foundation of China
文摘The adsorption behavior of ion exchange resin D301 in the extraction of hexavalent molybdenum from high acidic leach solution was investigated. SEM, EDS and Raman spectra analyses were applied to studying the adsorption capacity, reaction kinetics and possible adsorption mechanism in detail. Results showed that the adsorption capacity of D301 resin for molybdenum from high acidic leach solution was up to 463.63 mg/g. Results of the kinetic analysis indicated that the adsorption process was controlled by the particle diffusion with the activation energy 25.47 k J/mol（0.9-1.2 mm） and 20.38 k J/mol（0.6-0.9 mm）. Furthermore, the molybdenum loaded on the resin could be eluted by using 2 mol/L ammonia hydroxide solution. Besides, dynamic continuous column experiments verified direct extraction of molybdenum from acidic leach solutions by ion exchange resin D301 and the upstream flow improved dynamic continuous absorption.
文摘Electrochemical corrosion behavior of Nd-Fe-B sintered magnets in nitric acid, hydrochloric acid, sulfuric acid, phosphate acid and in oxalic acid was studied. Potentiodynamic polarization curves and immersion time dependence of corrosion rates of Nd-Fe-B sintered magnets in different acid solutions were tested. Microstructures of corroded Nd-Fe-B sintered magnets were investigated by means of SEM and AFM. The results indicate that in strong acid solutions of similar hydrogen ion concentration, the corrosion current increases in the order of HCl 〉 H3SO4 〉 HNO3 solution and Nd-Fe-B sintered magnets are passivated in phosphate acid and oxalic acid. Within 25 min, the corrosion rates of Nd-Fe-B sintered magnets in H2SO4 and H3PO4 solutions show a declining trend with immersion time, while in HNO3 and HCl solutions the corrosion rates are rising. And in H2C2O4 solution, weight of the magnets increases. The brim of Nd-Fe-B sintered magnets is corroded rather seriously and the size of the magnets changed greatly in nitric acid. The surfaces of the corroded magnets in the above mentioned acid solutions are all coarse.
基金supported by the Key Program of the National Natural Science Foundation of China(30930074)
文摘The reaction mechanisms of phenol with formaldehyde in the first and second addition at the ortho- and para-position in acid solution were theoretically investigated at the PW91/DNP level with solvent effects included. The reaction of phenol with protonated methanediol firstly forms an adduct intermediate, via a SN2 mechanism with a water molecule as the leaving group. From the adduct intermediate, there are two reaction channels involving a proton transfer to form the addition products. One is that a proton directly transfers via a four-membered ring transition state with a notable energy barrier （Four-member mechanism）. Another mechanism involving a water molecule as catalyst to mediate the proton transfer （WCP mechanism）, is a barrierless process, indicating that the formation of the adduct intermediate, the first reaction step, is rate-limiting. The reaction products are free hydroxymethyl phenols and/or hydroxybenzy carbocation （HOC6H4CH2＋） which plays an important role in the following formation of methylene and methylene ether linkages. The second addition reactions between formaldehyde and hydroxymethyl phenol at all possible reaction sites of the phenol ring in acid solution were also investigated and discussed.
文摘The dissolution of carbon steel in 5% HCl in the temperature range of 30~90℃ was inhibited by two organic compounds having the general formula: ClR NH2(CH2)n NH2 RCl where R is a benzyl group. The behaviour of these inhibitors in acidic medium were investigated using weight loss method, open circuit potential and linear polarization technique. These inhibitors provided satisfactory corrosion inhibition for carbon steel in hydrochloric acid solutions even at higher temperature and acid concentration (10%). The electrochemical results showed that the polarization resistance (Rp) values increased with increasing inhibitor concentration, also the corrosion current decreased and a higher inhibition efficiency was obtained. The protective properties of these two organic inhibitors were attributed to the chemisorption mechanism
基金the financial support of the National Natural Science Foundation of China(21962008)the Yunnan Province Excellent Youth Fund Project(202001AW070005)the Yunnan Ten Thousand Talents Plan Young & Elite Talents Project(YNWR-QNBJ-2018-346)。
文摘The oxygen evolution reaction(OER) is the basis of various sustainable energy conversion and storage techniques,especially hydrogen production by water electrolysis.To realize the practical application of hydrogen energy and mass-scale hydrogen production via water electrolysis,several obstacles,such as the multi-electron transfer OER process with sluggish kinetics and overall high reaction barrier,should be overcome.Manganese oxide-based(MnOx) materials,especially MnO_(2),have emerged as promising non-noble electrocatalysts for water electro-oxidation under acidic conditions due to their wellbalanced properties between catalytic activity and stability.This review introduces the fundamental understanding of the catalytic OER process on MnOx-based materials,including the conventional adsorbate evolution mechanism(AEM) and emerging lattice oxygen oxidation mechanism(LOM).The rational screening and prediction of MnOx-based catalysts that can stably catalyze OER in acid are summarized based on Pourbaix diagram analysis and thermodynamic density functional theory(DFT) calculations.Then,the up-to-date progress of upgrading the OER catalytic performance of MnOx-based catalysts by composite construction is reviewed.Afterward,feasible strategies to improve the electrocatalytic activity and lifetime of MnOx-based catalysts are systemically discussed in terms of crystal structure control,reasonable setting of working potential and electrolyte environment,optimal selection of acid-stable conductive supports,and self-healing engineering.Finally,future scientific challenges and research directions are outlined to guide the construction of advanced MnOx-based electrocatalysts for OER in acid.
基金financially supported by the National Natural Science Foundation of China(No.51371039)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD),Jiangsu Province,China
文摘Potentiodynamic polarization tests and slow strain rate test（SSRT） in combination with fracture morphology observations were conducted to investigate the stress corrosion cracking（SCC） behavior of 7003 aluminum alloy（AA7003） in acid and alkaline chloride solutions under various applied potentials（Ea）. The results show that AA7003 is to a certain extent susceptible to SCC via anodic dissolution（AD） at open-circuit potential（OCP） and is highly susceptible to hydrogen embrittlement（HE） at high negative Ea in the solutions with p H levels of 4 and 11. The susceptibility increases with negative shift in the potential when Ea is less than-1000 m V vs. SCE. However, the susceptibility distinctly decreases because of the inhibition of AD when Ea is equal to-1000 m V vs. SCE. In addition, the SCC susceptibility of AA7003 in the acid chloride solution is higher than that in the alkaline solution at each potential. Moreover, the effect of hydrogen on SCC increases with increasing hydrogen ion concentration.
文摘The acid gas absorption in four potassium based amino acid salt solutions was predicted using artificial neural network(ANN). Two hundred fifty-five experimental data points for CO_2 absorption in the four potassium based amino acid salt solutions containing potassium lysinate, potassium prolinate, potassium glycinate, and potassium taurate were used in this modeling. Amine salt solution's type, temperature, equilibrium partial pressure of acid gas, the molar concentration of the solution, molecular weight, and the boiling point were considered as inputs to ANN to prognosticate the capacity of amino acid salt solution to absorb acid gas. Regression analysis was employed to assess the performance of the network. Levenberg–Marquardt back-propagation algorithm was used to train the optimal ANN with 5:12:1 architecture. The model findings indicated that the proposed ANN has the capability to predict precisely the absorption of acid gases in various amino acid salt solutions with Mean Square Error(MSE) value of 0.0011, the Average Absolute Relative Deviation(AARD) percent of 5.54%,and the correlation coefficient(R^2) of 0.9828.
基金supported by the National Key Basic Research Program of China(973 Program,2012CB224802)the SINOPEC project(No.114013)
文摘The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.
基金supported by the National Natural Science Foundation of China(No.51104186)
文摘The existing form of molybdenum in acidic sulfate solution was studied by means of ion exchange, infrared （IR） spectra and X-ray photoelectron spectroscopy （XPS）. The results indicate that the anionic molybdenum species are predominant in acidic sulfate solution, and Mo（VI） can combine with sulfate radical to form heteropoly acid anions [Mo205（804）2]2- and [MoO2（HSO4）4]2-. With the decrease in solution pH from 1.92 to 0.06, the existing form of Mo（VI） changes from MovO21（OH）3^3- to [Mo205（S04）2]2- and then becomes [MoOz（HSO4）4]2-, which results in the decrease in the resin adsorption capacity for molybdenum.
基金supported by the National Natural Science Foundation of China(No.51201172)
文摘The corrosion-wear behavior of a nanocrystalline Fe_（88）Si_（12） alloy disc coupled with a Si_3N_4 ball was investigated in acid（pH 3） and alkaline（pH 9） aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe_（88）Si_（12） alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe_（88）Si_（12） alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe_（88）Si_（12） alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si_3N_4 ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe_（88）Si_（12） alloy in the pH 9 aqueous solution.
基金supported by the National Natural Science Foundation of China (No.21473175 and No.21273215)the Ministry of Science and Technology of China (No.2015CB932301)
文摘Hydrogen evolution reaction(HER)is the major cathodic reaction which competes CO2 reduction reaction(CO2 RR)on Pt electrode.Molecular level understanding on how these two reactions interact with each other and what the key factors are of CO2 RR kinetics and selectivity will be of great help in optimizing electrolysers for CO2 reduction.In this work,we report our results of hydrogen evolution and CO2 reduction on Pt(111)and Pt film electrodes in CO2 saturated acid solution by cyclic voltammetry and infrared spectroscopy.In solution with pH>2,the major process is HER and the interfacial pH increases abruptly during HER;COad is the only adsorbed intermediate detected in CO2 reduction by infrared spectroscopy;the rate for COad formation increases with the coverage of UPD-H and reaches maximum at the onset potential for HER;the decrease of COad formation under HER is attributed to the available limited sites and the limited residence time for the reduction intermediate(Had),which is necessary for CO2 adsorption and reduction.
基金jointly supported by the Science and Technology Development Project of PetroChina Hangzhou Institute of Petroleum Geology(No.RIPED-2020-JS-51008)the Naturacl Science Foundation of China(Nos.41872250,41802159)。
文摘Fluid-rock interaction plays a critical function in physical and chemical processes associated with the formation and evolution of oil and gas reservoir space.In the diagenetic stage of shallow burial,the dissolution of carbonate rocks by acidic fluids is conducive to the development of secondary pore space in reservoirs.In contrast,the free drift experiment based on water bath instrument can simulate the dissolution process of carbonate rocks in shallow burial environment effectively.In order to study the shallow burial dissolution mechanism of carbonate rocks in different acid solutions,14 samples of typical carbonate rocks of Sinian,Cambrian,Ordovician,Permian and Triassic ages in the Tarim and Sichuan basins,China were used.The dissolution experiments on carbonate rocks in sulfuric acid,acetic acid,hydrochloric acid,silicic acid and carbonic acid at shallow burial temperature(30℃≤T≤90℃)were carried out using a water bath instrument.The PHREEQC software was used to simulate the dissolution of carbonate minerals,in order to compare the results of constant temperature water bath experiment.The results show that acid solutions have significant dissolution effect on shallow burial carbonate rocks when T=50–60℃,which corresponds to the burial depth of 1500–2000 m in the Tarim Basin and 1110–1480 m in the Sichuan Basin.However,there were obvious differences in the dissolution and reformation of carbonate rocks in different acids.In particular,sulfuric acid solution produced by thermochemical sulfate reduction can significantly promote the dissolution of carbonate rocks,especially dolomitic limestone.Moreover,the dissolution of limestone reservoirs is stronger than that of dolomite reservoirs in shallow burial.The results will provide new insights into the study of dissolution laws and influencing factors of reservoir spaces and the evaluation and prediction of carbonate reservoirs in China.
基金Project(ZR2021QE136)supported by the Natural Science Foundation of Shandong Province,ChinaProject(52301106)supported by the National Natural Science Foundation of China+1 种基金Project(2022KJ273)supported by the Development Plan of Shandong Province Young Innovation Team of Higher Education Institutions,ChinaProject(2024HWYQ-074)supported by the Shandong Provincial Natural Science Fund for Excellent Young Scientists Fund Program(Overseas),China。
文摘This study investigates the effects of varying Sc content on phase composition,corrosion resistance and passive film characteristic of Al_(1.2)CoCrFeNiSc_(x)(x=0,0.1,0.2,0.3)high-entropy alloys in 0.5 mol/L H_(2)SO_(4) solution.The addition of Sc causes the alloys to form a Laves phase which is a(Ni,Co)_(2)Sc intermetallic compound with face centred cubic(FCC)structure and lattice parameter of 0.695 nm.During the potentiodynamic polarization process,Laves phase is severely corroded due to its large grain orientation spread value and high electrochemical activity.Sc deteriorates the corrosion resistance of the alloy primarily by significantly accelerating the corrosion rate rather than altering the corrosion tendency.Al_(1.2)CoCrFeNiSc_(x) alloys exhibit poorer corrosion resistance in 0.5 mol/L H_(2)SO_(4) than in 3.5 wt.%NaCl solution,with severe intergranular corrosion observed on the alloy surface.The passive films on Sc-free alloys primarily composed of Al_(2)O_(3) and Cr_(2)O_(3),while for Sc-containing alloys,the film mainly contains Al_(2)O_(3),Cr_(2)O_(3) and Sc_(2)O_(3).In addition,the passive films on Sc-free alloys behave as an n-type semiconductor,while the passive films on Sc-containing alloys surface exhibit the electronic characteristics of p-n junctions.As the Sc content rises,the defect density in passive film increases from 10^(21) cm^(-3) to 10^(23) cm^(-3),which leads to a less compact and less protective passive film,ultimately decreasing the alloy’s corrosion resistance.This work holds significant guiding significance for the engineering application of high-entropy alloys in acidic environments and is conducive to the development of high-performance corrosion-resistant alloys.
文摘The Hastelloy C22 coatings on Q235 steel substrate were produced by high power diode laser cladding technique. Their corrosion behaviors in static and cavitation hydrochloric, sulfuric and nitric acid solutions were investigated. The electrochemical results show that corrosion resistance of coatings in static acid solutions is higher than that in cavitation ones. In each case, coating corrosion resistance in descending order is in nitric, sulfuric and hydrochloric acid solutions. Obvious erosion-corrosion morphology and serious intercrystalline corrosion of coating are noticed in cavitation hydrochloric acid solution. This is mainly ascribed to the aggressive ions in hydrochloric acid solution and mechanical effect from cavitation bubbles collapse. While coating after corrosion test in cavitation nitric acid solution shows nearly unchanged surface morphology. The results indicate that the associated action of cavitation and property of acid solution determines the corrosion development of coating. Hastelloy C22 coating exhibits better corrosion resistance in oxidizing acid solution for the stable formation of dense oxide film on the surface.
基金support of the State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation,Southwest Petroleum University in Chinathe National Natural Science Foundation of China (Grant No.51004084)
文摘Variation and degradation of P-110 casing steel mechanical properties, due to sulfide stress cracking (SSC) in sour environments, was investigated using tensile and impact tests. These tests were carried out on specimens, which were pretreated under the following conditions for 168 hours: temperature, 60 ℃; pressure, 10 MPa; H2S partial pressure, 1 MPa and CO_(2) partial pressure, 1 MPa; preload stress, 80% of the yield strength (os); medium, simulated formation water. The reduction in tensile and impact strengths for P-110 casing specimens in corrosive environments were 28% and 54%, respectively. The surface morphology analysis indicated that surface damage and uniform plastic deformation occurred as a result of strain aging. Impact toughness of the casing decreased significantly and intergranular cracking occurred when specimens were maintained at a high stress level of 85% %.
