Rapid analysis of metal ions and organic compounds in strong acidic solutions by nano-ESI mass spectrometry

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.

Recent progress of advanced manganese oxide-based materials for acidic oxygen evolution reaction: Fundamentals, performance optimization,and prospects

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.

Progress on the mechanisms of Ru-based electrocatalysts for the oxygen evolution reaction in acidic media

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.

Ion-pair induced solvent extraction of lithium(Ⅰ)from acidic chloride solutions with tributyl phosphate

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.

Solvent extraction of vanadium from sulfuric acid solution

The behaviour of vanadium（V） extracted from sulfuric acid solution was investigated using Cyanex 923 as an extractant. The effects of the concentration of Cyanex 923 and the pH of the solution were studied. The extraction of vanadium（V） increases with the increase of Cyanex 923 concentration and shaking time. Cyanex 923 can extract vanadium（V） from sulfuric acid solution at low pH conditions, and the best pH conditions for extraction of vanadium（V） are at pH 1.0-2.0. The species extracted into the organic phase is VO2HSO4 with one molecule of Cyanex 923. Equilibrium studies were used to assess the extraction efficiency of vanadium（V） recovery from the sulfuric acid solution.

Electrochemical Corrosion Behavior of Nd-Fe-B Sintered Magnets in Different Acid Solutions

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.

Formation and Oxidation of Hydrogen Molybdenum Bronze on Platinum Electrode in Sulfuric Acid Solution

Hydrogen molybdenum bronze (HxMoO3) can be electrodeposited on platinum and oxidized in two steps to the hydrogen molybdenum bronze with less amount of hydrogen HyMoO3 (y<x) and MoO3 when platinum electrode is cycled from -0.2 to 1.3V (vs. SCE) in 0.05 mol/L Na2MoO4 + 0.5 mol/L H2SO4 solution. During the formation of HxMoO3, the electrochemical reduction of molybdate existing in the form of polymolydate is reversible and is about a five-electron transfer reaction.

Addition Mechanisms of Phenol toward Formaldehyde under Acidic Condition: a Theoretical Investigation

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.

Corrosion Inhibition of Carbon Steel in Hot Hydrochloric Acid Solutions

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

Effects of applied potential on the stress corrosion cracking behavior of 7003 aluminum alloy in acid and alkaline chloride solutions

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.

Dissolution kinetics of Si and Al from montmorillonite in carbonic acid solution

The reaction between carbonic acid and montmorillonite minerals was studied in order to provide a theoretical basis for analyzing changes in the physical properties of coal seams after CO_(2)injection and for optimizing CO_(2) pumping parameters.A single montmorillonite mineral of purity[90%was selected and subjected to reactions at 25,35,and 45℃in carbonic acid solutions of varying acidity.The Si and Al concentrations in the solutions and the structure and elemental compositions of the montmorillonite before and after the reactions were analyzed using a spectrophotometer,an X-ray diffractometer,and an energy-dispersive X-ray spectrometer;kinetic reaction models were established for the dissolution of Si and Al in carbonic acid solutions in order to estimate the apparent activation energy of Si dissolution under different acidity conditions.The results indicate that Al dissolved rapidly and soon reached solubility equilibrium.On the other hand,Si concentration in the solutions increased rapidly and then gradually declined with vibrations,with maximum values at 25,35,and 45℃,which were observed at approximately 96,72,and 48 h,respectively.In addition,Si dissolution fitted the diffusion-controlled reaction model well;as the pH value decreased,the apparent activation energy of Si dissolution decreased,and Si became easier to dissolve.Furthermore,it was concluded that as a weak acid,carbonic acid causes little damage to the mineral structure of montmorillonite.

Corrosion-wear behavior of nanocrystalline Fe88Si12 alloy in acid and alkaline solutions

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.

Liquid-liquid extraction of phosphorus from sulfuric acid solution using benzyl dimethyl amine

This study addresses the liquid-liquid extraction behavior of phosphorus from a sulfuric acid solution using benzyl dimethyl amine(BDMA)in kerosene.The extraction equilibria investigated with varied BDMA concentrations could reveal the formation of 3[BDMA]·[H_(3)PO_(4)]^(-)complex in the organic phase.The thermodynamic properties determined at various temperatures indicated that the process was exothermic with a calculated enthalpy(△H^(Θ))of−24.0 kJ·mol^(−1).The organic-to-aqueous phase(O/A)volume ratio was varied to elucidate the quantitative extraction of phosphorus.The McCabe-Thiele diagram plotted for the extraction isotherm was validated for the requirement of three counter-current stages in the extraction at an O/A volume ratio of 2.0/3.5.The back-extraction of phosphorus from the loaded organic phase was quantitatively achieved by contacting 4.0 mol·L−1 H2SO4 solution in three stages of counter-current contact at an O/A volume ratio of 3/2.This study can be applied to remove phosphorus from the sulfuric acid leach solutions of monazite processing,and many other solutions.

Electrochemical-Voltammetry Behavior of Several Aromatic Aldehydes in Acid Solution

The electrochemical-voltammetry behavior of vanillin, heliotropin, anisaldehyde on the surface of Pt, Au electrodes in acid solution has been studied by means of the electrochemical cyclic voltammetry method. It was found that the electrochemical processes of them are irreversible on both Pt and Au electrodes. The electrochemical activity of vanillin is stronger than heliotropin's and heliotropin's is stronger than anisaldehyde's on Pt electrode. While the electrochemical activity of anisaldehyde is stronger than heliotropin's and vanillin's is the weakest on Au. The results indicate that when they are used as additives for electroplating, they must be consumptive, and it will improve the leveling ability of plating solution and brightness of the deposition layer.

ELECTROANALYTICAL CIIARACTERISTICS OF NICOTINIC ACID IN MICELLAR SOLUTION

The electroanalytical characteristies of nicotinic acid in miceilar solution,were studied by cyclic voltammetry,constant potential coulometry and chron ocoulometry.A procedure of the absorptive voltammetric determination of the drug was worked out.

Topical Application of Ascorbic Acid Solution as an Adjunctive Method of Periodontal Therapy among Wet Snuff Users after Prosthodontics Therapy

Background: During several years, ascorbic acid (vitamin C) played a significant role in the health of periodontal tissues. The goals of prosthodontics management are to restore the missing teeth, provide the loss of teeth functions, and establish acceptable dental esthetics, and there are some evidences revealing the passive effects of snuff on the results of prosthodontics and periodontal treatment, so the present study is performed to evaluate the outcomes of topical application of ascorbic acid solution as an adjunctive method of periodontal therapy among wet sniff users after prosthodontics therapy. Methods: The clinical situation was evaluated in 150 moderate periodontitis patients after conventional periodontal and prosthodontics therapy. They were selected from outpatient clinics, college of dentistry, King Khalid University, and from some hospitals Ministry of Health in Tabuk, Jazan and Aseer regions. The study was conducted from September 2020 to December 2020. The time of post-treatment assessment was one year. The study was included 50 patients who don’t use wet snuff as a group I (GI) (control group), 50 patients wet snuff users as group II (GII), and 50 patients wet snuff users were treated with topical application of ascorbic acid solution as group III (GIII). The participants were aged over 20 years, with a mean age of 35 years. The duration of using wet snuff was at least one year. Plaque index (PLI), gingival index (GI), clinical attachment loss (CAL) were recorded at baseline (first visit), then after 4 weeks (second visit) and after 6 weeks (third visit) of conventional periodontal therapy and topical application of ascorbic acid solution. Statistical analysis was done using ANOVA test and paired t-test. Results: According to statistical analysis, there was the inclination of decrease in the mean and standard deviation of plaque index (PLI) from 2.8 ± 1.4 to 2.5 ± 0.51, and 2.7 ± 0.33 in group II, and decrease from 2.7 ± 0.34 to 2.5 ± 0.23 and 2.6 ± 0.65 in group III. Similarly in the gingival index (GI), there was a decrease in the mean and standard deviation from 2.8 ± 0.52 to 2.3 ± 0.62 and 2.5 ± 0.51 in group II and a decrease from 2.5 ± 0.8 to 2.3 ± 0.58 and 2.4 ± 0.47 in group III. Moreover, there was a decrease in the mean and standard deviation of clinical attachment loss (CAL) from 4.5 ± 0.26 to 3.9 ± 0.83 and 4.2 ± 0.83 in group II and from 4.2 ± 0.31 to 3.8 ± 0.46 and 3.8 ± 0.31 in group III;less than group I without significance differences (p > 0. 05) in all study groups at baseline and after 4 weeks, and 6 weeks of follow up except CAL. Conclusion: The results of our study displayed that periodontal parameters vary among wet snuff users after topical application of ascorbic acid solution as an adjunctive method of periodontal therapy

The effects of sulfide stress cracking on the mechanical properties and intergranular cracking of P110 casing steel in sour environments

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 CO2 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% %.

Role of dissolved oxygen reduction in improvement inhibition performance of ascorbic acid during copper corrosion in 0.50 mol/L sulphuric acid

The kinetics of dissolved O_2 reduction and hydrogen evolution reactions on copper surface was studied in naturally aerated and air and O_2-saturated 0.50 mol/L H_2SO_4 solutions using polarization measurements combined with the rotating disc electrode (RDE).The Koutecky-Levich plot indicated that the dissolved O_2 reduction at the copper electrode was an apparent four-electron process.A correlation between the presence of dissolved O_2 and the formation of Cu_2O,confirmed from XRD,was discussed. Ascorbic a...

Agglomeration and leaching behaviors of copper oxides with different chemical binders

The chemical binder is one of the critical factors affecting ore agglomeration behavior and leaching efficiency.In this study,we in-vestigated the effect of the type of binder and mass fraction of the H_(2)SO_(4)solution used on the curing,soaking,and leaching behavior of ag-glomerations.The results revealed that Portland cement(3CaO·SiO_(2),2CaO·SiO_(2),and 3CaO·Al_(2)O_(3))was the optimal binder for obtaining a well-shaped,stable agglomeration structure.A higher extraction rate was achieved when using Portland cement than that obtained using sodi-um silicate,gypsum,or acid-proof cement.An excessive geometric mean size is not conducive to obtaining well-shaped agglomerations and desirable porosity.Using computed tomography(CT)and MATLAB,the porosity of two-dimensional CT images in sample concentrations L1-L3 was observed to increase at least 4.5vol%after acid leaching.Ore agglomerations began to be heavily destroyed and even to disinteg-rate when the sulfuric acid solution concentration was higher than 30 g/L,which was caused by the excessive accumulation of reaction products and residuals.

Removing ammonia from air with a constant pH, slightly acidic water spray wet scrubber using recycled scrubbing solution

Previous research on wet scrubbers has only studied highly acidic scrubbing solutions because of their high ammonia capture efficiencies; however, the high acidity created practical problems. Lower acidity solutions would reduce corrosion, maintenance, and cost; however, designers may need to use strategies for increasing scrubber effectiveness, such as using lower air velocities. The objective of this studywas to determine if a spray scrubber with slightly acidic and higher p H scrubbing solution （pH from 2 to 8） could effectively remove NH3 from NH3 laden air （such as animal building exhaust air）, and also collect this valuable resource for rater use as a fertilizer. A bench-scale spray wet scrubber treated 20 ppmv NH3/air mixture in a countercurrent contact chamber. First, the solution pH was varied from 2 to 8while maintaining constant air velocity at 1.3 m. s-1. Next, air velocity was increased （2and 3 m.s-1） while solution pH remained constant at pH6. At 1.3 m.s -1, NH3 removal efficiencies ranged between 49.0% （pH8） and 84.3% （pH2）. This study has shown that slightly acidic scrubbing solutions are a practical means of removing ammonia from air especially if the scrubber is designed to increase collisions between solution droplets and NH3 molecules. The NH3 removed from the air was held in solution as NH4＋ and accumulates over time so the solution should be an excellent fertilizer.