Applications of carbonic acid solution for developing conversion coatings on Mg alloy

Works on exploring an environmentally clean method for producing an Mg,Al-hydrotalcite(Mg6Al2(OH) 16CO3·4H2O) layer and/or calcium carbonate(CaCO3) layer on Mg alloy in a carbonic acid solution system(aqueous HCO3-/CO3 2-or Ca 2+ /HCO3-) at 50℃ were reviewed.Conversion treatment for the Mg,Al-hydrotalcite conversion coating was as follows.Mg alloy was treated first in acidic HCO3-/CO3 2-aqueous for precursor layer formation on Mg alloy surface and then in alkaline HCO3-/CO3 2-aqueous to form a crystallized Mg,Al-hydrotalcite coating.Duration of an Mg,Al-hydrotalcite coating on Mg alloy surface was reduced from 12 h to 4 h by the conversion treatment.On the other hand,for reducing the formation time of CaCO3 coating on Mg alloy,the aqueous Ca 2+ /HCO3-with a saturated Ca 2+ content was employed for developing a CaCO3 coating on Mg alloy.A dense CaCO3 coating could yield on Mg alloy surface in 2 h.Corrosion rate(corrosion current density,Jcorr) of the Mg,Al-hydrotalcite-coated sample and CaCO3-coated AZ91D sample was 7-10μA/cm 2,roughly two orders less than the Jcorr of the as-diecast sample(about 200μA/cm 2) . No corrosion spot on the Mg,Al-hydrotalcite-coated sample and CaCO3-coated sample was observed after 72 h and 192 h salt spray test,respectively.

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.

Polymer efficiency and sulfate concentration for hybrid EOR application to an acidic carbonate reservoir

Polymers play an important role in hybrid enhanced oil recovery (EOR), which involves both a polymer and low-salinity water. Because the polymer commonly used for low-salinity polymer flooding (LSPF) is strongly sensitive to brine pH, its efficiency can deteriorate in carbonate reservoirs containing highly acidic formation water. In this study, polymer efficiency in an acidic carbonate reservoir was investigated experimentally for different salinity levels and SO42− concentrations. Results indicated that lowering salinity improved polymer stability, resulting in less polymer adsorption, greater wettability alteration, and ultimately, higher oil recovery. However, low salinity may not be desirable for LSPF if the injected fluid does not contain a sufficient number of sulfate (SO42−) ions. Analysis of polymer efficiency showed that more oil can be produced with the same polymer concentration by adjusting the SO42− content. Therefore, when river water, which is relatively easily available in onshore fields, is designed to be injected into an acidic carbonate reservoir, the LSPF method proposed in this study can be a reliable and environmentally friendly method with addition of a sufficient number of SO42− ions to river water.

Esterification of cyclohexene with formic acid over a peanut shell-derived carbon solid acid catalyst

A carbon solid acid catalyst was prepared by the sulfonation of partially carbonized peanut shell with concentrated H2SO4. The structure and acidity of the catalyst were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and elemental analysis, which showed that it was an amorphous carbon material composed of aromatic carbon sheets in random orientations. Sulfonic acid groups were present on the surface at a density of 0.81 mmol/g. The carbon solid acid catalyst showed better performance than HZSM‐5 for the esterification of cyclohexene with formic acid. At a3：1 molar ratio of formic acid to cyclohexene, catalyst loading of 0.07 g/mL of cyclohexene, and reaction time of 1 h at 413 K, the cyclohexene conversion was 88.4% with 97.3% selectivity to cyclohexyl formate. The carbon solid acid catalyst showed better reusability than HZSM‐5 because its large pores were minimally affected by the accumulation of oligomerized cyclohexene, which deactivated HZSM‐5. The activity of the carbon solid acid catalyst decreased somewhat in the first two recycles due to the leaching of polycyclic aromatic hydrocarbon containing –SO3H groups and then it remained constant in the following reuse.

Efficient hydrolysis of cellulose to glucose catalyzed by lignin-derived mesoporous carbon solid acid in water

Two kinds of mesoporous carbon solid acids(LDMCE-SO3H and LDMCS-SO3H)were successfully prepared using masson pine alkali lignin as carbon source by evaporation-induced self-assembly(EISA)and salt-induced selfassembly(SISA)followed by sulfonation,respectively.In terms of preparation process,SISA(self-assembly in water and preparation time of 2 days)is greener and simpler than EISA(self-assembly in ethanol and preparation time of 7 days).The prepared LDMCE-SO3H and LDMCS-SO3H exhibit obvious differences in structural characteristics such as pore channel structure,specific surface area,mesopore volume and the density of-SO3H groups.Furthermore,the catalytic performances of LDMCE-SO3H and LDMCS-SO3H were investigated in the hydrolysis of microcrystalline cellulose in water,and the glucose yields of 48.99%and 54.42%were obtained under the corresponding optimal reaction conditions.More importantly,the glucose yields still reached 28.85%and 30.35%after five runs,and restored to 39.02%and 45.98%through catalysts regeneration,respectively,demonstrating that LDMCE-SO3H and LDMCS-SO3H have excellent recyclability and regenerability.

Acetalization of carbonyl compounds with 2,2,4-trimethyl-1,3-pentanedio catalyzed by novel carbon based solid acid catalyst

The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol （TMPD） catalyzed by the novel carbon based acid was first carried out. High conversion （≥98%） and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover. the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.

Numerical investigation of fluid phase momentum transfer in carbonate acidizing

This work mainly studies the effect of fluid phase momentum transfer mechanisms on the acidizing results,including the retardation effect of the porous structure and the interaction between the fluid phase,such as viscous dissipation and inertial effect.The results show that the acid fluid momentum transfer is influenced by the complex porous structure and fluid viscous dissipation.Eventually,the Stokes-Darcy equation is recommended to be adopted to describe the fluid phase momentum transfer in the following numerical simulation studies of the carbonate acidizing process.Based on this model,a parametric research is carried out to investigate the impact of acid on rock physical characteristics in the stimulation process.Increasing the acid concentration appears to minimize the quantity of acid consumed for the breakthrough.The acid surface reaction rate has a considerable impact on the pore volume to breakthrough and the optimum acid injection rate.The influence of permeability on the acidizing results basically shows a negative correlation with the injection rate.The difference between the acidizing curves of different permeability gradually becomes insignificant with the decrease in injection rate.The existence of isolated fracture and vug significantly reduces acid consumption for the breakthrough.

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

Adsorption of acid and basic dyes by sludge-based activated carbon:Isotherm and kinetic studies

A batch experiment was conducted to investigate the adsorption of an acid dye(Acid Orange 51) and a basic dye(Safranine) from aqueous solutions by the sludge-based activated carbon(SBAC). The results show that the adsorption of Acid Orange 51 decreases at high p H values, whereas the uptake of Safranine is higher in neutral and alkaline solutions than that in acidic conditions. The adsorption time needed for Safranine to reach equilibrium is shorter than that for Acid Orange 51. The uptakes of the dyes both increase with temperature increasing, indicating that the adsorption process of the dyes onto SBAC is endothermic. The equilibrium data of the dyes are both best represented by the Redlich-Peterson model. At 25 °C, the maximum adsorption capacities of SBAC for Acid Orange 51 and Safranine are 248.70 mg/g and 525.84 mg/g, respectively. The Elovich model is found to best describe the adsorption process of both dyes, indicating that the rate-limiting step involves the chemisorption. It can be concluded that SBAC is a promising material for the removal of Acid Orange 51 and Safranine from aqueous solutions.

Adsorption of Folic Acid on the Single-walled Carbon Nanotubes: AIM and NBO Analyses via DFT

In the present work, the behavior of folic acid （FA） molecule adsorbed onto single-walled carbon nanotube （SWCNT） was examined using the DFT-B3LYP/6-31G＊ level. In order to obtain information about the binding features of SWCNT as adsorbent with FA molecule, several studies, including the structural and electronic parameters and also the Atoms in Molecules （AIM） analysis, were performed. It was observed that the FA molecule via hydrogen bond prefers to adsorb on SWCNT with adsorption energy of about -18.70 kcal/mol. The molecular orbitals （HOMO and LUMO）, natural bond orbital （NBO）,analysis, and density of states （DOS） plot indicated that a charge about 0.032 [ e [ is transferred from the FA molecule to the nanotube. After solvation energy calculations, it was found that the presence of a polar solvent causes an increase in FA adsorption on the single-walled carbon nanotube. Topological features such as electron energy density （Hc） and Laplacian of the electron density （V2p~） demonstrate partial covalent nature for H（ll6）...O（10） interaction in the FA/SWCNT complex. According to the calculated results, the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.

Square wave voltammetric quantification of folic acid,uric acid and ascorbic acid in biological matrix

Nowadays, modified electrodes with metal nanoparticles have appeared as an alternative for the electroanalysis of various compounds. In this study, gold nanoparticles（GNPs） were chosen as interesting metal nanoparticles for modifying carbon paste electrode（CPE）. GNPs and the gold nanoparticles-modified carbon paste electrode（GNPs/CPE） were characterized by UV–Vis spectroscopy, transmission electron microscopy（TEM） and scanning electron microscopy（SEM）. GNPs/CPE as a simple and sensitive electrode was used to study three important biological molecules： folic acid（FA）, uric acid（UA） and ascorbic acid（AA）. Square wave voltammetry（SWV） was used as an accurate technique for quantitative measurements. A good linear relation was observed between anodic peak current（ipa） and FA（5.2 × 10（-6）– 2.5 × 10（-5）M）, UA（1.2 × 10（-6）– 2.1 × 10（-5）M） and AA（1.2 × 10（-6）– 2.5 × 10（-5）M） concentrations in simultaneous determination of these molecules.

Adsorption Properties and Quantum Molecular Descriptors of the Folic Acid Drug Adsorbed onto Zigzag and Armchair Single Walled Carbon Nanotubes:DFT Simulations

The adsorption behavior of folic acid onto（5,0） zigzag and（5,5） armchair carbon nanotube（SWCNT） has been investigated using B3 LYP density functional at the 6-31G＊ level. The adsorption energies,molecular orbital analysis and structural changes at the adsorption site are indicative of covalent adsorption on the zigzag SWCNT surface,while the adsorption is physical on the armchair SWCNT surface. The density of states（DOS） Plot and the quantum molecular descriptors（QMD） are witness to the significant changes in the electronic properties of SWCNT systems after the attachment of adsorbed species to the tube surface. According to the calculated results,the single-walled carbon nanotubes are expected to be a potential efficient adsorbent for the adsorption of folic acid drug and also can be used as a suitable drug delivery vehicle within biological systems.

Adsorptive removal of tetracycline from water using Fe(Ⅲ)-functionalized carbonized humic acid

Humic acid(HA)was carbonized at 300,400 and 500℃ and then functionalized with 1 wt%–12 wt%Fe(Ⅲ)respectively[CHA300/400/500-Fe(Ⅲ)].Adsorption of such Fe(III)-functionalized carbonized HA as adsorbents to aqueous tetracycline(TC:25 mg·L^-1)was studied.The adsorption equilibrium time for CHA400-Fe(Ⅲ)to TC was 6 h faster and the adsorption removal efficiency(Re)was two times higher than that of HA/CHA.The adsorption Reof CHA400-Fe(Ⅲ)loaded 10%iron[CHA400-(10%)Fe(Ⅲ)]to TC could reach 99.8%at 8 h and still kept80.6%after 8 cycles.The adsorption kinetics were well fitted to the pseudo-second-order equation and the adsorption isotherms could be well delineated via Langmuir equations(R^2N 0.99),indicating that the homogeneous chemical adsorption of TC occurred on the adsorbents.The main adsorption mechanisms of TC were complexation Fe(III)and hydrophobic distribution.Electropositive and electronegative repulsion between TC and CHA400-(10%)Fe(Ⅲ)at lowly p H(2)and highly p H(8–10)respectively,leaded to the relatively low adsorption capacity and more notable influence of ion concentration.When the p H was between 4 and 8,TC mainly existed in neutral molecules(TCH2),so the influence of ion concentration was not obvious.The dynamic adsorption results showed that the CHA400-(10%)Fe(Ⅲ)could continuously treat about 2.4 L TC(27 mg·L^-1)wastewater with the effluent concentration as low as 0.068 mg·L^-1.Our study suggested a broad application prospect of a new,effective,lowcost and environment-friendly adsorbent CHA400-(10%)Fe(Ⅲ)for treatment of low-concentration TC polluted wastewater.

Ball-milling MoS_2/carbon black hybrid material for catalyzing hydrogen evolution reaction in acidic medium

Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS） and excellent electrical coupling to the underlving carbon network.

Cu(Ⅱ) Complex/Multiwall Carbon Nanotube Modified Electrode for the Determination of Ascorbic Acid

A sensitive and selective method for the determination of ascorbic acid（AA） using [Cu（phen）2]2＋/multiwalled carbon nanotubes modified glassy carbon electrode was developed. Electrochemical behavior and surface characteristics of the modified electrode were studied using scanning electrode microscopy（SEM）, electrochemical impedance spectroscopy（EIS） and cyclic voltammetry（CV）. The experimental results showed that the modified electrode enhanced the electrochemical response of AA and exhibited good analytical performance for AA determination from 10 to 1 042 ？mol/L with a low detection limit of 9.67μmol/L（S/N=3）. The modified electrode was also applied to the determination of AA in the Vitamin tablets and showed good recovery.

Studies on Zeolite Modified Electrode(Ⅰ)─Ascorbic Acid Sensor Based on Carbon Paste Electrode Containing Fe(Ⅲ)Y Zeolite

A new ascorbic acid sensor constituted of carbon paste and Fe(Ⅲ)Y zeolite was studied.The characters of the sensor such as linear range. potential window、apparen Michaelis constant、response time、stability and accuracy wee investigated. The experimental results indicate that the analytical performance of the sensor is satisfactory.

Single-Ni-atoms on nitrogenated humic acid based porous carbon for CO_(2) electroreduction

tWe proposed a facile synthesis of single-Ni-atom catalysts on low-cost porous carbon using a calcina-tion method at the temperatures of 850-1000°C,which were used for CO_(2) electrochemical reduction to CO.The porous carbon was prepared by carbonizing cheap and abundant humic acid.The structural characterizations of the as-synthesized catalysts and their electrocatalytic performances were analyzed.The results showed that the single-Ni-atom catalyst activated at 950°C showed an optimum catalytic performance,and it reached a CO Faradaic efficiency of 91.9% with a CO partial current density of 6.9 mAcm^(-2)at-0.9 V vs.reversible hydrogen electrode(RHE).Additionally,the CO Faradaic efficiency and current density of the optimum catalyst changed slightly after 8 h of continuous operation,suggesting that it possessed an excellent stability.The structure-activity relations indicate that the variation in the CO_(2) electroche-mical reduction performance for the as-synthesized catalysts is ascribed to the combined effects of the increase in the content of pyrrolic N,the evaporation of Ni and N,the decrease in pore volume,and the change in graphitization degree.

A Computational Study on the Mechanism for the K_2CO_3-catalyzed Reaction of Carbon Dioxide and 1-Chlo-2-propanol

The microcosmic reaction mechanism of K2CO3-catalyzed 1-chlo-2-propanol and carbon dioxide has been investigated by density functional theory（DFT） at the GGA/PW91/DNP level.We optimize the geometric configurations of reactants,intermediates,transition states,and products.The energy analysis calculation approves the authenticity of intermediates and transition states.According to our calculations,four feasible reaction pathways are found.The main pathway of the reaction is ReA → IMA1 → TSA1 → IMA2 → IMA5 → TSA5 → P.Besides,we also in-vestigate the reaction mechanism of 1-chlo-2-propanol and carbon dioxide without K2CO3-catalyzation by the same theory and level.The computational results indicate that the activation barrier with K2CO3-catalyzed is smaller than the activation barrier without K2CO3-catalyzed.That is to say,K2CO3 can promote the reaction to give the product in a high yield,which is in agreement with the experimental results.

Responses of soil nitrogen, phosphorous and organic matter to vegetation succession on the Loess Plateau of China

Revegetation is a traditional practice widely used for soil protection. We evaluated the effect of natural revegetation succession on soil chemical properties and carbon fractions （particulate organic carbon （POC）, humus carbon （HS-C）, humic acid carbon （HA-C） and fulvic acid carbon （FA-C）） on the Loess Plateau of China. The vegetation types, in order from the shortest to the longest enclosure duration, were： （a） abandoned overgrazed grassland （AbG3; 3 years）; （b） Hierochloe odorata Beauv. （HiO7; 7 years）; （c） Thymus mongoficus Ronnm （ThM15; 15 years）; （d） Artemisia sacrorum Ledeb （AtS25; 25 years）; （e） Stipa bungeana Trin Ledeb （StB36; 36 years） and （f） Stipa grandis P. Smirn （StG56; 56 years）. The results showed that the concentrations of soil organic carbon, total nitrogen and available phosphorus increased with the increase of restoration time except for ThM15. The concen- tration of NH4-N increased in the medium stage （for ThM15 and AtS25） and decreased in the later stage （for StB36 and StG56） of vegetation restoration. However, NO3-N concentration significantly increased in the later stage （for StB36 and StG56）. Carbon fractions had a similar increasing trend during natural vegetation restoration. The con- centrations of POC, HS-C, FA-C and HA-C accounted for 24.5%-49.1%, 10.6%-15.2%, 5.8%-9.1% and 4.6%-6.1% of total carbon, respectively. For AbG3, the relative changes of POC, HS-C and FA-C were significantly higher than that of total carbon during the process of revegetation restoration. The higher relative increases in POC, HS-C and FA-C confirmed that soil carbon induced by vegetation restoration was sequestrated by higher physical and chemical protection. The increases of soil C fractions could also result in higher ecological function in semiarid grassland ecosystems.

Experimental and modelling study of the solubility of CO_2 in various CaCl_2 solutions at different temperatures and pressures

Study of the thermodynamic behaviour of CaCl2-H2O-CO2 systems is important in different scientific areas in the chemical and petroleum engineering fields. For example, a system including salt- H20-CO2 is a common system in CO2 geological storage. During carbonate matrix acidizing, this mixture also appears as the spent acid. Hence, study of the behaviour of this system and the solubility of CO2 in CaCl2 brine in different thermodynamic conditions is critical. In this study, CO2 solubility in 0, 1.90 and 4.80 mol/L CaCl2 solutions at 328.15 to 375.15 K and 68.9 to 206.8 bar were measured. These values are normal for oil reservoirs. A popular thermodynamic model is available in the literature for estimating the CO2 solubility in pure water and NaC1 solutions. In this paper, the available model was modified by experimental work to be applicable for CaCl2 as well. Based on the measured data, the component interaction parameters in the base model were adjusted for a CaCl2-H2O-CO2 system. The developed model could predict CO2 solubility in different conditions with remarkable accuracy, particularly for high concentration solutions and at high pressures. This improvement is up to 65% better than in the base model. This model can be used in Darcy scale models for predicting wormhole propagation during carbonate matrix acidizing.