Acid-rock reaction kinetics in a two-scale model based on reaction order correction

The reaction order plays a crucial role in evaluating the response rate of acid-rock.However,the conventional two-scale model typically assumes that the reaction order is constant as one,which can lead to significant deviations from reality.To address this issue,this study proposes a novel multi-order dynamic model for acid-rock reaction by combining rotating disk experimental data with theoretical derivation.Through numerical simulations,this model allows for the investigation of the impact of acidification conditions on different orders of reaction,thereby providing valuable insights for on-site construction.The analysis reveals that higher response orders require higher optimal acid liquid flow rates,and lower optimal H+diffusion coefficients,and demonstrate no significant correlation with acid concentration.Consequently,it is recommended to increase the displacement and use high-viscosity acid for reservoirs with high calcite content,while reducing the displacement and using low-viscosity acid for reservoirs with high dolomite content.

Boric Acid-Assisted Pyrolysis for High-Loading Single-Atom Catalysts to Boost Oxygen Reduction Reaction in Zn-Air Batteries

The emerging of single-atom catalysts(SACs)offers a great opportunity for the development of advanced energy storage and conversion devices due to their excellent activity and durability,but the actual mass production of high-loading SACs is still challenging.Herein,a facile and green boron acid(H_(3)BO_(3))-assisted pyrolysis strategy is put forward to synthesize SACs by only using chitosan,cobalt salt and H_(3)BO_(3)as precursor,and the effect of H_(3)BO_(3)is deeply investigated.The results show that molten boron oxide derived from H_(3)BO_(3)as ideal high-temperature carbonization media and blocking media play important role in the synthesis process.As a result,the acquired Co/N/B tri-doped porous carbon framework(Co-N-B-C)not only presents hierarchical porous structure,large specific surface area and abundant carbon edges but also possesses high-loading single Co atom(4.2 wt.%),thus giving rise to outstanding oxygen catalytic performance.When employed as a catalyst for air cathode in Zn-air batteries,the resultant Co-N-B-C catalyst shows remarkable power density and long-term stability.Clearly,our work gains deep insight into the role of H_(3)BO_(3)and provides a new avenue to synthesis of high-performance SACs.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

A cleaner production strategy for acid mine drainage prevention of waste rock:A porphyry copper case

An in-process technology approach is proposed to identify the source of acid mine drainage(AMD)generation and prevent its formation in a porphyry copper waste rock(WR).Adopting actions before stockpiling the WR enables the establishment of potential contaminants and predicts the more convenient method for AMD prevention.A WR sample was separated into size fractions,and the WR’s net acidgenerating potential was quantified using chemical and mineralogical characterization.The diameter of physical locking of sulfides(DPLS)was determined,and the fractions below the DPLS were desulfurized using flotation.Finally,the WR fractions and tailing from the flotation test were submitted to acid-base accounting and weathering tests to evaluate their acid-generating potential.Results show that the WR’s main sulfide mineral is pyrite,and the DPLS was defined as 850μm.A sulfide recovery of 91%was achieved using a combination of HydroFloat^(®)and Denver cells for a size fraction lower than DPLS.No grinding was conducted.The results show that size fractions greater than DPLS and the desulfurized WR are unlikely to produce AMD.The outcomes show that in-processing technology can be a more proactive approach and an effective tool for avoiding AMD in a porphyry copper WR.

Steam reforming of acetic acid over Ni/biochar of low metal-loading:Involvement of biochar in tailoring reaction intermediates renders superior catalytic performance

Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming,which could influence the formation of reaction intermediates and modify catalytic behaviors.Herein,the Ni/biochar as well as two comparative catalysts,Ni/Al_(2)O_(3) and Ni/SiO_(2),with low nickel loading(2%(mass))was conducted to probe involvement of the varied carriers in the steam reforming.The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO_(2) and Ni/Al_(2)O_(3),as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C,resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance.In converse,strong adsorption of aliphatic intermediates over Ni/Al_(2)O_(3) and Ni/SiO_(2) induced serious coking with polymeric coke as the main type(21.5%and 32.1%,respectively),which was significantly higher than that over Ni/biochar(3.9%).The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity.The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam,which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al_(2)O_(3) and Ni/SiO_(2) catalysts.

Insights into kinetics and reaction mechanism of acid-catalyzed transesterification synthesis of diethyl oxalate

The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated.The effects of different factors(e.g.,acidity,electron accepting capacity,cations type and crystalline water)on the catalytic activity of acidic catalysts were investigated respectively.It was proposed and confirmed that the transesterification reaction catalyzed by a Lewis acid(FeCl3)and a Bronsted acid(H2SO4)follows a first-order kinetic reaction process.In addition,the Lewis acid-catalyzed transesterification processes with different ester structures were used to further explore and understand the speculated reaction mechanism.This work enriches the theoretical understanding of acid-catalyzed transesterification reactions and is of great significance for the development of highly active catalysts for diethyl oxalate synthesis,diminishing the industrial production cost of diethyl oxalate,and developing downstream bulk or high-value-added industrial products.

Effects of Oleanolic Acid on the Immune Complex Allergic Reaction and Inflammation

When oleanolic acid (OA) was administered ig before and after sensitization on d 1 to d 5 and d 11 to d 17,it had no apparent effect on Arthus reaction.When it was administered at 48,24 and 1 h before challenge,however,Arthus reaction was significantly inhibited.OA showed markedly suppressive effects on reversible passive Arthus reaction and leukocyte migratory response.It could significantly stabilize erythrocyte membrane,inhibit the swelling of the rat's hind paw induced by in- jecting mycostatin,reduce the acid phosphatase content in the inflammatory exudate,suppress the syn- thesis or release of PGE,histamine,LTB4 and kinin,and the phlogistic action of PGE_2,histamine,5- HT and kinin.In addition,it could decrease the content of malonyldialdehyde (MDA) in hepatic tissue of alcohol-intoxicated mice,and increase the activity of catalase (CAT) in hepatic tissue of mice.OA had no apparent effect on the activity of super-oxide dismutase (SOD) in rat serum,on the content of immune complex in serum of rat with Arthus reaction,on the phagocytosis of monocytc-macrophage system,on the clearance of enzyme-containing immune complex by macrophage,or on the activity of total complement.

Hydrothermal synthesis of titanium-supported nanoporous palladium-copper electrocatalysts for formic acid oxidation and oxygen reduction reaction

Nanoporous Pd and binary Pd-Cu particles were prepared by a hydrothermal method using ethylene glycol as a reduction agent and they were directly immobilized on Ti substrates named as Ti-supported Pd-based catalysts. Their electrocatalytic activity for formic acid oxidation and oxygen reduction reaction （ORR） in alkaline media was examined by voltammetric techniques. Among the as-prepared catalysts, nanoPdslCu19/Ti catalyst presents the highest current density of 39.8 mA/cm2 at -0.5 V or 66.4 mA/cm2 at -0.3 V for formic acid oxidation. The onset potential of ORR on the nanoPdslCU19/Ti catalyst presents an about 70 mV positive shift compared to that on the nanoPd/Ti, and the current density of ORR at -0.3 V is 2.12 mA/cm2, which is 3.7 times larger than that on the nanoPd/Ti.

益母草碱调节RhoA/ROCK信号通路对乙型肝炎大鼠的治疗作用

【目的】观察益母草碱对乙型肝炎大鼠的治疗作用及机制。【方法】将60只大鼠随机分为6组,即正常组,模型组,益母草碱低、中、高剂量组,益母草碱高剂量+溶血磷脂酸(LPA)组。除正常组外,其余各组大鼠构建乙型肝炎病毒(HBV)感染模型。造模成功后,各组对应干预。干预结束后,采用酶联免疫吸附分析(ELISA)检测血清乙型肝炎e抗原(HBeAg)、乙型肝炎表面抗原(HBsAg)及炎症因子白细胞介素(IL)-10、IL-6、肿瘤坏死因子α(TNF-α)水平,自动分析仪测定血清丙氨酸氨基转移酶(ALT)、天门冬氨酸氨基转移酶(AST)水平,实时定量聚合酶链反应(RT-qPCR)法检测肝组织HBV DNA水平,苏木素-伊红(HE)染色法观察肝组织病理变化,免疫组织化学法检测肝组织乙型肝炎核心抗原(HBcAg)表达水平,Western Blot法检测肝组织Ras同源基因家族成员A(RhoA)、Rho相关卷曲螺旋蛋白激酶(ROCK)1、ROCK2表达水平。【结果】与正常组比较,模型组大鼠肝小叶中心坏死,肝细胞水肿、变性,HBsAg、HBeAg、HBV DNA水平,HBcAg阳性细胞数,ALT、AST水平,IL-6、TNF-α、IL-10含量,RhoA、ROCK1、ROCK2表达水平均显著升高(均P<0.05);与模型组比较,益母草碱低、中、高剂量组大鼠肝损伤程度降低,肝细胞变性减轻,HBsAg、HBeAg、HBV DNA水平,HBcAg阳性细胞数,ALT、AST水平,IL-6、TNF-α含量,RhoA、ROCK1、ROCK2表达水平均显著降低,IL-10含量升高,差异均有统计学意义(P<0.05);与益母草碱高剂量组比较,益母草碱高剂量+LPA组肝损伤程度加重,HBsAg、HBeAg、HBV DNA水平,HBcAg阳性细胞数,ALT、AST水平,IL-6、TNF-α含量,RhoA、ROCK1、ROCK2表达水平升高,IL-10含量降低,差异均有统计学意义(P<0.05)。【结论】益母草碱能减轻乙型肝炎大鼠肝组织损伤,改善肝功能,减少炎症反应,其机制与抑制RhoA/ROCK通路有关。

Phosphorus release from phosphate rock and iron phosphate by low-molecular-weight organic acids

Low-molecular-weight(LMW) organic acids widely exist in soils, particularly in the rhizosphere. A series of batch experiments were carried out to investigate the phosphorus release from rock phosphate and iron phosphate by low-molecular-weight organic acids. Results showed that citric acid had the highest capacity to solubilize P from both rock and iron phosphate. P solubilization from rock phosphate and iron phosphate resulted in net proton consumption. P release from rock phosphate was positively correlated with the p K _a values. P release from iron phosphate was positively correlated with Fe-organic acid stability constants except for aromatic acids, but was not correlated with p K _a. Increase in the concentrations of organic acids enhanced P solubilization from both rock and iron phosphate almost linearly. Addition of phenolic compounds further increased the P release from iron phosphate. Initial solution pH had much more substantial effect on P release from rock phosphate than from iron phosphate.

The effects of temperature and acid number of crude oil on the wettability of acid volcanic reservoir rock from the Hailar Oilfi eld

Wettability of acid volcanic reservoir rock from the Hailar Oilfield, China, was studied with crude oils of different acid numbers generated from an original crude oil with an acid number of 3.05 mg KOH/g. The modifed oils and their resultant acid numbers were： A （2.09 mg KOH/g）, B （0.75 mg KOH/g）, C （0.47 mg KOH/g）, D （0.30 mg KOH/g）, and E （0.18 mg KOH/g）. Contact angles and improved Amott water indexes were measured to study the effects of temperature and acid number on the wettability of the acid volcanic reservoir rock. Experimental results indicated that the wettability was not sensitive to variation in temperature when using the same oil, but the acid number of the crude oil was a key factor in changing the wettability of the rock. The Amott water index, Iw was an exponential function of the acid number, and the Amott water index increased as the acid number decreased （i.e. Amott water index exponentially decreased with the acid number increase）. The Iw value of the core saturated with oil A, with an acid number of 2.09 mg KOH/g, ranged from 0.06 to 0.11, which indicated low water wetness. If the acid number of the oil decreased to 0.18 mg KOH/g, the Iw value increased to 0.95, which indicated strong water wetness. The contact angle decreased from 80~ to 35~ when the aid number decreased from 0.75 to 0.18 mg KOH/g, indicating a change towards more water wet conditions. The oil recovery by spontaneous imbibition of water also increased as the acid number of the oil decreased. As an example, at 80 ~C, the recovery of Oil A with an acid number of 2.09 mg KOH/g was only 7.6%, while Oil E with an acid number of 0.18 mg KOH/g produced 56.4%, i.e. an increase of 48.8%.

Steam reforming of acetic acid over Ni-Ba/Al2O3 catalysts:Impacts of barium addition on coking behaviors and formation of reaction intermediates

The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).

Ligand assisted copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines

Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.

Science Letters:Evaluation of a kinetic uricase method for serum uric acid assay by predicting background absorbance of uricase reaction solution with an integrated method

A patented kinetic uricase method was evaluated for serum uric acid assay. Initial absorbance of the reaction mixture before uricase action （A0） was obtained by correcting the absorbance at 293 nm measured before the addition of uricase solution, and background absorbance （Ab） was predicted by an integrated method. Uric acid concentration in reaction solution was calculated from AA, the difference between A0 and Ab, using the absorptivity preset for uric acid. This kinetic uricase method exhibited CV〈4.3% and recovery of 100%. Lipids, bilirubin, hemoglobin, ascorbic acid, reduced glutathione and xanthine 〈0.32 mmol/L in serum had no significant effects. △A linearly responded to 1.2 to 37.5 μmol/L uric acid in reaction solution containing 15 μl serum. The slope of linear response was consistent with the absorptivity preset for uric acid while the intercept was consistent with that for serum alone. Uric acid concentrations in clinic sera by different uricase methods positively correlated to each other. By Bland-Altman analysis, this kinetic uricase method accorded with that by quantifying the total change of UV absorbance on the completion of uricase reaction. These results demonstrated that this kinetic uricase method is reliable for serum uric acid assay with enhanced resistance to both xanthine and other common errors, wider range of linear response and much lower cost.

Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller（BET）surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.

Synthesis of a magnetic-separated chitosan-palladium complex and its catalytic activity in the reaction of acrylic acid with iodobenzene

A magnetic-separated catalyst of chitosan-palladium complex （Fe3O-CS-Pd） based on chitosan coated Fe3O4 microspheres was prepared by the ＂bottom-up＂ approach. The catalytic behavior of the catalyst in the cross coupling reaction of acrylic acid （AA） with iodobenzene （ArI） was investigated. Compared with the traditional homogeneous palladium catalysts, the catalyst was easily separated and reused.

N/S co-doped 3D carbon framework prepared by a facile morphology-controlled solid-state pyrolysis method for oxygen reduction reaction in both acidic and alkaline media

Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.

Theoretical study on the synthesis reaction mechanism of trichlorogermyl crylic acid

The synthesis reaction of trichlorogermyl crylic acid has been studied systematically by using quantum chemistry methods for the first time.Geometries of reactants,transition states,and products have been optimized,respectively at the B3LYP/6-311G（d,p） level.Vibrational frequencies,IR intensities and relative energies for various stationary points have been determined.The reaction pathways are identified by intrinsic reaction coordinate（IRC）calculations.Theoretical analysis provided conclusive evidence that the process is completed through five pathways of addition reaction of double bond,and the transition states are found to be four- membered ring compounds.Solvent effects are taken into account with the PCM model at the same level.This preliminary study shows that the complex formation is favored by the use of polar solvent.

Facile Aldol Reaction Between Unmodified Aldehydes and Ketones in Bronsted Acid Ionic Liquids

A series of condensation reactions of unmodified ketones and aromatic aldehydes to prepare α,β-unsaturated carbonyl compounds by means of Aldol reactions in Bronsted acid ionic liquids（BAILs）was explored.1-Butyl-3-methylimidazolium hydrogen sulphate（BMImHSO4）acting as an effective media and catalyst in aldol reactions was compared with other BAILs,with the advantages of high conversion and selectivity.The product was easily isolated and the left ionic liquid can be readily recovered and reused at least 3 times with almost the same efficiency.The scope and limitation of the present method were explored and the possible catalytic mechanism was speculated.

Preparation of Polystyrenylphosphonous Acid of Low Polymerization Degree and Influence of Initiators upon the Free Radical Reaction Mechanism

The polystyrenylphosphonous acid (PSPA) of low polymerization degree was prepared with one step reaction. The reaction mechanism was changed with different initiators. For the reaction with AIBN or BPO as the initiator, there are 2 or 3 series of radical reaction chains and 5 or 9 series of polystyrenyl products. The main products are PSPA without or with the fragment of the initiator H[CH(C6H5)-CH2]n-PO2H2 and C6H5CO2-[CH2CH (C6H5)]n-PO2H2 respectively.