Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Molybdosphoric Acid Mixed with Titania Used as a Catalyst to Synthesize Diphenyl Carbonate via Transesterification of Dimethyl Carbonate and Phenol

The 12-molybdosphoric acid mixed with titania （MPA-TiO2） was found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate （DPC） via transesterification of dimethyl carbonate （DMC） and phenol. The X-ray diffraction （XRD） and infrared （IR） techniques were employed to characterize the prepared catalysts. The effect of the weight ratio of the 12-molybdosphoric acid to titania on the transesterification was investigated. A 13.1% yield of DPC and an 11.6% yield of methyl phenyl carbonate （MPC） were obtained over MPA-TiO2 with the weight ratio of MPA to TiO2 as 5：1.

Absorption Characteristics of Novel Compound Calcium Carbonate Granules:Effects of Gastric Acid Deficiency and Exogenous Weak Acids

Calcium carbonates are commonly administered as supplements for conditions of calcium deficiency.We report here pharmacokinetic characteristics of a novel formulation,calcium carbonate compound granules(CCCGs).forming complexes of calcium carbonate and calcium citrate in water.CCCGs were compared to a kind of commonly?used calcium carbonate preparation(CC)in the market in 5-week-old mice that had been treated with omeprazole,to suppress gastric acid secretion,and in untreated control mice.The results showed that:(1)CCCGs had better water solubility than CC in vitro;(2)In control mice,calcium absorption rates after CCCGs administration were comparable to those after CC administration;(3)Inhibition of gastric acid secretion did not affect calcium absorption after CCCGs,but moderately decreased it after CC;(4)The presence of phytic acid or tannin did not affect calcium absorption rates after CCCGs but did for CC;and(5)In nonnal mice,CCCGs did not inhibit gastric emptying and intestinal propulsion,and did not alter the gastrointestinal honnones.The results suggest that CCCGs may be therapeutically advantageous over more commonly used calcium supplement formulations,particularly for adolescents,because of their stable calcium absorption characteristics and their relatively favorable adverse effect profile.

Biomediated Precipitation of Calcium Carbonate in a Slightly Acidic Hot Spring,Yunnan Province

A slightly acidic hot spring named ＂Female Tower＂（t=73.5°C, pH=6.64） is located in the Jifei Geothermal Field, Yunnan Province, southwestern China. The precipitates in the hot spring are composed of large amounts of calcite, aragonite and sulfur. Scanning electron microscopy（SEM） analyses reveal that the microbial mats were formed from various coccoid or rod-shaped filamentous microbes. Transmission electron microscopy（TEM） shows that the intracellular sulfur granules are commonly associated with these microbes. A culture-independent molecular phylogenetic analysis demonstrates that the majority of the bacteria in the spring are sulfur-oxidizing bacteria. In the spring water, H2S concentration is up to 60 ppm, while SO4-（2-） concentration is only about 10 ppm. We speculate that H2S might derive from sulfur-oxidizing bacteria in this hot spring water, leading to the intracellular formation of sulfur granules. Meanwhile, this reaction increased the p H in the micronscale microdomains, which fosters the precipitation of calcium carbonate in the microbial mats. The results of this study indicate that the sulfur-oxidizing bacteria might play an important role in calcium carbonate precipitation in slightly acidic hot spring environments.

Determination of Carbon and Nitrogen Isotope Fractions in Tartaric Acid, Oxalic Acid, Glucose and Fructose—National Center of High Technologies of Georgia

Tartaric acid, oxalic acid, glucose, and fructose are highly important compounds. A comprehensive study of these substances is fascinating from a scientific perspective. They are key components found in wine, vegetables, and fruits. Understanding the isotopic compositions in organic compounds is crucial for comprehending various biochemical processes and the nature of substances present in different natural products. Tartaric acid, oxalic acid, glucose, and fructose are widely distributed compounds, including in vegetables and fruits. Tartaric acid plays a significant role in determining the quality and taste properties of wine, while oxalic acid is also prevalent but holds great interest for further research, especially in terms of carbon isotopic composition. We can unveil the mechanisms of processes that were previously impossible to study. Glucose and fructose are the most common monosaccharides in the hexose group, and both are found in fruits, with sweeter fruits containing higher amounts of these substances. In addition to fruits, wheat, barley, rye, onions, garlic, lentils, peppers, dried fruits, beans, broccoli, cabbage, tomatoes, and other foods are also rich sources of fructose and glucose. To determine the mass fraction of the carbon-13 isotope in these compounds, it is important to study their changes during natural synthesis. These compounds can be modified with a carbon center. According to the existing isotopic analysis method, these compounds are converted into carbon oxide or dioxide [1]. At this point, the average carbon content in the given compound is determined, but information about isotope-modified centers is lost. Dilution may occur through the transfer of other carbon-containing organic compounds in the sample or by dilution with natural carbon or carbon dioxide during the transfer process. This article discusses the possibility of carbon-13 isotope propagation directly in these compounds, both completely modified and modified with individual carbon centers. The literature provides information on determining carbon-13 substance in organic compounds, both with a general approach and for individual compounds [2] [3].

Mepiquat chloride increases the Cry1Ac protein content of Bt cotton under high temperature and drought stress by regulating carbon and amino acid metabolism

The effects of mepiquat chloride(DPC)on the Cry1Ac protein content in Bacillus thuringiensis(Bt)cotton boll shells under high temperature and drought stress were investigated to provide a theoretical reference for Bt cotton breeding and high-yield and-efficiency cotton cultivation.This study was conducted using Bt cotton cultivar‘Sikang 3'during the 2020 and 2021 growing seasons at Yangzhou University Farm,Yangzhou,Jiangsu Province,China.Potted cotton plants were exposed to high temperature and drought stress,and sprayed with either 20 mg L^(-1)DPC or water(CK).Seven days after treatment,the Cry1Ac protein content,α-ketoglutarate content,pyruvic acid content,glutamate synthase activity,glutamic oxaloacetic transaminase activity,soluble protein content,and amino acid content were measured,and transcriptome sequencing was performed.DESeq was used for differential gene analysis.Under the DPC treatment,the Cry1Ac protein content increased by 4.7-11.9% compared to CK.Theα-ketoglutarate content,pyruvic acid content,glutamate synthase activity,glutamic oxaloacetic transaminase activity,soluble protein content,and amino acid content all increased.Transcriptome analysis revealed 7,542 upregulated genes and 10,449 downregulated genes for DPC vs.CK.Gene ontology(GO)and Kyoto Encyclopedia of Gene and Genomes(KEGG)analyses showed that the differentially expressed genes were mainly involved in biological processes,such as carbon and amino acid metabolism.For example,genes encoding 6-phosphofructokinase,pyruvate kinase,glutamic pyruvate transaminase,pyruvate dehydrogenase,citrate synthase,isocitrate dehydrogenase,2-oxoglutarate dehydrogenase,glutamate synthase,1-pyrroline-5-carboxylate dehydrogenase,glutamic oxaloacetic transaminase,amino-acid N-acetyltransferase,and acetylornithine deacetylase were all significantly upregulated.The DPC treatment increased pyruvate,α-ketoglutarate,and oxaloacetate by increasing the operational rate of the glycolytic pathway of the citric acid cycle.It also significantly upregulated the genes encoding glutamate synthase,pyrrolidine-5-carboxylic acid dehydrogenase,glutamate oxaloacetate transaminase,and N-acetylglutamate synthetase,while it downregulated the genes encoding glutamine synthetase.Therefore,the synthesis of aspartic acid,glutamic acid,pyruvate,and arginine increased after treatment with DPC,and the Cry1Ac protein content was increased by regulating carbon and amino acid metabolism.

Performance evaluation of microemulsion acid for integrated acid fracturing in Middle Eastern carbonate reservoirs

Considering the characteristics of carbonate reservoirs in the Middle East,a low-viscosity microemulsion acid that can be prepared on site and has an appropriate retardation ability was developed.It was compared with four conventional acid systems(hydrochloric acid,gelled acid,emulsified acid and surfactant acid)through experiments of rotating disk,multistage acid fracturing and core flooding with CT scanning.The micro-etching characteristics and conductivity of fracture surfaces were clarified,and the variation of saturation field during water invasion and flowback of spent acid and the recovery of oil phase relative permeability were quantitatively evaluated.The study shows that the addition of negatively charged agent to the oil core of microemulsion acid can enhance its adsorption capacity on the limestone surface and significantly reduce the H+mass transfer rate.Moreover,the negatively charged oil core is immiscible with the Ca^(2+)salt,so that the microemulsion acid can keep an overall structure not be damaged by Ca^(2+)salt generated during reaction,with adjustable adsorption capacity and stable microemulsion structure.With high vertical permeability along the fracture walls,the microemulsion acid can penetrate into deep fracture wall to form network etching,which helps greatly improve the permeability of reservoirs around the fractures and keep a high conductivity under a high closure pressure.The spent microemulsion acid is miscible with crude oil to form microemulsion.The microemulsion,oil and water are in a nearly miscible state,with basically no water block and low flowback resistance,the flowback of spent acid and the relative permeability of oil are recovered to a high degree.

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.

Carbamate synthesis from amines and dialkyl carbonate over inexpensive and clean acidic catalyst—Sulfamic acid

Sulfamic acid has been proved to be the most efficient and recyclable catalyst in carbamate synthesis from alkylamine and dialkyl carbonate.High selectivity,cost-efficiency and simple product separation were the advantageous features obtained in this process.Sulfamic acid could be reused several times and keep its initial activity in the recycle runs.In addition,sulfamic acid has also exhibited the potential catalytic ability for alkylation of aromatic amines.

PROPERTIES AND SYNTHESIS OF NEW SUPPORTS FOR IMMOBILIZATION OF ENZYMES BY COPOLYMERIZATION OF VINYLENE CARBONATE AND METHACRYLIC ACID

Methacrylic acid first was neutralized with an aqueous solution of NaOH to pH = 6.0 similar to 7.0, vinylene carbonate (VCA) was added to the solution, then monomers were copolymerized in paraffin oil by means of reverse-phase suspension polymerization and hydrophilic copolymeric supports were prepared. The properties of the supports were determined using trypsin and results show that the amount of enzymes coupled to the supports and the specific activity of immobilized trypsin are related to the content of VCA structure units, reaction time and concentration of enzyme solution, etc.

Electrokinetics Technology to Improve Acidizing of Carbonate Reservoir Rocks

A novel technology (electrokinetics) is proposed to improve acidizing operations, i.e., increase the penetration distance. The acid dissolves the carbonates (limestones/dolomites), enlarging the pores and increasing the width of pre-existing fractures. This gives rise to an increase in permeability. The principal acid commonly used is hydrochloric (HCl), which is pumped through tubing. Aqueous solutions of hydrochloric acid (usually 15%) are pumped into the carbonate formations to enlarge the pores and pre-existing fractures. Without application of D.C. current, the penetration distance is usually very short, especially in tight rocks. However, the penetration distance of acid is very short. By applying D.C. current, one can drive the acid for long distances into the formation being acidized.

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.

Development of Acidizing Techniques for Low－permeability Carbonate Reservoirs

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Formation of fractures in carbonate rocks by pad acid fracturing with different states of carbon dioxide

Carbonate outcrops were taken from Ma 51 sub-member in the Lower Paleozoic in the Yan’an gas field to conduct true tri-axial hydraulic fracturing experiments with water, liquid CO_(2) and supercritical CO_(2). CT scan was applied to analyze initiation and propagation laws of hydraulic fractures in carbonate rocks. The experiments show that supercritical CO_(2) has low viscosity, strong diffusivity and large filtration during fracturing, which is more liable to increase pore pressure of rocks around wellbore and decrease breakdown pressure of carbonate rocks. However, it would cost much more volume of supercritical CO_(2) than water to fracture rocks since the former increases the wellbore pressure more slowly during fracturing. For carbonate rocks with few natural fractures, tensional fractures are generated by fracturing with water and liquid CO_(2), and these fractures propagate along the maximum horizontal principal stress direction;while fracturing with supercritical CO_(2) can form shear fractures, whose morphology is rarely influenced by horizontal stress difference. Besides, the angle between propagation direction of these shear fractures near the wellbore and the maximum horizontal principal stress is 45°, and the fractures would gradually turn to propagate along the maximum horizontal principal stress when they extend to a certain distance from the wellbore, leading to an increase of fracture tortuosity compared with the former. For carbonate rocks with well-developed natural fractures, fracturing with fresh water is conducive to connect natural fractures with low approaching angle and form stepped fractures with simple morphology. The key to forming complex fractures after fracturing carbonate rocks is to connect the natural fractures with high approaching angle. It is easier for liquid CO_(2) with low viscosity to realize such connection. Multi-directional fractures with relatively complex morphology would be formed after fracturing with liquid CO_(2).

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.

Selective oxidation of glycerol to lactic acid over activated carbon supported Pt catalyst in alkaline solution

Pt/activated carbon （Pt/AC） catalyst combined with base works efficiently for lactic acid production from glycerol under mild conditions. Base type （LiOH, NaOH, KOH, or Ba（OH）2） and base/glycerol molar ratio significantly affected the catalytic performance. The corresponding lactic acid selectivity was in the order of LiOH〉NaOH〉KOH〉Ba（OH）2. An increase in LiOH/glycerol molar ratio ele‐vated the glycerol conversion and lactic acid selectivity to some degree, but excess LiOH inhibited the transformation of glycerol to lactic acid. In the presence of Pt/AC catalyst, the maximum selec‐tivity of lactic acid was 69.3% at a glycerol conversion of 100% after 6 h at 90 °C, with a Li‐OH/glycerol molar ratio of 1.5. The Pt/AC catalyst was recycled five times and was found to exhibit slightly decreased glycerol conversion and stable lactic acid selectivity. In addition, the experimental results indicated that reaction intermediate dihydroxyacetone was more favorable as the starting reagent for lactic acid formation than glyceraldehyde. However, the Pt/AC catalyst had adverse effects on the intermediate transformation to lactic acid, because it favored the catalytic oxidation of them to glyceric acid.

Photocatalytic activity and kinetics for acid yellow degradation over surface composites of TiO_2-coated activated carbon under different photocatalytic conditions

TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to estimate activity of catalysts and determine the kinetics. And the effects of parameters including the initial concentration of AY, light intensity and TiO2 content in catalysts were examined. The results indicate that TAs has a higher efficiency in decomposition of AY than P25, pure TiO2 particles as well as the mixture of TiO2 powder and active carbon. The photocatalytic degradation rate is found to follow the pseudo-first order kinetics with respect to the AY concentration. The new kinetic model fairly resembles the classic Langmuir-Hinshelwood equation, and the rate constant is proportional to the square root of the light intensity in a wide range. However, its absorption performance depends on the surface areas of catalysts. The model fits quite well with the experimental data and elucidates phenomena about the effects of the TiO2 content in TAs on the degradation rate.

VOLTAMMETRIC BEHAVIOR OF ASCORBIC ACID AT α-CYCLODEXTRIN INCORPORATED CARBON NANOTUBES-COATED ELECTRODE

制备了α -环糊精掺杂纳米碳管涂层电极并应用于抗坏血酸的电催化氧化 ,结果表明 ,氧化电位降低了 2 80mV ,电流响应明显增加。我们首次结合两种物质的特性 :纳米碳管的导电性及催化性能、α -环糊精的分子认知能力 ,对电极表面进行修饰。实验了抗坏血酸与α -环糊精超分子络合物的特性。差示脉冲技术用于定量分析抗坏血酸 ,线性范围为 2 .5× 10 -6～ 1.0× 10

Carbon dioxide capture by solvent absorption using amino acids: A review

The emission of large amounts of carbon dioxide is of major concern with regard to increasing the risk of climate change. Carbon capture, utilisation and storage (CCUS) has been proposed as an important pathway for slowing the rate of these emissions. Solvent absorption of CO_2 using amino acid solvents has drawn much attention over the last few years due to advantages including their ionic nature, low evaporation rate, low toxicity, high absorption rate and high biodegradation potential, compared to traditional amine solvents. In this review, recent progress on the absorption kinetics of amino acids is summarised, and the engineering potential of using amino acids as carbon capture solvents is discussed. The reaction orders between amino acids and carbon dioxide are typ- ically between 1 and 2. Glycine exhibits a reaction order of 1, whilst, by comparison, lysine, proline and sarcosine have the largest reaction constants with carbon dioxide which is much larger than that of the benchmark solvent monoethanolamine (MEA). Ionic strength, p H and cations such as sodium and potassium have been shown to be important factors influencing the reactivity of amino acids. Corrosivity and reactivity with impurities such as SOx and NOxare not considered to be significant problems for amino acids solvents. The precipitation of CO_2 loaded amino acid salts is thought to be a good pathway for increasing CO_2loading capacity and cutting desorption energy costs if well-controlled. It is recommended that more detailed research on amino acid degradation and overall process energy costs is conducted. Overall, amino acid solvents are recognised as promising potential solvents for car- bon dioxide capture.

Cytotoxicity effect assessment of acid purified carbon nanotubes modified with cetyltrimethyl ammonium bromide

The cytotoxicities of single-walled carbon nanotubes （SWNTs） and acid purified single-walled carbon nanotubes （SWNT-COOH） were investigated by spectroscopic analysis. Cell viability and cell apoptosis were applied to assessing the cytotoxicity of SWNT-COOH, cetyltrimethyl ammonium bromide （CTAB） and acid purified carbon nanotubes modified with cetyltrimethyl ammonium bromide （SWNT-COOH/CTAB）. The results indicate that SWNTs are more toxic than SWNT-COOH. Concentration and time-curve analyses indicate that cytotoxicity of SWNT-COOH/CTAB is more related to the toxicity of the surfactant CTAB. The cytotoxicity effect of CTAB and SWNT-COOH/CTAB is acceptable at low concentrations （0.5-25μg/mL）. The cytotoxicity observation suggests that SWNT-COOH/CTAB can safely applied to biomedical field at low concentrations （0.5-25μg/mL）.