Antibacterial powders of titanium dioxide/silver sulfate were produced by heat-treatment of the metatitanic acid, as precursor, into which the silver nitrate was added. The influences of heating temperature on the str...Antibacterial powders of titanium dioxide/silver sulfate were produced by heat-treatment of the metatitanic acid, as precursor, into which the silver nitrate was added. The influences of heating temperature on the structure and composition of the product were investigated through XRD and SEM. The results show that the powder is spherical in the phase of TiO2-Ag2SO4. The granularity of the particles increases from 10.7nm to 28.7nm with the temperature of heat-treatment increasing from 300℃ to 800℃. The antibacterial activity of the powder was judged in the way of the minimum inhibitory contents （MiCs）. When the content of silver sulfate is less than 2%, the photocatalysis of titanium dioxide and silver ions cooperate to kill bacteria. And the MiCs decrease and keep around 1.0×10 -41.5×10 -4 constantly with the increase of silver content. Furthermore, the MiCs decrease with the increase of temperature of heat-treatment when the temperature is lower than 500℃. But when the temperature is beyond 600℃ the MiCs increase quickly, which shows the inferior antibacterial performance.展开更多
Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
Photocatalytic carbon dioxide reduction reaction(CO_(2)RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated cata...Photocatalytic carbon dioxide reduction reaction(CO_(2)RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated catalysts for photocatalytic CO_(2)RR.Unfortunately,low CO_(2)adsorption ability and limited active sites of metal oxide and metal chalcogenide catalysts for CO_(2)RR make them less competitive compared to their industrial counterparts.Inspired by applications of porphyrin-based metal-organic framework(MOF)catalysts for hydrogen evolution and photodynamic therapy,the investigations of these porphyrin-based MOFs,including pristine and composite porphyrin-based MOFs in photocatalytic CO_(2)RR,have attracted significant attention in the last five years due to their excellent CO_(2)adsorption capacities,high porosity,high stability,exceptional optoelectronic properties,and multi-functionality.However,due to the difference in photocatalytic CO_(2)RR,several critical issues need to be addressed to achieve the rational design of advanced porphyrin-based MOF photocatalysts to improve activity,selectivity,and stability for CO_(2)RR.Here,we review recent developments in the field of porphyrin-based MOF CO_(2)RR photocatalysts,along with critical issues,challenges,and perspectives concerning porphyrin-based MOF catalysts for photocatalytic CO_(2)RR.展开更多
Artificial synthesis is an environment friendly photocatalytic strategy to converse carbon dioxide(CO_(2))into useful chemicals.However,water(H_(2)O)splitting,producing(hydrogen)H_(2) strongly,is always a competitive ...Artificial synthesis is an environment friendly photocatalytic strategy to converse carbon dioxide(CO_(2))into useful chemicals.However,water(H_(2)O)splitting,producing(hydrogen)H_(2) strongly,is always a competitive reaction to CO_(2) conversion.Therefore,proper cocatalysts are generally needed to enhance CO_(2) conversion but suppress H_(2) production.In this work,zinc/gallium(Zn/Ga)dual co-catalysts consisting of Zn0 and amorphous ZnGa_(2)O_(4) species were found to selectively produce carbon monoxide(CO)during the photocatalytic conversion of carbon dioxide(CO_(2))using water(H_(2)O)as an electron donor over photocatalysts such as NaTaO_(3),Ga_(2)O_(3),and ZnGa_(2)O_(4),and in the electrochemical reduction of CO_(2) over Zn0 electrodes.It is considered that there are two effects associated with the Zn/Ga dual co-catalysts:(1)a galvanic cell effect between Zn0 and amorphous ZnGa_(2)O_(4),and(2)a Z-scheme effect in NaTaO_(3)/Zn0/amorphous ZnGa_(2)O_(4).The coupling of these two effects favored the active and selective evolution of CO during the photocatalytic conversion of CO_(2) by H_(2)O.In the case of Ga_(2)O_(3) photocatalyst,480.8μmol/h of CO was produced with the presence of Zn/Ga dual cocatalysts.Moreover,the Zn/Ga dual cocatalysts universally worked in the electrochemical reduction of CO_(2).The partial current toward CO_(2) conversion was increased from 2.6 to 6.6 mA/cm,and the selectivity toward CO was promoted to from 46.4%to 74.2%.展开更多
As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and...As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and nickel(Ni)as sensitive metal cathode materials were evaluated for CO_(2) conversion in MES.The MES with Feelectrode as a promising electrode material demonstrated a superior CO_(2) reduction performance with a maximum acetate accumulation of 417.9±39.2 mg/L,which was 1.5 and 1.7 folds higher than that in the Ni-electrode and Cu-electrode groups,respectively.Furthermore,an outstanding electron recovery efficiency of 67.7%was shown in the Fe-electrode group.The electron transfer between electrode-suspended sludge was systematically cross-evaluated by the electrochemical behavior and extracellular polymeric substances.The Fe-electrode group had the highest electron transfer rate with 0.194 s-1(k_(app)),which was 17.6 and 21.5 times higher than that of the Cu-and Ni-electrode groups,respectively.Fe-electrode was beneficial for reducing electrochemical impedance between the electrode and suspended sludge.Additionally,redox substances in extracellular polymeric substances of the Fe-electrode group were increased,implying more favorable electron transport dynamics.Simultaneously,enrichments of functional bacteria Acetoanerobium and increased key enzymes involved in the carbonyl pathway of the Fe-electrode group were observed,which also promoted CO_(2) conversion in MES.This study provides a perspective on evaluating the promising sensitive metal electrode material for the process of CO_(2) valorization in MES and offers a reference for the subsequent electrode modification.展开更多
Colitis-associated colorectal cancer(CAC)is a major contributor to cancer-related mortality worldwide.Titanium dioxide(TiO_(2),E171),a widely used food additive,has been insufficiently studied regarding its effects on...Colitis-associated colorectal cancer(CAC)is a major contributor to cancer-related mortality worldwide.Titanium dioxide(TiO_(2),E171),a widely used food additive,has been insufficiently studied regarding its effects on macrophages within colon tumors during CAC development.In this study,CAC mouse models were used to investigate the biological impact of dietary E171 on macrophages in vivo,while lipopolysaccharide(LPS)-stimulated RAW264.7 macrophage cell lines were employed to elucidate the underlying mechanisms in vitro.We found that dietary E171 intake accelerated CAC development,exacerbated inflammatory responses and oxidative stress,and upregulated CAC-associated genes,including S100a8,S100a9,Lcn2,S100a11,Cxcl2,and interleukin-1α(Il-1α).E171 also increased the expression of S100A8,S100A9,NOD-like receptor family pyrin domain-containing 3(NLRP3),and gasdermin-D Nterminal(GSDMD-N)in macrophages within colon tumors.In inflammatory macrophages,E171 exposure enhanced cell viability,increased reactive oxygen species(ROS)levels,and elevated the expression and secretion of S100A8 and S100A9,consistent with in vivo histological observations.Furthermore,E171-induced secretion of S100A8 and S100A9 in macrophages was suppressed by specific inhibitors,including N-acetylcysteine(NAC,ROS inhibitor),MCC950(NLRP3 inhibitor),Z-YVAD-FMK(caspase 1 inhibitor),disulfiram(GSDMD inhibitor),and transfection of NLRP3 small interfering ribonucleic acid(siRNA).These results indicate that dietary E171 promotes CAC development by activating macrophages,with S100A8 and S100A9 serving as key mediators,and the NLRP3/caspase 1/GSDMD pathway acting as a critical mechanism.展开更多
An inorganic nanomaterials combination of Sm, Ag, and TiO2 was synthesized using supercritical fluid drying （SCFD） combined with solgel techniques. The structure, photocatalysis and bacteriostatic activity of the ma...An inorganic nanomaterials combination of Sm, Ag, and TiO2 was synthesized using supercritical fluid drying （SCFD） combined with solgel techniques. The structure, photocatalysis and bacteriostatic activity of the materials were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, X-ray photoelectron spectroscopy （XRPS）, photocatalytic performance, and antibacterial activity experiments. The XRD results showed that the average particle diameter of Sm/Ag/TiO2 was 14.62 nm and Ag and Sm ions were dispersed on the surface of TiO2 in a highly dispersed, amorphous form. The TEM image showed that the size of the particle was 12 nm using the scherer formula. The XPS result showed that the element Sm was doped and Ag was loaded inorganic nanomaterials successfully. Sm/Ag/TiO2 exhibited optimal photocatalytic properties at 600 oC, the photocatalytic optimal proportion of Sm/Ag/TiO2 was 2：2：100. When the molar ratio was 2：2：100, the bacteriostatic circle diameter was 16 mm for Staphylococcus aureus, the minimum bacteriostatic concentration was 200μg/mL for white beads coccus, and the minimum bactericidal concentration was 2×10^4μg/mL for white beads coccus. The SEM results showed that the antibacterial material attached to the candida albicans cell surface, cells appeared fold deformation. Therefore the inorganic nanomaterials Sm/Ag/TiO2 had high temperature resistance, good photocatalytic and antibacterial characteristics in visible light.展开更多
Solubility of the silver nitrate in the supercritical carbon dioxide containing ethanol and ethylene glycol as double cosolvents was measured under certain pressure and temperature range(10–25 MPa, 323.15–333.15 K)....Solubility of the silver nitrate in the supercritical carbon dioxide containing ethanol and ethylene glycol as double cosolvents was measured under certain pressure and temperature range(10–25 MPa, 323.15–333.15 K). The impact of the pressure and temperature on the solubility was also investigated. Based on the experiment data,a correlation model concerning solid's solubility in supercritical fluids was established by combining the solubility parameter with the thermodynamic equation when a binary interaction parameter and a mixed solvent solubility parameter were defined. Experiments show the solubility of AgNO_3 increases with the pressure at a certain temperature. However, the influence of temperature is related to a pressure defined as the turnover pressure(12.3 MPa). When the pressure is higher(or lower) than this turnover pressure, silver nitrate's solubility shows increasing(or decreasing) trend as the temperature rises. Satisfactory accuracy of our presented model was revealed by comparing experimental data with calculated results.展开更多
The adsorption behaviors of ciprofloxacin(CIP),a fluoroquinolone antibiotic,onto goethite(Gt)in the presence of silver and titanium dioxide nanoparticles(AgNPs and TiO_(2)NPs)were investigated.Results showed that CIP ...The adsorption behaviors of ciprofloxacin(CIP),a fluoroquinolone antibiotic,onto goethite(Gt)in the presence of silver and titanium dioxide nanoparticles(AgNPs and TiO_(2)NPs)were investigated.Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model.The presence of AgNPs or TiO_(2)NPs inhibited the adsorption of CIP by Gt.The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0.In contrast,in the presence of TiO_(2)NPs,CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0.The mechanisms of AgNPs and TiO_(2)NPs in inhibiting CIP adsorption by Gt were different,which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt,while TiO_(2)NPs could compete with Gt for CIP adsorption.Additionally,CIP was adsorbed by Gt or TiO_(2)NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring.These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.展开更多
Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the inte...Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the interface,further growth of hydrate due to the suction of water in the capillary system formed between the wall of the cuvette and the end boundary of the hydrate layer occurs.Most probably,substantial effects on the formation of this capillary system may be caused by variations in reactor wall properties,for example,hydrophobic-hydrophilic balance,roughness,etc.We found,that the rate of CO_(2) hydrate film growth on the surface of the humic acid aqueous solution is 4-fold to lower in comparison with the growth rate on the surface of pure water.We suppose that this is caused by the adsorption of humic acid associates on the surface of hydrate particles and,as a consequence,by the deceleration of the diffusion of dissolved carbon dioxide to the growing hydrate particle.展开更多
We report on the use of titanium dioxide nanoparticles (NPs) coated with poly-thiophene for the preconcentration of copper and silverions. The NPs were prepared by first modifying the surface of TiO2 NPs with vinyl gr...We report on the use of titanium dioxide nanoparticles (NPs) coated with poly-thiophene for the preconcentration of copper and silverions. The NPs were prepared by first modifying the surface of TiO2 NPs with vinyl groups and then copolymerizing them with vinyl thiophen. The resulting TiO2-polythiophene core-shell NPs were characterized by thermogravimetry, differential thermal analysis, scanning electron microscopy, Fourier transform infrared spectrometry and X-ray diffraction. The experimental conditions such as pH value, adsorption and desorption time, type, concentration and volume of the eluent, break through volume, and effect of potentially interfering ions were optimized. The ions were then desorbed with hydrochloric acid and determined by FAAS. The limits of detection are 0.4 and 1.2 μg·L_1 for Cu(II) and Ag(I), respectively, and recoveries and precisions are >98.0%展开更多
Nitrogen-doped activated carbon(N-AC)was successfully prepared by KOH-activation and nitrogen doping using ammonia(NH3)heat treatment.Coconut shell-derived activated carbon(AC)was heat-treated under NH3 gas in the tem...Nitrogen-doped activated carbon(N-AC)was successfully prepared by KOH-activation and nitrogen doping using ammonia(NH3)heat treatment.Coconut shell-derived activated carbon(AC)was heat-treated under NH3 gas in the temperature range of 700℃-900℃.Likewise,the mixture of potassium hydroxide(KOH)and AC was heated at 800℃,followed by heat treatment underNH3 gas at 800℃(hereafter referred to asKOH-N-AC800).Scanning electron microscopy(SEM),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS)and Brunauer-Emmett-Teller(BET)method were utilized to analyze morphology,crystallinity,chemical bonding,chemical composition and surface area.The surface area and porosity of N-AC increased with increasing NH3 heat treatment.Similarly,the nitrogen content in the N-AC increased from 3.23%to 4.84 at%when the NH3 heat treatment was raised from 700℃ to 800℃.However,the nitrogen content of N-AC decreased to 3.40 at% after using NH3 heat treatment at 900℃.The nitrogen content of KOH-N-AC800 is 5.43 at%.KOH-N-AC800 and N-AC800 exhibited improvements of 33.66% and 26.24%,respectively,in CO_(2) adsorption compared with AC.The enhancement of CO_(2) adsorption of KOH-N-AC800 is attributed to the synergic effect of the nitrogen doping,high surface area,and porosity.The results exhibited that nitrogen sites on the surface play a more significant role in CO_(2) adsorption than surface area and porosity.This work proposes the potential synergistic effect of KOH-activation and nitrogen doping for enhancing the CO_(2) adsorption capacity of activated carbon.展开更多
A single component molybdenum catalyst was synthesized and its activity in the cycloaddition reaction of CO_(2)and epoxide was tested.The results show that the molybdenum catalysts exhibit high activity and a broad su...A single component molybdenum catalyst was synthesized and its activity in the cycloaddition reaction of CO_(2)and epoxide was tested.The results show that the molybdenum catalysts exhibit high activity and a broad substrate scope under the reaction conditions of 80℃and 0.5 MPa of CO_(2),solvent-free,and and no nucleophilic cocatalysts,affording a wide range of cyclic carbonates in yields of 42%~94%.The reaction mechanism was investigated using in situ infrared(in situ IR),high-resolution mass spectrometry(HRMS)and Fourier transform infrared spectroscopy(FT-IR).展开更多
Confinement effect is an effective method to enhance carbon dioxide(CO_(2))solubility.In this study,a hybrid sorbent of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([Hmim][NTf_2])/mesoporous titanium ...Confinement effect is an effective method to enhance carbon dioxide(CO_(2))solubility.In this study,a hybrid sorbent of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([Hmim][NTf_2])/mesoporous titanium dioxide(M-TiO_(2))/water(H_2O)was developed,and its confinement effect was regulated by changing the pore structure of M-TiO_(2).CO_(2) solubility in the hybrid sorbent was measured experimentally,and the thermodynamic properties including Henry's constant and desorption enthalpy were calculated.Furthermore,the confinement effect in the hybrid sorbent was quantified.Additionally,the hybrid sorbent was recycled with a multi-cycle experiment.The results showed that M-TiO_(2) calcined at 773.2 K(MT500)could lead to an efficient confinement effect.CO_(2) solubility in the hybrid sorbent increased by 49.8%compared to that of H_2O when the mass fraction of[Hmim][NTf_2]/MT500 was 5.0%(mass),where the contribution of confinement effect on Gibbs free energy occupied 5.2%.展开更多
This study investigates the application of carbon dioxide (CO2) sequestration to address challenges in water-drive gas reservoirs, specifically focusing on improving gas recovery and mitigating water invasion. Traditi...This study investigates the application of carbon dioxide (CO2) sequestration to address challenges in water-drive gas reservoirs, specifically focusing on improving gas recovery and mitigating water invasion. Traditional methods like blow-down and co-production have limitations, including sand production, water coning, and inefficiency in strong aquifers. To overcome these issues, this research explores CO2 injection near the edge aquifer, aiming to reduce water influx and enhance gas recovery through the propagation of a CO2 plume in the gas-water contact zone. Both synthetic and real compositional reservoir models were studied, with CO2 injection performed while maintaining reservoir pressure below 90% of the initial level. Results show that CO2 sequestration significantly improved recovery, particularly in higher permeability reservoirs, where it reduced aquifer influx and increased gas production by 26% under challenging conditions. While CO2 dissolution in water decreased aquifer influx by 39%, its adverse effect on sweep efficiency led to a reduction in gas and water production by 4.2% and 10%, respectively. The method's effectiveness was not significantly impacted by aquifer permeability, but it was sensitive to vertical-to-horizontal permeability ratios. When applied to a real gas reservoir, the proposed method increased gas production by 14% compared to conventional techniques, with minimal CO2 production over a 112-year period. This study demonstrates the potential of CO2 sequestration as a comprehensive solution for enhancing gas recovery, reducing water production, and mitigating environmental impacts in water-drive gas reservoirs.展开更多
The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative...The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.展开更多
The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduct...The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduction pathways for CO_(2)are well explored,the single electron reduction to produce the highly reactive carbon dioxide radical anion(CO_(2)^(·-))remains challenging yet promising for green organic transformations.This review contributes to the field by providing a comprehensive analysis of the mechanisms,materials,and reaction pathways involved in CO_(2)^(·-)generation,focusing on the use of visible-lightdriven photocatalytic materials to circumvent the need for high-energy ultraviolet irradiation.Through a systematic examination of CO_(2)^(·-)production,detection methods,and chemical utilization in photocatalytic carboxylation reactions,this review advances understanding of the chemistry of CO_(2)^(·-)and its applications in sustainable chemical synthesis.In addition,it highlights existing key challenges,such as redox potential limitations,and proposes strategies for scaling up photocatalytic systems to enable practical application.By illuminating the pathway to effectively photocatalyze CO_(2)^(·-)generation and its transformative potential in sustainable chemical synthesis,this review equips scientists with critical insights and strategic approaches for overcoming current limitations,driving innovation in photocatalytic materials for solar-to-chemical energy conversion.展开更多
Mineral exploration under exotic overburden has been a great challenge in exploration geochemistry.Gas geochemical measurement is a potential method for mineral exploration due to the characteristics of strong penetra...Mineral exploration under exotic overburden has been a great challenge in exploration geochemistry.Gas geochemical measurement is a potential method for mineral exploration due to the characteristics of strong penetrability and vertical migration.The previous rapid gas analyzer cannot determine low concentrations of soil gases because of inadequate sensitivity,therefore,it is necessary to develop a more sensitive analytical technique.In this paper,the pilot studies on CO_(2) and SO_(2) geochemical measurements were performed at the Zhuxi W-(Cu)deposit,Jiapigou gold ore-concentrated area,and Tukuzbay gold deposit.This study employed rapid gas analyzer based on Infrared Absorption Spectroscopy and Electrochemical Analysis,which can detect low concentrations of CO_(2) and SO_(2) and greatly improve the reliability of test data.The results show that CO_(2) and SO_(2) show clear anomalies over deeply concealed ore bodies and faults,demonstrating that CO_(2) and SO_(2) anomalies can reveal indicative information about concealed mineralization and faults.Moreover,CO_(2) and SO_(2) anomalies can identify mineralization information exceeding 1,000 m in depth,suggesting that this method has large detection depth.Therefore,CO_(2) and SO_(2) geochemical measurement method is a feasible tool to discern deeply concealed mineralization and faults,and can provide a new idea in prospecting for concealed ore deposits in covered areas.展开更多
The tetranuclear complex[Ag4（μ-Ph2PNHPPh2）2（μ-OPh2PNPPh2O）2] （PF6）2·CH3COCH3 containing bis（diphenylphosphino）amine （Ph2PNHPPh2） and deprotonated bis- （diphenylphosphino）amine-dioxide （OPh2PNPPh2O...The tetranuclear complex[Ag4（μ-Ph2PNHPPh2）2（μ-OPh2PNPPh2O）2] （PF6）2·CH3COCH3 containing bis（diphenylphosphino）amine （Ph2PNHPPh2） and deprotonated bis- （diphenylphosphino）amine-dioxide （OPh2PNPPh2O） was isolated and characterized by X-ray crystallography. The deprotonated OPh2PNPPh2O acts as a tridentate ligand in a chelating and bridging mode. Two of the four Ag atoms are in a trigonal planar environment composed of PO2 chromophore, whereas the other two are coordinated with PN donors in a distorted linear arrangement. The title complex （C51H47Ag2F6N2O3P5） crystallizes in triclinic, space group P1^- with a = 12.9552 （2）, b = 14.1691（3）, c = 15.8110（3）A°, α = 68.7500（10）, β= 86.8840（10）, γ = 75.6170（10）°, V= 2618.16 （8） A°^3, Mr= 1220.50, Z = 2, Dc= 1.548 g/cm^3, F（000） = 1228 and μ（MoKα） = 0.965 mm^-1. The final refinements converged at R = 0.0679 and wR = 0.1528 for 7001 observed reflections （I〉 2σ（I））.展开更多
Using thermogravimetric experiments,the kinetic characteristics of magnesite thermal decomposition were investigated under the condition of 10%(vol) CO_(2) in the actual production atmosphere of an entrained-flow dyna...Using thermogravimetric experiments,the kinetic characteristics of magnesite thermal decomposition were investigated under the condition of 10%(vol) CO_(2) in the actual production atmosphere of an entrained-flow dynamic roasting furnace.Based on a multi-method collaborative framework,the three kinetic factors in the magnesite thermal decomposition process were systematically calculated through parameter cross-verification between the Hu-Gao-Zhang integral method and the Kissinger differential method.The kinetic mechanism was initially screened by the double equal and double step method and further determined by combining with the Malek maximum probability method.The study revealed that CO_(2) in the atmosphere exerts an inhibitory effect on the decomposition of carbonate species within magnesite.Furthermore,the presence of impurities(e.g.,calcium carbonate)was found to interfere with the determination of reaction mechanisms via Malek's method at elevated temperatures.The results show that in a 10%(vol)CO_(2)atmosphere,the main decomposition temperature of magnesite ranges from 550℃ to 650℃,the average activation energy is 66.00 k J·mol^(-1),the pre-exponential factor is 1.05×10^(5)s^(-1),and the decomposition process conforms to the random nucleation and growth model.展开更多
文摘Antibacterial powders of titanium dioxide/silver sulfate were produced by heat-treatment of the metatitanic acid, as precursor, into which the silver nitrate was added. The influences of heating temperature on the structure and composition of the product were investigated through XRD and SEM. The results show that the powder is spherical in the phase of TiO2-Ag2SO4. The granularity of the particles increases from 10.7nm to 28.7nm with the temperature of heat-treatment increasing from 300℃ to 800℃. The antibacterial activity of the powder was judged in the way of the minimum inhibitory contents （MiCs）. When the content of silver sulfate is less than 2%, the photocatalysis of titanium dioxide and silver ions cooperate to kill bacteria. And the MiCs decrease and keep around 1.0×10 -41.5×10 -4 constantly with the increase of silver content. Furthermore, the MiCs decrease with the increase of temperature of heat-treatment when the temperature is lower than 500℃. But when the temperature is beyond 600℃ the MiCs increase quickly, which shows the inferior antibacterial performance.
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金financially supported by the National Natural Science Foundation of China(No.22305009)the Science and Technology Development Fund,Macao SAR(File no.FDCT-0125/2022/A and FDCT-0006/2023/RIB1)Hong Kong Research Grant Council(RGC)General Research Fund(GRF)City U 11305419,11306920,CityU 11308721,CityU 11316522,and SIRG7020022。
文摘Photocatalytic carbon dioxide reduction reaction(CO_(2)RR)is a carbon-neutral strategy to address global energy use and its impact on climate.Metal oxide and metal chalcogenide catalysts are the most investigated catalysts for photocatalytic CO_(2)RR.Unfortunately,low CO_(2)adsorption ability and limited active sites of metal oxide and metal chalcogenide catalysts for CO_(2)RR make them less competitive compared to their industrial counterparts.Inspired by applications of porphyrin-based metal-organic framework(MOF)catalysts for hydrogen evolution and photodynamic therapy,the investigations of these porphyrin-based MOFs,including pristine and composite porphyrin-based MOFs in photocatalytic CO_(2)RR,have attracted significant attention in the last five years due to their excellent CO_(2)adsorption capacities,high porosity,high stability,exceptional optoelectronic properties,and multi-functionality.However,due to the difference in photocatalytic CO_(2)RR,several critical issues need to be addressed to achieve the rational design of advanced porphyrin-based MOF photocatalysts to improve activity,selectivity,and stability for CO_(2)RR.Here,we review recent developments in the field of porphyrin-based MOF CO_(2)RR photocatalysts,along with critical issues,challenges,and perspectives concerning porphyrin-based MOF catalysts for photocatalytic CO_(2)RR.
基金supported by the National Key R&D Program of China(No.2023YFC3710800)the National Natural Science Foundation of China(No.22376207)+1 种基金the Research Fund of High-Level Training Talents of“333”Project in Jiangsu provinceFunding for school-level research projects of Yancheng Institute of Technology(Nos.xjr2024008 and xjr2023055).
文摘Artificial synthesis is an environment friendly photocatalytic strategy to converse carbon dioxide(CO_(2))into useful chemicals.However,water(H_(2)O)splitting,producing(hydrogen)H_(2) strongly,is always a competitive reaction to CO_(2) conversion.Therefore,proper cocatalysts are generally needed to enhance CO_(2) conversion but suppress H_(2) production.In this work,zinc/gallium(Zn/Ga)dual co-catalysts consisting of Zn0 and amorphous ZnGa_(2)O_(4) species were found to selectively produce carbon monoxide(CO)during the photocatalytic conversion of carbon dioxide(CO_(2))using water(H_(2)O)as an electron donor over photocatalysts such as NaTaO_(3),Ga_(2)O_(3),and ZnGa_(2)O_(4),and in the electrochemical reduction of CO_(2) over Zn0 electrodes.It is considered that there are two effects associated with the Zn/Ga dual co-catalysts:(1)a galvanic cell effect between Zn0 and amorphous ZnGa_(2)O_(4),and(2)a Z-scheme effect in NaTaO_(3)/Zn0/amorphous ZnGa_(2)O_(4).The coupling of these two effects favored the active and selective evolution of CO during the photocatalytic conversion of CO_(2) by H_(2)O.In the case of Ga_(2)O_(3) photocatalyst,480.8μmol/h of CO was produced with the presence of Zn/Ga dual cocatalysts.Moreover,the Zn/Ga dual cocatalysts universally worked in the electrochemical reduction of CO_(2).The partial current toward CO_(2) conversion was increased from 2.6 to 6.6 mA/cm,and the selectivity toward CO was promoted to from 46.4%to 74.2%.
基金supported by the Science and Technology Commission of Shanghai Municipality Foundation(No.22230710500)the Interdisciplinary joint research project of Tongji University(No.2023-3-YB-07).
文摘As the core of cathode materials,sensitive metals play important roles in the optimization of acetate production from carbon dioxide(CO_(2))in microbial electrochemical system(MES).In this work,iron(Fe),copper(Cu),and nickel(Ni)as sensitive metal cathode materials were evaluated for CO_(2) conversion in MES.The MES with Feelectrode as a promising electrode material demonstrated a superior CO_(2) reduction performance with a maximum acetate accumulation of 417.9±39.2 mg/L,which was 1.5 and 1.7 folds higher than that in the Ni-electrode and Cu-electrode groups,respectively.Furthermore,an outstanding electron recovery efficiency of 67.7%was shown in the Fe-electrode group.The electron transfer between electrode-suspended sludge was systematically cross-evaluated by the electrochemical behavior and extracellular polymeric substances.The Fe-electrode group had the highest electron transfer rate with 0.194 s-1(k_(app)),which was 17.6 and 21.5 times higher than that of the Cu-and Ni-electrode groups,respectively.Fe-electrode was beneficial for reducing electrochemical impedance between the electrode and suspended sludge.Additionally,redox substances in extracellular polymeric substances of the Fe-electrode group were increased,implying more favorable electron transport dynamics.Simultaneously,enrichments of functional bacteria Acetoanerobium and increased key enzymes involved in the carbonyl pathway of the Fe-electrode group were observed,which also promoted CO_(2) conversion in MES.This study provides a perspective on evaluating the promising sensitive metal electrode material for the process of CO_(2) valorization in MES and offers a reference for the subsequent electrode modification.
基金supported by the National Natural Science Foundation of China(Nos.81974441 and 82203619)the Science and Technology Planning Project of Shenzhen Municipality(Nos.JCYJ20190814105619048 and JCYJ20220530154202005)。
文摘Colitis-associated colorectal cancer(CAC)is a major contributor to cancer-related mortality worldwide.Titanium dioxide(TiO_(2),E171),a widely used food additive,has been insufficiently studied regarding its effects on macrophages within colon tumors during CAC development.In this study,CAC mouse models were used to investigate the biological impact of dietary E171 on macrophages in vivo,while lipopolysaccharide(LPS)-stimulated RAW264.7 macrophage cell lines were employed to elucidate the underlying mechanisms in vitro.We found that dietary E171 intake accelerated CAC development,exacerbated inflammatory responses and oxidative stress,and upregulated CAC-associated genes,including S100a8,S100a9,Lcn2,S100a11,Cxcl2,and interleukin-1α(Il-1α).E171 also increased the expression of S100A8,S100A9,NOD-like receptor family pyrin domain-containing 3(NLRP3),and gasdermin-D Nterminal(GSDMD-N)in macrophages within colon tumors.In inflammatory macrophages,E171 exposure enhanced cell viability,increased reactive oxygen species(ROS)levels,and elevated the expression and secretion of S100A8 and S100A9,consistent with in vivo histological observations.Furthermore,E171-induced secretion of S100A8 and S100A9 in macrophages was suppressed by specific inhibitors,including N-acetylcysteine(NAC,ROS inhibitor),MCC950(NLRP3 inhibitor),Z-YVAD-FMK(caspase 1 inhibitor),disulfiram(GSDMD inhibitor),and transfection of NLRP3 small interfering ribonucleic acid(siRNA).These results indicate that dietary E171 promotes CAC development by activating macrophages,with S100A8 and S100A9 serving as key mediators,and the NLRP3/caspase 1/GSDMD pathway acting as a critical mechanism.
基金supported by National Natural Science Foundation of China(21346006)National College Students' Innovation and Entrepreneurship Training Major Project(201310222013)+3 种基金the Department of Scientific Research Projects in Heilongjiang Province(B201015)Scientific Research Project in Heilongjiang Province’s Department of Education(125418211254178312543078)
文摘An inorganic nanomaterials combination of Sm, Ag, and TiO2 was synthesized using supercritical fluid drying （SCFD） combined with solgel techniques. The structure, photocatalysis and bacteriostatic activity of the materials were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, X-ray photoelectron spectroscopy （XRPS）, photocatalytic performance, and antibacterial activity experiments. The XRD results showed that the average particle diameter of Sm/Ag/TiO2 was 14.62 nm and Ag and Sm ions were dispersed on the surface of TiO2 in a highly dispersed, amorphous form. The TEM image showed that the size of the particle was 12 nm using the scherer formula. The XPS result showed that the element Sm was doped and Ag was loaded inorganic nanomaterials successfully. Sm/Ag/TiO2 exhibited optimal photocatalytic properties at 600 oC, the photocatalytic optimal proportion of Sm/Ag/TiO2 was 2：2：100. When the molar ratio was 2：2：100, the bacteriostatic circle diameter was 16 mm for Staphylococcus aureus, the minimum bacteriostatic concentration was 200μg/mL for white beads coccus, and the minimum bactericidal concentration was 2×10^4μg/mL for white beads coccus. The SEM results showed that the antibacterial material attached to the candida albicans cell surface, cells appeared fold deformation. Therefore the inorganic nanomaterials Sm/Ag/TiO2 had high temperature resistance, good photocatalytic and antibacterial characteristics in visible light.
基金Supported by the National Natural Science Foundation of China(U1662130,21506027)China Postdoctoral Science Foundation(2017T100175,2015M571307)the Fundamental Research Funds for the Central Universities(DUT17JC34)
文摘Solubility of the silver nitrate in the supercritical carbon dioxide containing ethanol and ethylene glycol as double cosolvents was measured under certain pressure and temperature range(10–25 MPa, 323.15–333.15 K). The impact of the pressure and temperature on the solubility was also investigated. Based on the experiment data,a correlation model concerning solid's solubility in supercritical fluids was established by combining the solubility parameter with the thermodynamic equation when a binary interaction parameter and a mixed solvent solubility parameter were defined. Experiments show the solubility of AgNO_3 increases with the pressure at a certain temperature. However, the influence of temperature is related to a pressure defined as the turnover pressure(12.3 MPa). When the pressure is higher(or lower) than this turnover pressure, silver nitrate's solubility shows increasing(or decreasing) trend as the temperature rises. Satisfactory accuracy of our presented model was revealed by comparing experimental data with calculated results.
基金supported by the National Key Research and Development Program of China (No. 2020YFC1808300)the Fundamental Research Fund for the Central Universities (No. 2652019115)+1 种基金Guangxi Key Research Project (Guike AB18050026)the Natural Science Foundation of China (No. 41731282)。
文摘The adsorption behaviors of ciprofloxacin(CIP),a fluoroquinolone antibiotic,onto goethite(Gt)in the presence of silver and titanium dioxide nanoparticles(AgNPs and TiO_(2)NPs)were investigated.Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model.The presence of AgNPs or TiO_(2)NPs inhibited the adsorption of CIP by Gt.The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0.In contrast,in the presence of TiO_(2)NPs,CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0.The mechanisms of AgNPs and TiO_(2)NPs in inhibiting CIP adsorption by Gt were different,which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt,while TiO_(2)NPs could compete with Gt for CIP adsorption.Additionally,CIP was adsorbed by Gt or TiO_(2)NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring.These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.
基金supported by the Russian Science Foundation(23-29-00830).
文摘Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the interface,further growth of hydrate due to the suction of water in the capillary system formed between the wall of the cuvette and the end boundary of the hydrate layer occurs.Most probably,substantial effects on the formation of this capillary system may be caused by variations in reactor wall properties,for example,hydrophobic-hydrophilic balance,roughness,etc.We found,that the rate of CO_(2) hydrate film growth on the surface of the humic acid aqueous solution is 4-fold to lower in comparison with the growth rate on the surface of pure water.We suppose that this is caused by the adsorption of humic acid associates on the surface of hydrate particles and,as a consequence,by the deceleration of the diffusion of dissolved carbon dioxide to the growing hydrate particle.
文摘We report on the use of titanium dioxide nanoparticles (NPs) coated with poly-thiophene for the preconcentration of copper and silverions. The NPs were prepared by first modifying the surface of TiO2 NPs with vinyl groups and then copolymerizing them with vinyl thiophen. The resulting TiO2-polythiophene core-shell NPs were characterized by thermogravimetry, differential thermal analysis, scanning electron microscopy, Fourier transform infrared spectrometry and X-ray diffraction. The experimental conditions such as pH value, adsorption and desorption time, type, concentration and volume of the eluent, break through volume, and effect of potentially interfering ions were optimized. The ions were then desorbed with hydrochloric acid and determined by FAAS. The limits of detection are 0.4 and 1.2 μg·L_1 for Cu(II) and Ag(I), respectively, and recoveries and precisions are >98.0%
基金funded by Burapha University,grant number SDG 4/2568.
文摘Nitrogen-doped activated carbon(N-AC)was successfully prepared by KOH-activation and nitrogen doping using ammonia(NH3)heat treatment.Coconut shell-derived activated carbon(AC)was heat-treated under NH3 gas in the temperature range of 700℃-900℃.Likewise,the mixture of potassium hydroxide(KOH)and AC was heated at 800℃,followed by heat treatment underNH3 gas at 800℃(hereafter referred to asKOH-N-AC800).Scanning electron microscopy(SEM),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS)and Brunauer-Emmett-Teller(BET)method were utilized to analyze morphology,crystallinity,chemical bonding,chemical composition and surface area.The surface area and porosity of N-AC increased with increasing NH3 heat treatment.Similarly,the nitrogen content in the N-AC increased from 3.23%to 4.84 at%when the NH3 heat treatment was raised from 700℃ to 800℃.However,the nitrogen content of N-AC decreased to 3.40 at% after using NH3 heat treatment at 900℃.The nitrogen content of KOH-N-AC800 is 5.43 at%.KOH-N-AC800 and N-AC800 exhibited improvements of 33.66% and 26.24%,respectively,in CO_(2) adsorption compared with AC.The enhancement of CO_(2) adsorption of KOH-N-AC800 is attributed to the synergic effect of the nitrogen doping,high surface area,and porosity.The results exhibited that nitrogen sites on the surface play a more significant role in CO_(2) adsorption than surface area and porosity.This work proposes the potential synergistic effect of KOH-activation and nitrogen doping for enhancing the CO_(2) adsorption capacity of activated carbon.
文摘A single component molybdenum catalyst was synthesized and its activity in the cycloaddition reaction of CO_(2)and epoxide was tested.The results show that the molybdenum catalysts exhibit high activity and a broad substrate scope under the reaction conditions of 80℃and 0.5 MPa of CO_(2),solvent-free,and and no nucleophilic cocatalysts,affording a wide range of cyclic carbonates in yields of 42%~94%.The reaction mechanism was investigated using in situ infrared(in situ IR),high-resolution mass spectrometry(HRMS)and Fourier transform infrared spectroscopy(FT-IR).
基金the National Natural Science Foundation of China(22108115,22478415,and 21978134)Natural Science Foundation of Jiangsu Province(BK20241744)。
文摘Confinement effect is an effective method to enhance carbon dioxide(CO_(2))solubility.In this study,a hybrid sorbent of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([Hmim][NTf_2])/mesoporous titanium dioxide(M-TiO_(2))/water(H_2O)was developed,and its confinement effect was regulated by changing the pore structure of M-TiO_(2).CO_(2) solubility in the hybrid sorbent was measured experimentally,and the thermodynamic properties including Henry's constant and desorption enthalpy were calculated.Furthermore,the confinement effect in the hybrid sorbent was quantified.Additionally,the hybrid sorbent was recycled with a multi-cycle experiment.The results showed that M-TiO_(2) calcined at 773.2 K(MT500)could lead to an efficient confinement effect.CO_(2) solubility in the hybrid sorbent increased by 49.8%compared to that of H_2O when the mass fraction of[Hmim][NTf_2]/MT500 was 5.0%(mass),where the contribution of confinement effect on Gibbs free energy occupied 5.2%.
文摘This study investigates the application of carbon dioxide (CO2) sequestration to address challenges in water-drive gas reservoirs, specifically focusing on improving gas recovery and mitigating water invasion. Traditional methods like blow-down and co-production have limitations, including sand production, water coning, and inefficiency in strong aquifers. To overcome these issues, this research explores CO2 injection near the edge aquifer, aiming to reduce water influx and enhance gas recovery through the propagation of a CO2 plume in the gas-water contact zone. Both synthetic and real compositional reservoir models were studied, with CO2 injection performed while maintaining reservoir pressure below 90% of the initial level. Results show that CO2 sequestration significantly improved recovery, particularly in higher permeability reservoirs, where it reduced aquifer influx and increased gas production by 26% under challenging conditions. While CO2 dissolution in water decreased aquifer influx by 39%, its adverse effect on sweep efficiency led to a reduction in gas and water production by 4.2% and 10%, respectively. The method's effectiveness was not significantly impacted by aquifer permeability, but it was sensitive to vertical-to-horizontal permeability ratios. When applied to a real gas reservoir, the proposed method increased gas production by 14% compared to conventional techniques, with minimal CO2 production over a 112-year period. This study demonstrates the potential of CO2 sequestration as a comprehensive solution for enhancing gas recovery, reducing water production, and mitigating environmental impacts in water-drive gas reservoirs.
基金supported by the National Natural Science Foundation of China(21878038)the Natural Science Foundation of Liaoning Province(20170540156)the Program for Changjiang Scholars and Innovative Research Team in University(IRT-17R14)~~
文摘The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.
基金funding programs,the Walter Benjamin Programme(DFG,German Research Foundation,project number:530742479)the ProChancecareer Programme for the Promotion of Equal Opportunities in Academia for providing the financial support+1 种基金financial support by the Deutsche Forschungsgemeinschaft via the TRR 234 Cata Light(DFG,German Research Foundation)-Projektnummer 364549901-TRR 234[B6]the financial support taken from the CSIR and UGC,Delhi,India。
文摘The photocatalytic reduction of CO_(2)is a crucial area of research aimed at addressing the dual challenges of mitigating rising CO_(2)emissions and producing sustainable chemical feedstocks.While multielectron reduction pathways for CO_(2)are well explored,the single electron reduction to produce the highly reactive carbon dioxide radical anion(CO_(2)^(·-))remains challenging yet promising for green organic transformations.This review contributes to the field by providing a comprehensive analysis of the mechanisms,materials,and reaction pathways involved in CO_(2)^(·-)generation,focusing on the use of visible-lightdriven photocatalytic materials to circumvent the need for high-energy ultraviolet irradiation.Through a systematic examination of CO_(2)^(·-)production,detection methods,and chemical utilization in photocatalytic carboxylation reactions,this review advances understanding of the chemistry of CO_(2)^(·-)and its applications in sustainable chemical synthesis.In addition,it highlights existing key challenges,such as redox potential limitations,and proposes strategies for scaling up photocatalytic systems to enable practical application.By illuminating the pathway to effectively photocatalyze CO_(2)^(·-)generation and its transformative potential in sustainable chemical synthesis,this review equips scientists with critical insights and strategic approaches for overcoming current limitations,driving innovation in photocatalytic materials for solar-to-chemical energy conversion.
基金the Key Laboratory of Geochemical Exploration, Institute of Geophysical and Geochemical Exploration, China Geological Survey, and Ministry of Natural Resources of the People’s Republic of China for funding this researchsupported by National Nonprofit Institute Research Grant of Institute of Geophysical and Geochemical Exploration (AS2022P03)Key Laboratory of Ionic Rare Earth Resources and Environment, Ministry of Natural Resources of the People’s Republic of China (No. 2022IRERE101 and No. 2023IRERE102)
文摘Mineral exploration under exotic overburden has been a great challenge in exploration geochemistry.Gas geochemical measurement is a potential method for mineral exploration due to the characteristics of strong penetrability and vertical migration.The previous rapid gas analyzer cannot determine low concentrations of soil gases because of inadequate sensitivity,therefore,it is necessary to develop a more sensitive analytical technique.In this paper,the pilot studies on CO_(2) and SO_(2) geochemical measurements were performed at the Zhuxi W-(Cu)deposit,Jiapigou gold ore-concentrated area,and Tukuzbay gold deposit.This study employed rapid gas analyzer based on Infrared Absorption Spectroscopy and Electrochemical Analysis,which can detect low concentrations of CO_(2) and SO_(2) and greatly improve the reliability of test data.The results show that CO_(2) and SO_(2) show clear anomalies over deeply concealed ore bodies and faults,demonstrating that CO_(2) and SO_(2) anomalies can reveal indicative information about concealed mineralization and faults.Moreover,CO_(2) and SO_(2) anomalies can identify mineralization information exceeding 1,000 m in depth,suggesting that this method has large detection depth.Therefore,CO_(2) and SO_(2) geochemical measurement method is a feasible tool to discern deeply concealed mineralization and faults,and can provide a new idea in prospecting for concealed ore deposits in covered areas.
基金This work was supported by NSF of Fujian Province (E0310029 and E0420002)
文摘The tetranuclear complex[Ag4（μ-Ph2PNHPPh2）2（μ-OPh2PNPPh2O）2] （PF6）2·CH3COCH3 containing bis（diphenylphosphino）amine （Ph2PNHPPh2） and deprotonated bis- （diphenylphosphino）amine-dioxide （OPh2PNPPh2O） was isolated and characterized by X-ray crystallography. The deprotonated OPh2PNPPh2O acts as a tridentate ligand in a chelating and bridging mode. Two of the four Ag atoms are in a trigonal planar environment composed of PO2 chromophore, whereas the other two are coordinated with PN donors in a distorted linear arrangement. The title complex （C51H47Ag2F6N2O3P5） crystallizes in triclinic, space group P1^- with a = 12.9552 （2）, b = 14.1691（3）, c = 15.8110（3）A°, α = 68.7500（10）, β= 86.8840（10）, γ = 75.6170（10）°, V= 2618.16 （8） A°^3, Mr= 1220.50, Z = 2, Dc= 1.548 g/cm^3, F（000） = 1228 and μ（MoKα） = 0.965 mm^-1. The final refinements converged at R = 0.0679 and wR = 0.1528 for 7001 observed reflections （I〉 2σ（I））.
基金supported by the Natural Science Foundation of Liaoning Province(2024-MSLH-360)。
文摘Using thermogravimetric experiments,the kinetic characteristics of magnesite thermal decomposition were investigated under the condition of 10%(vol) CO_(2) in the actual production atmosphere of an entrained-flow dynamic roasting furnace.Based on a multi-method collaborative framework,the three kinetic factors in the magnesite thermal decomposition process were systematically calculated through parameter cross-verification between the Hu-Gao-Zhang integral method and the Kissinger differential method.The kinetic mechanism was initially screened by the double equal and double step method and further determined by combining with the Malek maximum probability method.The study revealed that CO_(2) in the atmosphere exerts an inhibitory effect on the decomposition of carbonate species within magnesite.Furthermore,the presence of impurities(e.g.,calcium carbonate)was found to interfere with the determination of reaction mechanisms via Malek's method at elevated temperatures.The results show that in a 10%(vol)CO_(2)atmosphere,the main decomposition temperature of magnesite ranges from 550℃ to 650℃,the average activation energy is 66.00 k J·mol^(-1),the pre-exponential factor is 1.05×10^(5)s^(-1),and the decomposition process conforms to the random nucleation and growth model.
