Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are st...Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions.Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products.In this study,we aim to regulate the surface electronic structure of Bi_(2)WO_(6)by doping surface chlorine atoms to achieve effective photocatalytic CO_(2)reduction.Surface Cl atoms can enhance the absorption ability of light,affect its energy band structure and promote charge separation.Combined with DFT calculations,it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H_(2)O and CO_(2),but also lower the formation energy barrier of intermediate products to generate more intermediate*COOH,thus facilitating CO production.Overall,this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO_(2)reduction activity of a layered structure Bi-based catalyst.展开更多
"Carbon peaking and carbon neutrality"is an essential national strategy,and the geological storage and utilization of CO_(2)is a hot issue today.However,due to the scarcity of pure CO_(2)gas sources in China..."Carbon peaking and carbon neutrality"is an essential national strategy,and the geological storage and utilization of CO_(2)is a hot issue today.However,due to the scarcity of pure CO_(2)gas sources in China and the high cost of CO_(2)capture,CO_(2)-rich industrial waste gas(CO_(2)-rich IWG)is gradually emerging into the public's gaze.CO_(2)has good adsorption properties on shale surfaces,but acidic gases can react with shale,so the mechanism of the CO_(2)-rich IWG-water-shale reaction and the change in reservoir properties will determine the stability of geological storage.Therefore,based on the mineral composition of the Longmaxi Formation shale,this study constructs a thermodynamic equilibrium model of water-rock reactions and simulates the regularity of reactions between CO_(2)-rich IWG and shale minerals.The results indicate that CO_(2)consumed 12%after reaction,and impurity gases in the CO_(2)-rich IWG can be dissolved entirely,thus demonstrating the feasibility of treating IWG through water-rock reactions.Since IWG inhibits the dissolution of CO_(2),the optimal composition of CO_(2)-rich IWG is 95%CO_(2)and 5%IWG when CO_(2)geological storage is the main goal.In contrast,when the main goal is the geological storage of total CO_(2)-rich IWG or impurity gas,the optimal CO_(2)-rich IWG composition is 50%CO_(2)and 50%IWG.In the CO_(2)-rich IWG-water-shale reaction,temperature has less influence on the water-rock reaction,while pressure is the most important parameter.SO2 has the greatest impact on water-rock reaction in gas.For minerals,clay minerals such as illite and montmorillonite had a significant effect on water-rock reaction.The overall reaction is dominated by precipitation and the volume of the rock skeleton has increased by 0.74 cm3,resulting in a decrease in shale porosity,which enhances the stability of CO_(2)geological storage to some extent.During the reaction between CO_(2)-rich IWG-water-shale at simulated temperatures and pressures,precipitation is the main reaction,and shale porosity decreases.However,as the reservoir water content increases,the reaction will first dissolve and then precipitate before dissolving again.When the water content is less than 0.0005 kg or greater than 0.4 kg,it will lead to an increase in reservoir porosity,which ultimately reduces the long-term geological storage stability of CO_(2)-rich IWG.展开更多
In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction m...In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.展开更多
A ternary system of PTFE/Al/Bi_(2)O_(3)is constructed by incorporating PTFE-based reactive material and thermite for enhancing the energy release of the PTFE-based reactive material.The effects of Bi_(2)O_(3)in the PT...A ternary system of PTFE/Al/Bi_(2)O_(3)is constructed by incorporating PTFE-based reactive material and thermite for enhancing the energy release of the PTFE-based reactive material.The effects of Bi_(2)O_(3)in the PTFE/Al/Bi_(2)O_(3)on both mechanical properties and the energy release were investigated through various tests such as thermogravimetry-differential scanning calorimetry,adiabatic oxygen bomb test and split Hopkinson pressure bar test.The microstructure observed through scanning electron microscope and Xray diffraction results are used to analyze the ignition and reaction mechanism of PTFE/Al/Bi_(2)O_(3).The results indicate that the PTFE/Al/Bi_(2)O_(3)are capable of triggering the exothermic reaction of molten PTFE/Bi_(2)O_(3)and Al/Bi_(2)O_(3)over the PTFE/Al reactive materials,thereby promoting reactions.The excessive aluminum in the ternary system is beneficial for increasing energy release.The ignition of shock-induced chemical reactions in PTFE/Al/Bi_(2)O_(3)is closely related to the material fracture.The dominant mechanism for hot-spot generation under Split Hopkinson Pressure Bar test is the frictional temperature rise at the microcrack after failure.展开更多
Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the...Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the input energy is"wasted"at the anode due to the high overpotential requirement and the recovery of low-value oxygen.To make efficient use of the electricity during electrolysis,coupling CO_(2)RR with anodic alternatives that have low energy demands and/or profitable returns with high-value products is then promising.Herein,we review the latest advances in paired systems for simultaneous CO_(2) reduction and anode valorization.We start with the cases integrating CO_(2)RR with concurrent alternative oxidation,such as inorganic oxidation using chloride,sulfide,ammonia and urea,and organic oxidation using alcohols,aldehydes and primary amines.The paired systems that couple CO_(2)RR with on-site oxidative upgrading of CO_(2)-reduced chemicals are also introduced.The coupling mechanism,electrochemical performance and economic viability of these co-electrolysis systems are discussed.Thereby,we then point out the mismatch issues between the cathodic and anodic reactions regrading catalyst ability,electrolyte solution and reactant supply that will challenge the applications of these paired electrolysis systems.Opportunities to address these issues are further proposed,providing some guidance for future research.展开更多
The Lucaogou Formation,located in the Jimsar Sag,Junggar Basin,NW China,has great potential for shale oil resources.In the process of CO_(2)-EOR(CO_(2) enhance oil recovery),mineral dissolution,precipitation and trans...The Lucaogou Formation,located in the Jimsar Sag,Junggar Basin,NW China,has great potential for shale oil resources.In the process of CO_(2)-EOR(CO_(2) enhance oil recovery),mineral dissolution,precipitation and transformation,leading to the local corrosion or blockage of reservoirs,have a significant influence on recovery.In this study,a combination of high-temperature and high-pressure laboratory experiments and coupled temperature/fluid-chemistry multifield numerical simulations are used to investigate CO_(2)-water-rock reactions under various reservoir conditions in the upper and lower ’sweet spots’,to reveal the mechanisms underlying CO_(2)-induced mineral dissolution,precipitation and transformation.In addition,we quantitatively calculated the evolution of porosity over geological timescales;compared and analyzed the variability of CO_(2) transformation in the reservoir under a variety of temperature,lithology and solution conditions;and identified the main factors controlling CO_(2)-water-rock reactions,the types of mineral transformation occurring during long-term CO_(2) sequestration and effective carbon sequestration minerals.The results demonstrate that the main minerals undergoing dissolution under the influence of supercritical CO_(2) are feldspars,while the main minerals undergoing precipitation include carbonate rock minerals,clay minerals and quartz.Feldspar minerals,especially the initially abundant plagioclase in the formation,directly affects total carbon sequestration,feldspar-rich clastic rocks therefore having considerable sequestration potential.展开更多
Metal–N_(2) battery can be applied in both energy storage and electrochemical nitrogen reduction reaction(NRR);however,there has been only extraordinarily little study on metal–N_(2) battery since its electrochemica...Metal–N_(2) battery can be applied in both energy storage and electrochemical nitrogen reduction reaction(NRR);however,there has been only extraordinarily little study on metal–N_(2) battery since its electrochemical reversibility still needs further proofs.And its electrochemical performances also need to be enhanced.Herein,we investigated the discharge–charge reactions between Li anode and N_(2) cathode via designing an efficient catalyst of nanosized SnO_(2) particles dispersed on N-doped carbon nanosheets(SnO 2@NC)for the Li-N_(2) battery,with good cyclic stability and a high specific capacity of 0.25 mA h(~500 mA h g^(−1))at a large current density of 1000 mA g^(−1).The electrochemical reversibility of both NRR in the discharge process and nitrogen extraction reaction in the charge process for Li-N 2 battery is discussed.Time-of-flight secondary ion mass spectrometry results imply that the SnO_(2)@NC can effectively promote the adsorption of N_(2) and the activation of NRR in the discharge process.Furthermore,ex situ X-ray photoelectron spectroscopy and Fourier transform infrared tests are performed to study the electrochemical reversibility of Li-N_(2) battery.It can be proved that the formation and decomposition of discharging product Li_(3)N are electrochemical reversible during cycling in our deigned Li-N_(2) battery system with SnO_(2)@NC catalyst.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.51708078)Natural Science Foundation of Chongqing(Grant No.CSTB2022NSCQ-MSX0815)+2 种基金Science and Technology Research Program of Chongqing Municipal Education Commission(Grant No.KJQN202200542)the Chongqing Innovative Research Group Project(Grant No.CXQT21015)Foundation of Chongqing Normal University(22XLB022).
文摘Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions.Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products.In this study,we aim to regulate the surface electronic structure of Bi_(2)WO_(6)by doping surface chlorine atoms to achieve effective photocatalytic CO_(2)reduction.Surface Cl atoms can enhance the absorption ability of light,affect its energy band structure and promote charge separation.Combined with DFT calculations,it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H_(2)O and CO_(2),but also lower the formation energy barrier of intermediate products to generate more intermediate*COOH,thus facilitating CO production.Overall,this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO_(2)reduction activity of a layered structure Bi-based catalyst.
基金The work was supported by the National Natural Science Foundation of China(No.52074316)PetroChina Company Limited(No.2019E-2608).
文摘"Carbon peaking and carbon neutrality"is an essential national strategy,and the geological storage and utilization of CO_(2)is a hot issue today.However,due to the scarcity of pure CO_(2)gas sources in China and the high cost of CO_(2)capture,CO_(2)-rich industrial waste gas(CO_(2)-rich IWG)is gradually emerging into the public's gaze.CO_(2)has good adsorption properties on shale surfaces,but acidic gases can react with shale,so the mechanism of the CO_(2)-rich IWG-water-shale reaction and the change in reservoir properties will determine the stability of geological storage.Therefore,based on the mineral composition of the Longmaxi Formation shale,this study constructs a thermodynamic equilibrium model of water-rock reactions and simulates the regularity of reactions between CO_(2)-rich IWG and shale minerals.The results indicate that CO_(2)consumed 12%after reaction,and impurity gases in the CO_(2)-rich IWG can be dissolved entirely,thus demonstrating the feasibility of treating IWG through water-rock reactions.Since IWG inhibits the dissolution of CO_(2),the optimal composition of CO_(2)-rich IWG is 95%CO_(2)and 5%IWG when CO_(2)geological storage is the main goal.In contrast,when the main goal is the geological storage of total CO_(2)-rich IWG or impurity gas,the optimal CO_(2)-rich IWG composition is 50%CO_(2)and 50%IWG.In the CO_(2)-rich IWG-water-shale reaction,temperature has less influence on the water-rock reaction,while pressure is the most important parameter.SO2 has the greatest impact on water-rock reaction in gas.For minerals,clay minerals such as illite and montmorillonite had a significant effect on water-rock reaction.The overall reaction is dominated by precipitation and the volume of the rock skeleton has increased by 0.74 cm3,resulting in a decrease in shale porosity,which enhances the stability of CO_(2)geological storage to some extent.During the reaction between CO_(2)-rich IWG-water-shale at simulated temperatures and pressures,precipitation is the main reaction,and shale porosity decreases.However,as the reservoir water content increases,the reaction will first dissolve and then precipitate before dissolving again.When the water content is less than 0.0005 kg or greater than 0.4 kg,it will lead to an increase in reservoir porosity,which ultimately reduces the long-term geological storage stability of CO_(2)-rich IWG.
基金supported by the Qingdao Postdoctoral Program Funding(QDBSH20220202045)Shandong provincial Natural Science Foundation(ZR2021ME049,ZR2022ME176)+1 种基金National Natural Science Foundation of China(22078176)Taishan Industrial Experts Program(TSCX202306135).
文摘In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.
基金the National Natural Science Foundation of China (Grant No.12002045)State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology (Grant No.QNKT22-09)。
文摘A ternary system of PTFE/Al/Bi_(2)O_(3)is constructed by incorporating PTFE-based reactive material and thermite for enhancing the energy release of the PTFE-based reactive material.The effects of Bi_(2)O_(3)in the PTFE/Al/Bi_(2)O_(3)on both mechanical properties and the energy release were investigated through various tests such as thermogravimetry-differential scanning calorimetry,adiabatic oxygen bomb test and split Hopkinson pressure bar test.The microstructure observed through scanning electron microscope and Xray diffraction results are used to analyze the ignition and reaction mechanism of PTFE/Al/Bi_(2)O_(3).The results indicate that the PTFE/Al/Bi_(2)O_(3)are capable of triggering the exothermic reaction of molten PTFE/Bi_(2)O_(3)and Al/Bi_(2)O_(3)over the PTFE/Al reactive materials,thereby promoting reactions.The excessive aluminum in the ternary system is beneficial for increasing energy release.The ignition of shock-induced chemical reactions in PTFE/Al/Bi_(2)O_(3)is closely related to the material fracture.The dominant mechanism for hot-spot generation under Split Hopkinson Pressure Bar test is the frictional temperature rise at the microcrack after failure.
基金financially supported by the National Natural Science Foundation of China(22002084,22072081)the China Postdoctoral Science Foundation(2020M683420)+1 种基金the Fundamental Research Funds for the Central Universities(GK202103111)the 111 Project(B21005)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the input energy is"wasted"at the anode due to the high overpotential requirement and the recovery of low-value oxygen.To make efficient use of the electricity during electrolysis,coupling CO_(2)RR with anodic alternatives that have low energy demands and/or profitable returns with high-value products is then promising.Herein,we review the latest advances in paired systems for simultaneous CO_(2) reduction and anode valorization.We start with the cases integrating CO_(2)RR with concurrent alternative oxidation,such as inorganic oxidation using chloride,sulfide,ammonia and urea,and organic oxidation using alcohols,aldehydes and primary amines.The paired systems that couple CO_(2)RR with on-site oxidative upgrading of CO_(2)-reduced chemicals are also introduced.The coupling mechanism,electrochemical performance and economic viability of these co-electrolysis systems are discussed.Thereby,we then point out the mismatch issues between the cathodic and anodic reactions regrading catalyst ability,electrolyte solution and reactant supply that will challenge the applications of these paired electrolysis systems.Opportunities to address these issues are further proposed,providing some guidance for future research.
基金funded by grants from the Beijing Natural Science Foundation (Grant No. 8232044)the Natural Science Foundation of the Xinjiang Uygur Autonomous Region (Grant No. 2021D01F38)China Geological Survey Second-level Project (Grant No. DD20230025)。
文摘The Lucaogou Formation,located in the Jimsar Sag,Junggar Basin,NW China,has great potential for shale oil resources.In the process of CO_(2)-EOR(CO_(2) enhance oil recovery),mineral dissolution,precipitation and transformation,leading to the local corrosion or blockage of reservoirs,have a significant influence on recovery.In this study,a combination of high-temperature and high-pressure laboratory experiments and coupled temperature/fluid-chemistry multifield numerical simulations are used to investigate CO_(2)-water-rock reactions under various reservoir conditions in the upper and lower ’sweet spots’,to reveal the mechanisms underlying CO_(2)-induced mineral dissolution,precipitation and transformation.In addition,we quantitatively calculated the evolution of porosity over geological timescales;compared and analyzed the variability of CO_(2) transformation in the reservoir under a variety of temperature,lithology and solution conditions;and identified the main factors controlling CO_(2)-water-rock reactions,the types of mineral transformation occurring during long-term CO_(2) sequestration and effective carbon sequestration minerals.The results demonstrate that the main minerals undergoing dissolution under the influence of supercritical CO_(2) are feldspars,while the main minerals undergoing precipitation include carbonate rock minerals,clay minerals and quartz.Feldspar minerals,especially the initially abundant plagioclase in the formation,directly affects total carbon sequestration,feldspar-rich clastic rocks therefore having considerable sequestration potential.
基金This work was financially supported by the National Natural Science Foundation of China (52071144,51621001,and 51822104).
文摘Metal–N_(2) battery can be applied in both energy storage and electrochemical nitrogen reduction reaction(NRR);however,there has been only extraordinarily little study on metal–N_(2) battery since its electrochemical reversibility still needs further proofs.And its electrochemical performances also need to be enhanced.Herein,we investigated the discharge–charge reactions between Li anode and N_(2) cathode via designing an efficient catalyst of nanosized SnO_(2) particles dispersed on N-doped carbon nanosheets(SnO 2@NC)for the Li-N_(2) battery,with good cyclic stability and a high specific capacity of 0.25 mA h(~500 mA h g^(−1))at a large current density of 1000 mA g^(−1).The electrochemical reversibility of both NRR in the discharge process and nitrogen extraction reaction in the charge process for Li-N 2 battery is discussed.Time-of-flight secondary ion mass spectrometry results imply that the SnO_(2)@NC can effectively promote the adsorption of N_(2) and the activation of NRR in the discharge process.Furthermore,ex situ X-ray photoelectron spectroscopy and Fourier transform infrared tests are performed to study the electrochemical reversibility of Li-N_(2) battery.It can be proved that the formation and decomposition of discharging product Li_(3)N are electrochemical reversible during cycling in our deigned Li-N_(2) battery system with SnO_(2)@NC catalyst.
