The oxidative dehydrogenation of propane with carbon dioxide(CO2-ODP)has received significant attention as an environmentally benign route for the propene production.However,the development of high-performance cata...The oxidative dehydrogenation of propane with carbon dioxide(CO2-ODP)has received significant attention as an environmentally benign route for the propene production.However,the development of high-performance catalysts remains a critical challenge hindering its industrial implementation.In this work,CeO2 samples with distinct morphologies resembling flowers(F-CeO2),rods(R-CeO2),spindles(SP-CeO2),and sheets(SH-CeO2)were successfully synthesized by simply changing the hydrothermal conditions,and the shape-dependent impact of oxygen-defect contents over CeO2 on the structural and electronic properties of the impregnated PtSn/CeO2 catalysts was studied for CO2-ODP.Characterizations reveal a positive correlation between the Pt electron density and oxygen-defect contents in an increasing order of PtSn/F-CeO2<PtSn/R-CeO2<PtSn/SP-CeO2<PtSn/SH-CeO2.In the case of the catalytic results,the same changing pattern is observed for the initial C3H8 conversion and C3H6selectivity.Moreover,the highest initial propene space-time yield of 0.71 kg_((C3H6))/(kg(cat)·h)achieving over the PtSn/SH-CeO2 catalyst is still retained at 0.35 kg_((C3H6))/(kg(cat)·h)after a time on stream of 200min.This perfo rmance surpasses those of most reported CO2-ODP catalysts.The morphology-dependent catalytic phenomena are attributed mainly to the varied activation energies of CO2-ODP,which are determined by the oxygen defect-induced electronic and structural interplay between Pt,Sn,and CeO2.These findings provide valuable insights for the rational design and optimization of Pt-based catalysts for CO2-ODP,particularly in the selection of oxide supports.展开更多
To date,the question of how to address the challenges associated with urgent global carbon emissions while harnessing renewable energy remains unanswered,a challenge that our world has so far failed to solve.Among man...To date,the question of how to address the challenges associated with urgent global carbon emissions while harnessing renewable energy remains unanswered,a challenge that our world has so far failed to solve.Among many strategies,artificial photosynthesis systems that mimic natural processes to enable the in-situ generation of protons(H+)for hydrogenation of CO2 into value-added carbonaceous fuels represent a promising route.Herein,this review highlights recent advancements in solar-driven photoreduction of CO2 in the presence of H+.Emphasis is placed on photocatalysts and their funda-mental mechanisms governing the photoreduction of CO2,including light absorption,charge-carrier dynamics,surface adsorption,and photocatalytic efficiency.The concept of dual-functional photo-catalytic active CO2 via in-situ generation of H+provides a sustainable and carbon-neutral pathway to produce renewable energy.Although many efforts have been made,the overall energy conversion ef-ficiency remains limited by the complexity of multistep reactions,rapid electron-hole recombination rates,and low quantum efficiencies.This review critically examines the key technical challenges and current strategies for further improving solar-to-fuel efficiency,with a focus on developing novel photocatalysts.Additionally,combining photocatalysis with biocatalysis,electrocatalysis,photo-electrochemical architectures,or membrane-assisted processes may enable the practical applications of artificial photosynthesis and help bridge the efficiency gap between lab-scale to industrial-scale.展开更多
Although supercritical carbon dioxide(SC-CO2)fracturing shows tremendous potential for maximizing injection efficiency and enhancing storage volumes,few investigations have been reported on the SC-CO2 fracturing...Although supercritical carbon dioxide(SC-CO2)fracturing shows tremendous potential for maximizing injection efficiency and enhancing storage volumes,few investigations have been reported on the SC-CO2 fracturing characteristics of tight basalts and the reactions between fractured basalt and SC-CO2.In this study,hydraulic fracturing experiments were conducted on cylindrical basalt specimens using water and SC-CO2 as fracturing fluids.Geometric parameters were proposed to characterize the fracture morphologies based on the three-dimensional(3D)reconstructions of fracture networks.The rock slices with induced fractures after SC-CO2 fracturing were then processed for fluid(deionized water/SC-CO2)-basalt reaction tests.The experimental results demonstrate that SC-CO2 fracturing can induce complex and tortuous fractures with spatially dispersed morphologies.Other fracturing behaviors accompanying the acoustic emission(AE)signals and pump pressure changes show that the AE activity responds almost simultaneously to variation in the pump pressure.The fractured basalt blocks exposed to both SC-CO2 and water exhibit rough and uneven surfaces,along with decreased intensities in the element peaks,indicating that solubility trapping predominantly occurs during the early injection stage.The above findings provide a laboratory research basis for understanding the fracturing and sequestration issues related to effective CO2 utilization.展开更多
The corrosion behavior of 304LN austenitic stainless steel in supercritical CO2 at 650℃ was investigated.The results show that 304LN follows Wagner’s law kinetics,forming a protective oxide flm consisting of SiO_...The corrosion behavior of 304LN austenitic stainless steel in supercritical CO2 at 650℃ was investigated.The results show that 304LN follows Wagner’s law kinetics,forming a protective oxide flm consisting of SiO2,(Cr,Mn)3O4,and Cr2O3 from the inner to outer layers.A shallow carburization depth of approximately 130 nm indicates excellent resistance to carburization.The roles of key elements in 18/8 austenitic stainless steel represented by 304LN,such as Cr,Ni,and Si,were analyzed,highlighting their contributions to anti-carburization performance and corrosion resistance under harsh conditions.展开更多
The electrocatalytic CO2 reduction reaction(CO2RR)offers a promising sustainable route for producing high-value C2+chemicals and fuels by using renewable electricity.However,boosting C2+product yields has ...The electrocatalytic CO2 reduction reaction(CO2RR)offers a promising sustainable route for producing high-value C2+chemicals and fuels by using renewable electricity.However,boosting C2+product yields has been significantly hindered by insufficient*CO intermediate generation in confined spaces and limited activity of sites for subsequent hydrogenation and C-C coupling processes.Herein,we introduce an efficient strategy that involves carbene dual-function bridging of Ag-Cu sites to enable*CO pooling and facilitate*COCHO coupling.As a result,a remarkable C2+Faradaic efficiency of 80.3%at 400 mA cm-2 was achieved.In-situ surface-enhanced Raman spectroscopy,in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy,and density functional theory calculations collectively uncover the underlying mechanism.Carbene facilitates CO spillover from Ag to Cu sites,modulates the electronic structure of Cu,stabilizes CO intermediates,and reduces the energy barrier for CO hydrogenation.These effects synergistically enhance C-C coupling,thereby improving the Faradaic efficiency for C2+product formation.展开更多
The injection of substantial quantities of carbon dioxide into subsurface reservoirs may alter the stress state of geological formations,potentially reactivating pre-existing faults and triggering induced seismicity.C...The injection of substantial quantities of carbon dioxide into subsurface reservoirs may alter the stress state of geological formations,potentially reactivating pre-existing faults and triggering induced seismicity.Comprehensive hydromechanical coupling analytical approaches for predicting CO2 injectioninduced earthquakes remain underdeveloped.This study proposed an analytical solution for fullycoupled hydromechanical modeling of a saline aquifer due to CO2 injection and applied it to the assessment of fault-related seismicity induced by CO2 geological storage.Firstly,we derived the analytical solutions for pore pressure buildup and stress change,considering not only pore pressure diffusion but also poroelastic stressing and caprock stiffness.Then,we quantifiedthe relative seismicity rates from Coulomb failure stress change using Dieterich's rate-and-state seismicity model.Subsequently,we investigated the occurrence rates and exceedance probabilities of CO2 injection-induced earthquakes with different magnitudes according to a hybrid physical-statistical approach.Finally,we conducted a series of parametric studies to reveal the influenceof several factors on induced seismicity.The results demonstrate several key findings.First,the proposed analytical solutions showed good agreement with multiphysics multiphase numerical simulation.Second,the traditional pure-hydraulic diffusion model overestimated the relative seismicity rate compared to the fully-coupled hydromechanical poroelastic model under a normal faulting stress regime.Third,the newly presented formula for the radius of the perturbed region was appropriate in reflectingthe spatial-temporal evolution of seismicity rate.Finally,among the factors,the CO2 injection rate had the largest impact on the occurrence rate and exceedance probability of induced earthquakes.In summary,this study established a comprehensive framework for evaluating CO2 injection-induced seismicity according to fully-coupled hydromechanical analytical solutions.展开更多
Cellular senescence plays a crucial role in respiratory diseases.Nitrogen dioxide(NO2),a major air pollutant,causes multi-system toxicity,primarily affecting the respiratory system.However,the association between N...Cellular senescence plays a crucial role in respiratory diseases.Nitrogen dioxide(NO2),a major air pollutant,causes multi-system toxicity,primarily affecting the respiratory system.However,the association between NO2and pulmonary senescence remains unclear.This study systematically explored the association between NO2exposure and premature pulmonary senescence using animal and cellular models.Rats were exposed for 45 days(4 h/day)to filtered air,0.5 ppmV,or 5.0 ppmV NO2.Human bronchial epithelial(HBE)cells were treated with 0 or 120μmol/L NaNO3,a stable metabolite of NO2,for 96 h.HBE cells exhibited hallmark senescence phenotypes,including elevated reactive oxygen species(ROS),increased expression of senescence-associated proteins(Fibronectin 1(Fn1),Clusterin(CLU),senescence Marker Protein 30(SMP30)),elevated β-galactosidase(β-gal)activity,increased developmentally regulated GTP-binding protein 1(DRG1)and cyclin-dependent protein kinase 5(CDK5)expression,and G1-phase cell cycle arrest.Treatment with the ROS inhibitor N-acetylcysteine(NAC),si-DRG1,or a CDK5 inhibitor alleviated these effects.Co-immunoprecipitation assays revealed that NaNO3promoted the interaction between DRG1 and CDK5 during senescence.The study demonstrated that NO2/NaNO3induces bronchial epithelial cellular senescence,contributing to pulmonary senescence via ROS-dependent upregulation of DRG1 and CDK5 expression and interaction.Targeting the ROS-DRG1/CDK5 axis may represent a therapeutic strategy for environmental pollutant-induced premature respiratory senescence and provide new insights for the management of related disorders.展开更多
基金Project supported by the National Natural Science Foundation of China(22338010)。
摘要The oxidative dehydrogenation of propane with carbon dioxide(CO2-ODP)has received significant attention as an environmentally benign route for the propene production.However,the development of high-performance catalysts remains a critical challenge hindering its industrial implementation.In this work,CeO2 samples with distinct morphologies resembling flowers(F-CeO2),rods(R-CeO2),spindles(SP-CeO2),and sheets(SH-CeO2)were successfully synthesized by simply changing the hydrothermal conditions,and the shape-dependent impact of oxygen-defect contents over CeO2 on the structural and electronic properties of the impregnated PtSn/CeO2 catalysts was studied for CO2-ODP.Characterizations reveal a positive correlation between the Pt electron density and oxygen-defect contents in an increasing order of PtSn/F-CeO2<PtSn/R-CeO2<PtSn/SP-CeO2<PtSn/SH-CeO2.In the case of the catalytic results,the same changing pattern is observed for the initial C3H8 conversion and C3H6selectivity.Moreover,the highest initial propene space-time yield of 0.71 kg_((C3H6))/(kg(cat)·h)achieving over the PtSn/SH-CeO2 catalyst is still retained at 0.35 kg_((C3H6))/(kg(cat)·h)after a time on stream of 200min.This perfo rmance surpasses those of most reported CO2-ODP catalysts.The morphology-dependent catalytic phenomena are attributed mainly to the varied activation energies of CO2-ODP,which are determined by the oxygen defect-induced electronic and structural interplay between Pt,Sn,and CeO2.These findings provide valuable insights for the rational design and optimization of Pt-based catalysts for CO2-ODP,particularly in the selection of oxide supports.
摘要To date,the question of how to address the challenges associated with urgent global carbon emissions while harnessing renewable energy remains unanswered,a challenge that our world has so far failed to solve.Among many strategies,artificial photosynthesis systems that mimic natural processes to enable the in-situ generation of protons(H+)for hydrogenation of CO2 into value-added carbonaceous fuels represent a promising route.Herein,this review highlights recent advancements in solar-driven photoreduction of CO2 in the presence of H+.Emphasis is placed on photocatalysts and their funda-mental mechanisms governing the photoreduction of CO2,including light absorption,charge-carrier dynamics,surface adsorption,and photocatalytic efficiency.The concept of dual-functional photo-catalytic active CO2 via in-situ generation of H+provides a sustainable and carbon-neutral pathway to produce renewable energy.Although many efforts have been made,the overall energy conversion ef-ficiency remains limited by the complexity of multistep reactions,rapid electron-hole recombination rates,and low quantum efficiencies.This review critically examines the key technical challenges and current strategies for further improving solar-to-fuel efficiency,with a focus on developing novel photocatalysts.Additionally,combining photocatalysis with biocatalysis,electrocatalysis,photo-electrochemical architectures,or membrane-assisted processes may enable the practical applications of artificial photosynthesis and help bridge the efficiency gap between lab-scale to industrial-scale.
基金supported by the National Key Research and Development Project(Grant No.2023YFE0110900)the National Natural Science Foundation of China(Grant No.42320104003)the Shanghai Pujiang Programme(Grant No.23PJD105).
摘要Although supercritical carbon dioxide(SC-CO2)fracturing shows tremendous potential for maximizing injection efficiency and enhancing storage volumes,few investigations have been reported on the SC-CO2 fracturing characteristics of tight basalts and the reactions between fractured basalt and SC-CO2.In this study,hydraulic fracturing experiments were conducted on cylindrical basalt specimens using water and SC-CO2 as fracturing fluids.Geometric parameters were proposed to characterize the fracture morphologies based on the three-dimensional(3D)reconstructions of fracture networks.The rock slices with induced fractures after SC-CO2 fracturing were then processed for fluid(deionized water/SC-CO2)-basalt reaction tests.The experimental results demonstrate that SC-CO2 fracturing can induce complex and tortuous fractures with spatially dispersed morphologies.Other fracturing behaviors accompanying the acoustic emission(AE)signals and pump pressure changes show that the AE activity responds almost simultaneously to variation in the pump pressure.The fractured basalt blocks exposed to both SC-CO2 and water exhibit rough and uneven surfaces,along with decreased intensities in the element peaks,indicating that solubility trapping predominantly occurs during the early injection stage.The above findings provide a laboratory research basis for understanding the fracturing and sequestration issues related to effective CO2 utilization.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA0410000)the CAS Project for Young Scientists in Basic Research(No.YSBR-043)+1 种基金the CNNC Science Fund for Talented Young Scholars,the National Funding Program for Postdoctoral Researchers(GZC20232747)the Youth Innovation Promotion Association CAS(2022187).
摘要The corrosion behavior of 304LN austenitic stainless steel in supercritical CO2 at 650℃ was investigated.The results show that 304LN follows Wagner’s law kinetics,forming a protective oxide flm consisting of SiO2,(Cr,Mn)3O4,and Cr2O3 from the inner to outer layers.A shallow carburization depth of approximately 130 nm indicates excellent resistance to carburization.The roles of key elements in 18/8 austenitic stainless steel represented by 304LN,such as Cr,Ni,and Si,were analyzed,highlighting their contributions to anti-carburization performance and corrosion resistance under harsh conditions.
摘要The electrocatalytic CO2 reduction reaction(CO2RR)offers a promising sustainable route for producing high-value C2+chemicals and fuels by using renewable electricity.However,boosting C2+product yields has been significantly hindered by insufficient*CO intermediate generation in confined spaces and limited activity of sites for subsequent hydrogenation and C-C coupling processes.Herein,we introduce an efficient strategy that involves carbene dual-function bridging of Ag-Cu sites to enable*CO pooling and facilitate*COCHO coupling.As a result,a remarkable C2+Faradaic efficiency of 80.3%at 400 mA cm-2 was achieved.In-situ surface-enhanced Raman spectroscopy,in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy,and density functional theory calculations collectively uncover the underlying mechanism.Carbene facilitates CO spillover from Ag to Cu sites,modulates the electronic structure of Cu,stabilizes CO intermediates,and reduces the energy barrier for CO hydrogenation.These effects synergistically enhance C-C coupling,thereby improving the Faradaic efficiency for C2+product formation.
基金the Joint Funds of the National Natural Science Foundation of China(Grant No.U2344226)the National Key R&D Program of China(Grant No.2022YFE0128300)the National Key R&D Program of China(Grant No.2023YFB4104100).
摘要The injection of substantial quantities of carbon dioxide into subsurface reservoirs may alter the stress state of geological formations,potentially reactivating pre-existing faults and triggering induced seismicity.Comprehensive hydromechanical coupling analytical approaches for predicting CO2 injectioninduced earthquakes remain underdeveloped.This study proposed an analytical solution for fullycoupled hydromechanical modeling of a saline aquifer due to CO2 injection and applied it to the assessment of fault-related seismicity induced by CO2 geological storage.Firstly,we derived the analytical solutions for pore pressure buildup and stress change,considering not only pore pressure diffusion but also poroelastic stressing and caprock stiffness.Then,we quantifiedthe relative seismicity rates from Coulomb failure stress change using Dieterich's rate-and-state seismicity model.Subsequently,we investigated the occurrence rates and exceedance probabilities of CO2 injection-induced earthquakes with different magnitudes according to a hybrid physical-statistical approach.Finally,we conducted a series of parametric studies to reveal the influenceof several factors on induced seismicity.The results demonstrate several key findings.First,the proposed analytical solutions showed good agreement with multiphysics multiphase numerical simulation.Second,the traditional pure-hydraulic diffusion model overestimated the relative seismicity rate compared to the fully-coupled hydromechanical poroelastic model under a normal faulting stress regime.Third,the newly presented formula for the radius of the perturbed region was appropriate in reflectingthe spatial-temporal evolution of seismicity rate.Finally,among the factors,the CO2 injection rate had the largest impact on the occurrence rate and exceedance probability of induced earthquakes.In summary,this study established a comprehensive framework for evaluating CO2 injection-induced seismicity according to fully-coupled hydromechanical analytical solutions.
基金supported by Hunan Provincial Natural Science Foundation for Distinguished Young Scholars(No.2024JJ2082)the National Natural Science Foundation of China(No.42277438)the Postgraduate Independent Exploration and Innovation Project of Hunan Province,China(No.CX20230121).
摘要Cellular senescence plays a crucial role in respiratory diseases.Nitrogen dioxide(NO2),a major air pollutant,causes multi-system toxicity,primarily affecting the respiratory system.However,the association between NO2and pulmonary senescence remains unclear.This study systematically explored the association between NO2exposure and premature pulmonary senescence using animal and cellular models.Rats were exposed for 45 days(4 h/day)to filtered air,0.5 ppmV,or 5.0 ppmV NO2.Human bronchial epithelial(HBE)cells were treated with 0 or 120μmol/L NaNO3,a stable metabolite of NO2,for 96 h.HBE cells exhibited hallmark senescence phenotypes,including elevated reactive oxygen species(ROS),increased expression of senescence-associated proteins(Fibronectin 1(Fn1),Clusterin(CLU),senescence Marker Protein 30(SMP30)),elevated β-galactosidase(β-gal)activity,increased developmentally regulated GTP-binding protein 1(DRG1)and cyclin-dependent protein kinase 5(CDK5)expression,and G1-phase cell cycle arrest.Treatment with the ROS inhibitor N-acetylcysteine(NAC),si-DRG1,or a CDK5 inhibitor alleviated these effects.Co-immunoprecipitation assays revealed that NaNO3promoted the interaction between DRG1 and CDK5 during senescence.The study demonstrated that NO2/NaNO3induces bronchial epithelial cellular senescence,contributing to pulmonary senescence via ROS-dependent upregulation of DRG1 and CDK5 expression and interaction.Targeting the ROS-DRG1/CDK5 axis may represent a therapeutic strategy for environmental pollutant-induced premature respiratory senescence and provide new insights for the management of related disorders.