Ce-TiO2/CA（carbon aerogel） electrode was prepared by sol impregnation approach. The XRD（X-ray diffraction） and Raman spectra reveal that the TiO2 is anatase. The UV-vis diffuse reflectance spectra show that the op...Ce-TiO2/CA（carbon aerogel） electrode was prepared by sol impregnation approach. The XRD（X-ray diffraction） and Raman spectra reveal that the TiO2 is anatase. The UV-vis diffuse reflectance spectra show that the optical absorption edge for Ce-TiO_2/CA is red-shifted to 535 nm compared with TiO_2/CA. Under visible light irradiation, the photocurrent density increment on Ce-TiO_2/CA is 75 times that on Ce-TiO_2/FTO（fluorine-doped tin oxide）. The electrochemical impedance spectroscopy reveals that the conductivity of CeTiO_2/CA is much better than the Ce-TiO_2/FTO. Furthermore, the Ce-TiO_2/CA can be used to the highest electrosorptive photodegradation for 4-chlorophenol wastewater degradation, which is ascribed predominantly to the efficient reduction of electron-hole pair recombination in the photocatalysts.展开更多
Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2)...Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.展开更多
Synergy strategy of photocatalysts and polymer resins are promising technology for marine antifouling.However,it is still a main challenge to obtain a green,safe,and efficient antifouling coatings.Herein,carbon(graphe...Synergy strategy of photocatalysts and polymer resins are promising technology for marine antifouling.However,it is still a main challenge to obtain a green,safe,and efficient antifouling coatings.Herein,carbon(graphene or CNT)modified Ti O_(2)photocatalyst was synthesized via hydrothermal and annealing process and has successfully applied in acrylate fluoroboron polymer(ABFP)composite coating.Morphology and chemical composition were detailed characterized.The graphene or CNT acted as a bridge with supplemental spatial structures(petal gaps,entanglement)and new functional groups(C-O,C-Ti-O,etc.)on Ti O_(2)particle.Carbon nanotube(CNT)modified TiO_(2)-ABFP coatings(BTCP)achieved excellent antibacterial and anti-diatom adhesion rate of 89.3%-96.70%and 99.00%-99.50%,which was 1.84-4.94-fold more than that of the single ABFP.CNT or graphene served as electronic bridges was considered as the crucial mechanism,which significantly improved the light absorption range and capacity,conductivity,and photoelectric response of Ti O_(2),and further accelerated the generation and transfer of free radicals to the surface of BTCP or FTGP.Moreover,the improvement of catalyst activity synergizes with the smooth surface,hydrophilicity,and slow hydrolysis of composite coatings,achieved long-term and efficient antifouling performance.This work provides a new insight into the modification of Ti O_(2)and antifouling mechanism of polymer coating.展开更多
This paper proposes that China,under the challenge of balancing its development and security,can aim for the Paris Agreement's goal to limit global warming to no more than 2℃by actively seeking carbonpeak and car...This paper proposes that China,under the challenge of balancing its development and security,can aim for the Paris Agreement's goal to limit global warming to no more than 2℃by actively seeking carbonpeak and carbon-neutrality pathways that align with China's national conditions,rather than following the idealized path toward the 1.5℃target by initially relying on extensive negative-emission technologies such as direct air carbon capture and storage(DACCS).This work suggests that pursuing a 1.5℃target is increasingly less feasible for China,as it would potentially incur 3–4 times the cost of pursuing the 2℃target.With China being likely to achieve a peak in its emissions around 2028,at about 12.8 billion tonnes of anthropogenic carbon dioxide(CO_(2)),and become carbon neutral,projected global warming levels may be less severe after the 2050s than previously estimated.This could reduce the risk potential of climate tipping points and extreme events,especially considering that the other two major carbon emitters in the world(Europe and North America)have already passed their carbon peaks.While natural carbon sinks will contribute to China's carbon neutrality efforts,they are not expected to be decisive in the transition stages.This research also addresses the growing focus on climate overshoot,tipping points,extreme events,loss and damage,and methane reductions in international climate cooperation,emphasizing the need to balance these issues with China's development,security,and fairness considerations.China's pursuit of carbon neutrality will have significant implications for global emissions scenarios,warming levels,and extreme event projections,as well as for climate change hotspots of international concern,such as climate tipping points,the climate crisis,and the notion that the world has moved from a warming to a boiling era.Possible research recommendations for global emissions scenarios based on China's 2℃target pathway are also summarized.展开更多
Carbon capture is an important strategy and is implemented to achieve the goals of CO_(2)reduction and carbon neutrality.As a high energy-efficient technology,membrane-based separation plays a crucial role in CO_(2)ca...Carbon capture is an important strategy and is implemented to achieve the goals of CO_(2)reduction and carbon neutrality.As a high energy-efficient technology,membrane-based separation plays a crucial role in CO_(2)capture.It is urgently needed for membrane-based CO_(2)capture to develop the high-performance membrane materials with high permeability,selectivity,and stability.Herein,ultrapermeable carbon molecular sieve(CMS)membranes are fabricated by py roly zing a finely-engineered benzoxazole-containing copolyimide precursor for efficient CO_(2)capture.The microstructure of CMS membrane has been optimized by initially engineering the precursor-chemistry and subsequently tuning the pyrolysis process.Deep insights into the structure-property relationship of CMSs are provided in detail by a combination of experimental characterization and molecular simulations.We demonstrate that the intrinsically high free volume environment of the precursor,coupled with the steric hindrance of thermostable contorted fragments,promotes the formation of loosely packed and ultramicroporous carbon structures within the resultant CMS membrane,thereby enabling efficient CO_(2)discrimination via size sieving and affinity.The membrane achieves an ultrahigh CO_(2)permeability,good selectivity,and excellent stability.After one month of long-term operation,the CO_(2)permeability in the mixed gas is maintained at 11,800 Barrer,with a CO_(2)/N_(2)selectivity exceeding 60.This study provides insights into the relationship between precursor-chemistry and CMS performance,and our ultrapermeable CMS membrane,which is scalable using thin film manufacturing,holds great potential for industrial CO_(2)capture.展开更多
In the background of the low-carbon transformation of the energy structure,the problem of operational uncertainty caused by the high proportion of renewable energy sources and diverse loads in the integrated energy sy...In the background of the low-carbon transformation of the energy structure,the problem of operational uncertainty caused by the high proportion of renewable energy sources and diverse loads in the integrated energy systems(IES)is becoming increasingly obvious.In this case,to promote the low-carbon operation of IES and renewable energy consumption,and to improve the IES anti-interference ability,this paper proposes an IES scheduling strategy that considers CCS-P2G and concentrating solar power(CSP)station.Firstly,CSP station,gas hydrogen doping mode and variable hydrogen doping ratio mode are applied to IES,and combined with CCS-P2G coupling model,the IES low-carbon economic dispatch model is established.Secondly,the stepped carbon trading mechanism is applied,and the sensitivity analysis of IES carbon trading is carried out.Finally,an IES optimal scheduling strategy based on fuzzy opportunity constraints and an IES risk assessment strategy based on CVaR theory are established.The simulation shows that the gas-hydrogen doping model proposed in this paper reduces the operating cost and carbon emission of IES by 1.32%and 7.17%,and improves the carbon benefit by 5.73%;variable hydrogen doping ratio model reduces the operating cost and carbon emission of IES by 3.75%and 1.70%,respectively;CSP stations reduce 19.64%and 38.52%of the operating costs of IES and 1.03%and 1.80%of the carbon emissions of IES respectively compared to equal-capacity photovoltaic and wind turbines;the baseline price of carbon trading of IES and its rate of change jointly affect the carbon emissions of IES;evaluating the anti-interference capability of IES through trapezoidal fuzzy number and weighting coefficients,enabling IES to guarantee operation at the lowest cost.展开更多
Electromagnetic interference,which necessitates the rapid advancement of substances with exceptional capabilities for bsorbing electromagnetic waves,is of urgent concern in contemporary society.In this work,CoFe_(2)O_...Electromagnetic interference,which necessitates the rapid advancement of substances with exceptional capabilities for bsorbing electromagnetic waves,is of urgent concern in contemporary society.In this work,CoFe_(2)O_(4)/residual carbon from coal gasification fine slag(CFO/RC)composites were created using a novel hydrothermal method.Various mechanisms for microwave absorption,including conductive loss,natural resonance,interfacial dipole polarization,and magnetic flux loss,are involved in these composites.Consequently,compared with pure residual carbon materials,this composite offers superior capabilities in microwave absorption.At 7.76GHz,the CFO/RC-2 composite achieves an impressive minimum reflection loss(RL_(min))of-43.99 dB with a thickness of 2.44 mm.Moreover,CFO/RC-3 demonstrates an effective absorption bandwidth(EAB)of up to 4.16 GHz,accompanied by a thickness of 1.18mm.This study revealed the remarkable capability of the composite to diminish electromagnetic waves,providing a new generation method for microwave absorbing materials of superior quality.展开更多
Herein,we report a simple self-charging hybrid power system(SCHPS)based on binder-free zinc copper selenide nanostructures(ZnCuSe_(2) NSs)deposited carbon fabric(CF)(i.e.,ZnCuSe_(2)/CF),which is used as an active mate...Herein,we report a simple self-charging hybrid power system(SCHPS)based on binder-free zinc copper selenide nanostructures(ZnCuSe_(2) NSs)deposited carbon fabric(CF)(i.e.,ZnCuSe_(2)/CF),which is used as an active material in the fabrication of supercapacitor(SC)and triboelectric nanogenerator(TENG).At first,a binder-free ZnCuSe_(2)/CF was synthesized via a simple and facial hydrothermal synthesis approach,and the electrochemical properties of the obtained ZnCuSe_(2)/CF were evaluated by fabricating a symmetric quasi-solid-state SC(SQSSC).The ZCS-2(Zn:Cu ratio of 2:1)material deposited CF-based SQSSC exhibited good electrochemical properties,and the obtained maximum energy and power densities were 7.5 Wh kg^(-1)and 683.3 W kg^(-1),respectively with 97.6%capacitance retention after 30,000 cycles.Furthermore,the ZnCuSe_(2)/CF was coated with silicone rubber elastomer using a doctor blade technique,which is used as a negative triboelectric material in the fabrication of the multiple TENG(M-TENG).The fabricated M-TENG exhibited excellent electrical output performance,and the robustness and mechanical stability of the device were studied systematically.The practicality and applicability of the proposed M-TENG and SQSSC were systematically investigated by powering various low-power portable electronic components.Finally,the SQSSC was combined with the M-TENG to construct a SCHPS.The fabricated SCHPS provides a feasible solution for sustainable power supply,and it shows great potential in self-powered portable electronic device applications.展开更多
Manganese(Mn),an essential trace element in the human body,plays critical roles in many biological processes.Recent studies have discovered that Mn^(2+)may promote or directly activate the cGAS-STING pathway,thereby s...Manganese(Mn),an essential trace element in the human body,plays critical roles in many biological processes.Recent studies have discovered that Mn^(2+)may promote or directly activate the cGAS-STING pathway,thereby subsequently initiating the natural immune response and augmenting antitumor therapy.However,the current lack of accurate methods for Mn^(2+)determination in cells significantly limits their mechanism investigation;hence,it is urgent to establish novel tools to detect Mn^(2+)in cells.In this study,the dual-emission carbon dots were initially synthesized via the one-pot hydrothermal method employing L-aspartic acid and p-phenylenediamine as raw materials.In the presence of Mn^(2+),the emission peak centered at 350 nm exhibited significant enhancement,whereas another peak at 610 nm remained stable.Consequently,a ratiometric sensor for Mn^(2+)determination was established using the signal at 350 nm as the responsive signal and the signal at 610 nm as an internal reference.Under the optimal condition,a good linear relationship was achieved between the F350/F610 value and Mn^(2+)concentration ranging from 0.9 to 15μmol/L,with a calculated LOD of 61 nmol/L.Benefiting from the special Mn^(2+)-induced ratiometric approach,this method demonstrates outstanding sensitivity,selectivity,and stability,rendering it applicable for Mn^(2+)determination in complex biological samples,as well as Mn^(2+)imaging in MKN-45 and LO2 cells.展开更多
The need for bi-functional catalysts that facilit-ate both the oxygen reduction(ORR)and carbon dioxide re-duction(CO_(2)RR)reactions arises from their potential to help solve the critical problems of carbon neutrality...The need for bi-functional catalysts that facilit-ate both the oxygen reduction(ORR)and carbon dioxide re-duction(CO_(2)RR)reactions arises from their potential to help solve the critical problems of carbon neutrality and renew-able energy conversion.However,there are few reports on the development of bi-functional catalysts for zinc-air bat-tery-driven CO_(2)RR devices.We introduce a novel approach for synthesizing Fe_(2)N/Fe_(3)C species embedded in nitrogen-doped carbon nanofibers by electrospinning a solution of Hemin and polyacrylonitrile in N,N-dimethylformamide.The material has an exceptional catalytic performance,with a half-wave potential of 0.91 V versus RHE for the ORR and values of over 90%for both the selectivity and Faradaic efficiency for the CO_(2)RR.The high catalytic performances are attrib-uted to the strong coupling between the Fe_(3)C/Fe_(2)N heterostructure and the Fe-N-C sites in the nitrogen-doped carbon nan-ofibers.Notably,both Fe_(3)C and Fe_(2)N play distinct roles in both the ORR and CO_(2)RR.This investigation indicates a way for designing advanced carbon-based bi-functional catalysts for use in this field.展开更多
The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace K...The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.展开更多
The advancement of planar micro-supercapacitors(PMSCs)for micro-electromechanical systems(MEMS)has been significantly hindered by the challenge of achieving high energy and power densities.This study addresses this is...The advancement of planar micro-supercapacitors(PMSCs)for micro-electromechanical systems(MEMS)has been significantly hindered by the challenge of achieving high energy and power densities.This study addresses this issue by leveraging screen-printing technology to fabricate high-performance PMSCs using innovative composite ink.The ink,a synergistic blend of few-layer graphene(Gt),carbon black(CB),and NiCo_(2)O_(4),was meticulously mixed to form a conductive and robust coating that enhanced the capacitive performance of the PMSCs.The optimized ink formulation and printing process result in a micro-supercapacitor with an exceptional areal capacitance of 18.95 mF/cm^(2)and an areal energy density of 2.63μW·h/cm^(2)at a current density of 0.05 mA/cm^(2),along with an areal power density of 0.025 mW/cm^(2).The devices demonstrated impressive durability with a capacitance retention rate of 94.7%after a stringent 20000-cycle test,demonstrating their potential for long-term applications.Moreover,the PMSCs displayed excellent mechanical flexibility,with a capacitance decrease of only 3.43%after 5000 bending cycles,highlighting their suitability for flexible electronic devices.The ease of integrating these PMSCs into series and parallel configurations for customized power further underscores their practicality for integrated power supply solutions in various technologies.展开更多
China is the largest emitter of anthropogenic CO_(2) globally,with its cities recognized as significant emission hotspots.Consequently,evaluating anthropogenic CO_(2) emissions and the carbon neutral capability(CNC)of...China is the largest emitter of anthropogenic CO_(2) globally,with its cities recognized as significant emission hotspots.Consequently,evaluating anthropogenic CO_(2) emissions and the carbon neutral capability(CNC)of Chinese cities is critical for climate change mitigation.Despite this importance,no studies to date have assessed recent and future city-scale CNCs using the top-down atmospheric inversion approach,revealing substantial knowledge gaps regarding regional CO_(2) budgets.To address these issues,this research focused on Hangzhou,a megacity known for having the highest forest cover among China’s provincial capitals,as study region.Year-round atmospheric CO_(2) concentration measurements were conducted from December 2020 to November 2021 at two sites:one urban and one suburban.These observations,along with their difference,were utilized to derive city-scale posterior anthropogenic CO_(2) emissions and to evaluate recent and future CNCs.Our key findings are as follows:(1)The manufacturing industry,energy industry and oil refineries/transformation industry were identified as the largest contributors to urban-suburban CO_(2) difference,accounting for 36.5%,21.3%,and 16.6%,respectively.Additionally,82.5%,65.2%,81.2%and 86.3%of total anthropogenic CO_(2) enhancements were attributed to emissions within Hangzhou city in winter,spring,summer and autumn,respectively.(2)The posterior annual anthropogenic CO_(2) emission for Hangzhouwas estimated at 4.65(±0.72)×10^(10) kg/a,indicating significant biases among different prior CO_(2) emission inventories.The annual biological CO_(2) sink,derived from multiple products,was estimated at-0.48(±0.16)×10^(10) kg.(3)The calculated CNC for 2021was 10.3%±3.4%,highlighting a substantial gap towards achieving full carbon neutrality.Considering potential increases in ecosystem carbon sinks due to forest age and uncertainties from climate change,it was predicted that at least 65.2%-82.6%of anthropogenic CO_(2) emissions must be reduced to achieve the goal of full carbon neutrality by year of 2060.展开更多
The catalytic direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol is a crucial approach to utilizing CO_(2)and producing high-value chemicals.However,the high stability of the CO_(2)molecule imposes the...The catalytic direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol is a crucial approach to utilizing CO_(2)and producing high-value chemicals.However,the high stability of the CO_(2)molecule imposes thermodynamic limitations on this reaction pathway,along with challenges related to insufficient catalyst activity and stability.Currently,solutions primarily focus on developing efficient catalyst.Herein,La-doped CeO_(2)nanoflower catalysts(La_(x)CeO_(2))were synthesized via hydrothermal method.Characterization reveals that La doping optimizes the pore structure and enriched oxygen vacancies,thereby enhancing catalytic performance.Notably,La_(0.1)CeO_(2)exhibits the largest pore size and highest oxygen vacancy content,achieving a remarkable DMC productivity of 9.42 mmol/g under 140℃,4 MPa of CO_(2),and 3 h of reactio n,surpassing pure CeO_(2)nano flowers.Based on experimental findings and in-situ diffuse infrared Fourier transform analysis,a plausible reaction pathway was proposed.This work underscores the potential of La_(x)CeO_(2)nano flowers as efficient catalysts for sustainable CO_(2)conversion to DMC.展开更多
Mitigating climate change demands innovative solutions,and carbon sequestration technologies are at the forefront.Among these,basalt,a mafic volcanic rock packed with calcium,magnesium,and iron,emerges as a powerful c...Mitigating climate change demands innovative solutions,and carbon sequestration technologies are at the forefront.Among these,basalt,a mafic volcanic rock packed with calcium,magnesium,and iron,emerges as a powerful candidate for carbon dioxide(CO_(2))sequestration through mineral carbonation.This method transforms CO_(2)into stable carbonate minerals,ensuring a permanent and environmentally safe storage solution.While extensive research has explored into basalt’s potential under high hydration conditions,the untapped promise of low water content scenarios remains largely unexplored.Our ground-breaking study investigates the mineral carbonation of basalt powder under low water condi-tions using supercritical CO_(2)(sc-CO_(2)).Conducted at 50℃ and 15 MPa with a controlled moisture content of 30%,our experiment spans various time points(0,7,14,21,and 28 days).Utilising advanced X-ray diffraction(XRD)and scanning electron microscopy with energy-dispersive X-ray spectroscopy(SEM-EDS),we unveil the mineralogical and morphological transformations.The results are striking:even under low water conditions,basalt efficiently forms valuable carbonate minerals such as calcite,siderite,magnesite,and ankerite.The carbonation efficiency evolves over time,reflecting the dynamic transfor-mation of the basalt matrix.These findings offer pivotal insights into optimising CO_(2)sequestration in basalt under low hydration,marking a significant leap toward sustainable carbon capture and storage.展开更多
The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportio...The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.展开更多
Transition metal-carbonate interfaces often act as active sites in heterogeneous catalytic reactions.The interface between transition metal and metal carbonate exhibits a dynamic equilibrium during the CO_(2)hydrogena...Transition metal-carbonate interfaces often act as active sites in heterogeneous catalytic reactions.The interface between transition metal and metal carbonate exhibits a dynamic equilibrium during the CO_(2)hydrogenation reaction,involving surface carbonate hydrogenation and CO_(2)chemisorption.Nonetheless,there have been few reports on engineering the activity of the interface between transition metal and alkaline earth metal carbonate for catalytic CO_(2)conversion.This work demonstrated that the incorporation of CaH_(2)in Ni/CaCO_(3)enhances the CO_(2)methanation activity of the catalysts.The CO_(2)conversion for Ni/CaH_(2)-CaCO_(3)reached 68.5%at 400°C,which was much higher than that of the Ni/CaCO_(3)(31.6%) and Ni/CaH_(2)-CaO (42.4%) catalysts.Furthermore,the Ni/CaH_(2)-CaCO_(3)catalysts remained stable during the stability test for 24 h at 400°C and 8 bar.Our research revealed that CaH_(2)played a crucial role in promoting the activity of the Ni-carbonate interface for CO_(2)methanation.CaH_(2)could modify the electronic structure of Ni and tune the structural properties of CaCO_(3)to generate medium basic sites (OH groups),which are favorable for the activation of H2and CO_(2).In-situ Fourier transform infrared spectroscopy (FTIR) analysis combined with density functional theory calculations demonstrated that CO_(2)activation occurs at the hydroxyl group (OH) on the CaH_(2)-modified Ni-carbonate surface,leading to the formation of CO_(3)H*species.Furthermore,our study has confirmed that CO_(2)methanation over the Ni/CaH_(2)-CaCO_(3)catalysts proceeds via the formate pathway.展开更多
基金Project supported jointly by the Foundation of He'nan Educational Committee(15A150071)
文摘Ce-TiO2/CA（carbon aerogel） electrode was prepared by sol impregnation approach. The XRD（X-ray diffraction） and Raman spectra reveal that the TiO2 is anatase. The UV-vis diffuse reflectance spectra show that the optical absorption edge for Ce-TiO_2/CA is red-shifted to 535 nm compared with TiO_2/CA. Under visible light irradiation, the photocurrent density increment on Ce-TiO_2/CA is 75 times that on Ce-TiO_2/FTO（fluorine-doped tin oxide）. The electrochemical impedance spectroscopy reveals that the conductivity of CeTiO_2/CA is much better than the Ce-TiO_2/FTO. Furthermore, the Ce-TiO_2/CA can be used to the highest electrosorptive photodegradation for 4-chlorophenol wastewater degradation, which is ascribed predominantly to the efficient reduction of electron-hole pair recombination in the photocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.22106105 and 22201180)the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-E00015)+2 种基金Shanghai Science and Technology Innovation Program(No.21DZ1206300)the Central Local Science and Technology Development Guidance Fund(No.YDZX20213100003002)Shanghai Science and Technology Commission Program(No.20060502200).
文摘Photocatalytic conversion of CO_(2) is pivotal for mitigating the global greenhouse effect and fostering sustainable energy development.Nowadays,polymeric carbon nitride(PCN)has gained widespread application in CO_(2) solar reduction due to its excellent visible light response,suitable conduction band position,and good cost-effectiveness.However,the amorphous nature and low conductivity of PCN limit its photocatalytic efficiency by leading to low carrier concentrations and facile electron–hole recombination during photocatalysis.Addressing this bottleneck,in this study,potassium-doped PCN(KPCN)/copper(Ⅱ)-complexed bipyridine hydroxyquinoline carboxylic acid(Cu(Ⅱ)(bpy)(H_(2)hqc))composite catalysts were synthesized through a multistep microwave heating process.In the composite,the formation of an S-scheme junction facilitates the enrichment of more negative electrons on the conduction band of KPCN via intermolecular electron–hole recombination between Cu(Ⅱ)(bpy)(H_(2)hqc)(CuPyQc)and KPCN,thereby promoting efficient photoreduction of CO_(2) to CO.Microwave heating enhances the amidation reaction between these two components,achieving the immobilization of homogeneous molecular catalysts and forming amidation chemical bonds that serve as key channels for the S-scheme charge transfer.This work not only presents a new PCN-based catalytic system for CO_(2) reduction applications,but also offers a novel microwave-practical approach for immobilizing homogeneous catalysts.
基金supported by the National Natural Science Foundation of China(Nos.42277315,22066009)the Scientific Research Startup Fund of Hainan University(Nos.XJ2300005916,kyqd(zr)22185)+1 种基金supported by Scientific Research Project of Hainan Higher Education Institutions(No.Hnky2023-9)Innovational Fund for Scientific and Technological Personnel of Hainan Province(No.KJRC2023C12)。
文摘Synergy strategy of photocatalysts and polymer resins are promising technology for marine antifouling.However,it is still a main challenge to obtain a green,safe,and efficient antifouling coatings.Herein,carbon(graphene or CNT)modified Ti O_(2)photocatalyst was synthesized via hydrothermal and annealing process and has successfully applied in acrylate fluoroboron polymer(ABFP)composite coating.Morphology and chemical composition were detailed characterized.The graphene or CNT acted as a bridge with supplemental spatial structures(petal gaps,entanglement)and new functional groups(C-O,C-Ti-O,etc.)on Ti O_(2)particle.Carbon nanotube(CNT)modified TiO_(2)-ABFP coatings(BTCP)achieved excellent antibacterial and anti-diatom adhesion rate of 89.3%-96.70%and 99.00%-99.50%,which was 1.84-4.94-fold more than that of the single ABFP.CNT or graphene served as electronic bridges was considered as the crucial mechanism,which significantly improved the light absorption range and capacity,conductivity,and photoelectric response of Ti O_(2),and further accelerated the generation and transfer of free radicals to the surface of BTCP or FTGP.Moreover,the improvement of catalyst activity synergizes with the smooth surface,hydrophilicity,and slow hydrolysis of composite coatings,achieved long-term and efficient antifouling performance.This work provides a new insight into the modification of Ti O_(2)and antifouling mechanism of polymer coating.
基金supported by the top-level design of the National Natural Science Foundation of China(NSFC)Major Project“Realization of optimal carbon neutral pathway and coupling of multi-scale interaction patterns of natural-social systems in China”(42341202)the Basic Scientific Research Fund of the Chinese Academy of Meteorological Sciences(2021Z014)。
文摘This paper proposes that China,under the challenge of balancing its development and security,can aim for the Paris Agreement's goal to limit global warming to no more than 2℃by actively seeking carbonpeak and carbon-neutrality pathways that align with China's national conditions,rather than following the idealized path toward the 1.5℃target by initially relying on extensive negative-emission technologies such as direct air carbon capture and storage(DACCS).This work suggests that pursuing a 1.5℃target is increasingly less feasible for China,as it would potentially incur 3–4 times the cost of pursuing the 2℃target.With China being likely to achieve a peak in its emissions around 2028,at about 12.8 billion tonnes of anthropogenic carbon dioxide(CO_(2)),and become carbon neutral,projected global warming levels may be less severe after the 2050s than previously estimated.This could reduce the risk potential of climate tipping points and extreme events,especially considering that the other two major carbon emitters in the world(Europe and North America)have already passed their carbon peaks.While natural carbon sinks will contribute to China's carbon neutrality efforts,they are not expected to be decisive in the transition stages.This research also addresses the growing focus on climate overshoot,tipping points,extreme events,loss and damage,and methane reductions in international climate cooperation,emphasizing the need to balance these issues with China's development,security,and fairness considerations.China's pursuit of carbon neutrality will have significant implications for global emissions scenarios,warming levels,and extreme event projections,as well as for climate change hotspots of international concern,such as climate tipping points,the climate crisis,and the notion that the world has moved from a warming to a boiling era.Possible research recommendations for global emissions scenarios based on China's 2℃target pathway are also summarized.
基金financial support from the National Key R&D Program of China(2021YFB3801200)the National Natural Science Foundation of China(22278051,22178044,22308043)CNPC Innovation Found(2022DQ02-0608)。
文摘Carbon capture is an important strategy and is implemented to achieve the goals of CO_(2)reduction and carbon neutrality.As a high energy-efficient technology,membrane-based separation plays a crucial role in CO_(2)capture.It is urgently needed for membrane-based CO_(2)capture to develop the high-performance membrane materials with high permeability,selectivity,and stability.Herein,ultrapermeable carbon molecular sieve(CMS)membranes are fabricated by py roly zing a finely-engineered benzoxazole-containing copolyimide precursor for efficient CO_(2)capture.The microstructure of CMS membrane has been optimized by initially engineering the precursor-chemistry and subsequently tuning the pyrolysis process.Deep insights into the structure-property relationship of CMSs are provided in detail by a combination of experimental characterization and molecular simulations.We demonstrate that the intrinsically high free volume environment of the precursor,coupled with the steric hindrance of thermostable contorted fragments,promotes the formation of loosely packed and ultramicroporous carbon structures within the resultant CMS membrane,thereby enabling efficient CO_(2)discrimination via size sieving and affinity.The membrane achieves an ultrahigh CO_(2)permeability,good selectivity,and excellent stability.After one month of long-term operation,the CO_(2)permeability in the mixed gas is maintained at 11,800 Barrer,with a CO_(2)/N_(2)selectivity exceeding 60.This study provides insights into the relationship between precursor-chemistry and CMS performance,and our ultrapermeable CMS membrane,which is scalable using thin film manufacturing,holds great potential for industrial CO_(2)capture.
基金State Grid Gansu Electric Power Company Science and Technology Program(Grant No.W24FZ2730008)National Natural Science Foundation of China(Grant No.51767017).
文摘In the background of the low-carbon transformation of the energy structure,the problem of operational uncertainty caused by the high proportion of renewable energy sources and diverse loads in the integrated energy systems(IES)is becoming increasingly obvious.In this case,to promote the low-carbon operation of IES and renewable energy consumption,and to improve the IES anti-interference ability,this paper proposes an IES scheduling strategy that considers CCS-P2G and concentrating solar power(CSP)station.Firstly,CSP station,gas hydrogen doping mode and variable hydrogen doping ratio mode are applied to IES,and combined with CCS-P2G coupling model,the IES low-carbon economic dispatch model is established.Secondly,the stepped carbon trading mechanism is applied,and the sensitivity analysis of IES carbon trading is carried out.Finally,an IES optimal scheduling strategy based on fuzzy opportunity constraints and an IES risk assessment strategy based on CVaR theory are established.The simulation shows that the gas-hydrogen doping model proposed in this paper reduces the operating cost and carbon emission of IES by 1.32%and 7.17%,and improves the carbon benefit by 5.73%;variable hydrogen doping ratio model reduces the operating cost and carbon emission of IES by 3.75%and 1.70%,respectively;CSP stations reduce 19.64%and 38.52%of the operating costs of IES and 1.03%and 1.80%of the carbon emissions of IES respectively compared to equal-capacity photovoltaic and wind turbines;the baseline price of carbon trading of IES and its rate of change jointly affect the carbon emissions of IES;evaluating the anti-interference capability of IES through trapezoidal fuzzy number and weighting coefficients,enabling IES to guarantee operation at the lowest cost.
基金financially supported by the Key Project of Natural Science Research in Colleges and Universities of Anhui Province,China(No.2022AH050816)the Open Research Grant of Joint National-Local Engineering Research Centre for Safe and Precise Coal Mining(Nos.EC2023013 and EC2022018)+1 种基金the National Natural Science Foundation of China(No.52200139)the Introduction of Talent in Anhui University of Science and Technology,China(Nos.2021yjrc18 and 2023yjrc79)。
文摘Electromagnetic interference,which necessitates the rapid advancement of substances with exceptional capabilities for bsorbing electromagnetic waves,is of urgent concern in contemporary society.In this work,CoFe_(2)O_(4)/residual carbon from coal gasification fine slag(CFO/RC)composites were created using a novel hydrothermal method.Various mechanisms for microwave absorption,including conductive loss,natural resonance,interfacial dipole polarization,and magnetic flux loss,are involved in these composites.Consequently,compared with pure residual carbon materials,this composite offers superior capabilities in microwave absorption.At 7.76GHz,the CFO/RC-2 composite achieves an impressive minimum reflection loss(RL_(min))of-43.99 dB with a thickness of 2.44 mm.Moreover,CFO/RC-3 demonstrates an effective absorption bandwidth(EAB)of up to 4.16 GHz,accompanied by a thickness of 1.18mm.This study revealed the remarkable capability of the composite to diminish electromagnetic waves,providing a new generation method for microwave absorbing materials of superior quality.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(No.2018R1A6A1A03025708)partly supported by the GRRC program of Gyeonggi province(GRRCKyungHee2023-B03).
文摘Herein,we report a simple self-charging hybrid power system(SCHPS)based on binder-free zinc copper selenide nanostructures(ZnCuSe_(2) NSs)deposited carbon fabric(CF)(i.e.,ZnCuSe_(2)/CF),which is used as an active material in the fabrication of supercapacitor(SC)and triboelectric nanogenerator(TENG).At first,a binder-free ZnCuSe_(2)/CF was synthesized via a simple and facial hydrothermal synthesis approach,and the electrochemical properties of the obtained ZnCuSe_(2)/CF were evaluated by fabricating a symmetric quasi-solid-state SC(SQSSC).The ZCS-2(Zn:Cu ratio of 2:1)material deposited CF-based SQSSC exhibited good electrochemical properties,and the obtained maximum energy and power densities were 7.5 Wh kg^(-1)and 683.3 W kg^(-1),respectively with 97.6%capacitance retention after 30,000 cycles.Furthermore,the ZnCuSe_(2)/CF was coated with silicone rubber elastomer using a doctor blade technique,which is used as a negative triboelectric material in the fabrication of the multiple TENG(M-TENG).The fabricated M-TENG exhibited excellent electrical output performance,and the robustness and mechanical stability of the device were studied systematically.The practicality and applicability of the proposed M-TENG and SQSSC were systematically investigated by powering various low-power portable electronic components.Finally,the SQSSC was combined with the M-TENG to construct a SCHPS.The fabricated SCHPS provides a feasible solution for sustainable power supply,and it shows great potential in self-powered portable electronic device applications.
基金Supported by National Natural Science Foundation of China(22264023)Natural Science Foundation of Shaanxi Province(2024JC-YBQN-0150)+2 种基金Yan'an Science and Technology Bureau Project(2023-SFGG-057)Scientific Research Projects of Education Department of Shaanxi Province(22JK0614)PhD Start Fund of Yan'an University(YDBK2022-15)。
文摘Manganese(Mn),an essential trace element in the human body,plays critical roles in many biological processes.Recent studies have discovered that Mn^(2+)may promote or directly activate the cGAS-STING pathway,thereby subsequently initiating the natural immune response and augmenting antitumor therapy.However,the current lack of accurate methods for Mn^(2+)determination in cells significantly limits their mechanism investigation;hence,it is urgent to establish novel tools to detect Mn^(2+)in cells.In this study,the dual-emission carbon dots were initially synthesized via the one-pot hydrothermal method employing L-aspartic acid and p-phenylenediamine as raw materials.In the presence of Mn^(2+),the emission peak centered at 350 nm exhibited significant enhancement,whereas another peak at 610 nm remained stable.Consequently,a ratiometric sensor for Mn^(2+)determination was established using the signal at 350 nm as the responsive signal and the signal at 610 nm as an internal reference.Under the optimal condition,a good linear relationship was achieved between the F350/F610 value and Mn^(2+)concentration ranging from 0.9 to 15μmol/L,with a calculated LOD of 61 nmol/L.Benefiting from the special Mn^(2+)-induced ratiometric approach,this method demonstrates outstanding sensitivity,selectivity,and stability,rendering it applicable for Mn^(2+)determination in complex biological samples,as well as Mn^(2+)imaging in MKN-45 and LO2 cells.
文摘The need for bi-functional catalysts that facilit-ate both the oxygen reduction(ORR)and carbon dioxide re-duction(CO_(2)RR)reactions arises from their potential to help solve the critical problems of carbon neutrality and renew-able energy conversion.However,there are few reports on the development of bi-functional catalysts for zinc-air bat-tery-driven CO_(2)RR devices.We introduce a novel approach for synthesizing Fe_(2)N/Fe_(3)C species embedded in nitrogen-doped carbon nanofibers by electrospinning a solution of Hemin and polyacrylonitrile in N,N-dimethylformamide.The material has an exceptional catalytic performance,with a half-wave potential of 0.91 V versus RHE for the ORR and values of over 90%for both the selectivity and Faradaic efficiency for the CO_(2)RR.The high catalytic performances are attrib-uted to the strong coupling between the Fe_(3)C/Fe_(2)N heterostructure and the Fe-N-C sites in the nitrogen-doped carbon nan-ofibers.Notably,both Fe_(3)C and Fe_(2)N play distinct roles in both the ORR and CO_(2)RR.This investigation indicates a way for designing advanced carbon-based bi-functional catalysts for use in this field.
基金supported by the National Natural Science Foundation of China(52376103,542B2081).
文摘The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.
基金supported by the Shanxi Province Central Guidance Fund for Local Science and Technology Development Project(YDZJSX2024D030)the National Natural Science Foundation of China(22075197,22278290)+2 种基金the Shanxi Province Key Research and Development Program Project(2021020660301013)the Shanxi Provincial Natural Science Foundation of China(202103021224079)the Research and Development Project of Key Core and Common Technology of Shanxi Province(20201102018).
文摘The advancement of planar micro-supercapacitors(PMSCs)for micro-electromechanical systems(MEMS)has been significantly hindered by the challenge of achieving high energy and power densities.This study addresses this issue by leveraging screen-printing technology to fabricate high-performance PMSCs using innovative composite ink.The ink,a synergistic blend of few-layer graphene(Gt),carbon black(CB),and NiCo_(2)O_(4),was meticulously mixed to form a conductive and robust coating that enhanced the capacitive performance of the PMSCs.The optimized ink formulation and printing process result in a micro-supercapacitor with an exceptional areal capacitance of 18.95 mF/cm^(2)and an areal energy density of 2.63μW·h/cm^(2)at a current density of 0.05 mA/cm^(2),along with an areal power density of 0.025 mW/cm^(2).The devices demonstrated impressive durability with a capacitance retention rate of 94.7%after a stringent 20000-cycle test,demonstrating their potential for long-term applications.Moreover,the PMSCs displayed excellent mechanical flexibility,with a capacitance decrease of only 3.43%after 5000 bending cycles,highlighting their suitability for flexible electronic devices.The ease of integrating these PMSCs into series and parallel configurations for customized power further underscores their practicality for integrated power supply solutions in various technologies.
基金supported by the National Natural Science Foundation of China(Nos.42475125,42105117,42021004 and 41975143)the National Key R&D Program of China(Nos.2019YFA0607202 and 2020YFA0607501)+4 种基金Jiangsu Science Foundation for Distinguished Young Scholar(No.BK20220055)the 333 Project of Jiangsu Province(No.BRA2017402)the R&D Foundation of Jiangsu Province,China(No.BK20220020)Zhejiang Provincial Basic Public Welfare Research Project(No.LGF22D050004)the Key Laboratory of Ecosystem Carbon Source and Sink,China Meteorological Administration(ECSSCMA).
文摘China is the largest emitter of anthropogenic CO_(2) globally,with its cities recognized as significant emission hotspots.Consequently,evaluating anthropogenic CO_(2) emissions and the carbon neutral capability(CNC)of Chinese cities is critical for climate change mitigation.Despite this importance,no studies to date have assessed recent and future city-scale CNCs using the top-down atmospheric inversion approach,revealing substantial knowledge gaps regarding regional CO_(2) budgets.To address these issues,this research focused on Hangzhou,a megacity known for having the highest forest cover among China’s provincial capitals,as study region.Year-round atmospheric CO_(2) concentration measurements were conducted from December 2020 to November 2021 at two sites:one urban and one suburban.These observations,along with their difference,were utilized to derive city-scale posterior anthropogenic CO_(2) emissions and to evaluate recent and future CNCs.Our key findings are as follows:(1)The manufacturing industry,energy industry and oil refineries/transformation industry were identified as the largest contributors to urban-suburban CO_(2) difference,accounting for 36.5%,21.3%,and 16.6%,respectively.Additionally,82.5%,65.2%,81.2%and 86.3%of total anthropogenic CO_(2) enhancements were attributed to emissions within Hangzhou city in winter,spring,summer and autumn,respectively.(2)The posterior annual anthropogenic CO_(2) emission for Hangzhouwas estimated at 4.65(±0.72)×10^(10) kg/a,indicating significant biases among different prior CO_(2) emission inventories.The annual biological CO_(2) sink,derived from multiple products,was estimated at-0.48(±0.16)×10^(10) kg.(3)The calculated CNC for 2021was 10.3%±3.4%,highlighting a substantial gap towards achieving full carbon neutrality.Considering potential increases in ecosystem carbon sinks due to forest age and uncertainties from climate change,it was predicted that at least 65.2%-82.6%of anthropogenic CO_(2) emissions must be reduced to achieve the goal of full carbon neutrality by year of 2060.
基金supported by Jiangsu Province Science and Technology Plan Special Fund(BZ2022053)National Natural Science Foundation of China(42476239)+1 种基金Natural Science Research Projects of Universities in Jiangsu Province(24KJD530004)the Dean/Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021K008)。
文摘The catalytic direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol is a crucial approach to utilizing CO_(2)and producing high-value chemicals.However,the high stability of the CO_(2)molecule imposes thermodynamic limitations on this reaction pathway,along with challenges related to insufficient catalyst activity and stability.Currently,solutions primarily focus on developing efficient catalyst.Herein,La-doped CeO_(2)nanoflower catalysts(La_(x)CeO_(2))were synthesized via hydrothermal method.Characterization reveals that La doping optimizes the pore structure and enriched oxygen vacancies,thereby enhancing catalytic performance.Notably,La_(0.1)CeO_(2)exhibits the largest pore size and highest oxygen vacancy content,achieving a remarkable DMC productivity of 9.42 mmol/g under 140℃,4 MPa of CO_(2),and 3 h of reactio n,surpassing pure CeO_(2)nano flowers.Based on experimental findings and in-situ diffuse infrared Fourier transform analysis,a plausible reaction pathway was proposed.This work underscores the potential of La_(x)CeO_(2)nano flowers as efficient catalysts for sustainable CO_(2)conversion to DMC.
基金supported by the National Natural Science Foundation of China(Grant No.52374192)the Henan Province Funds for Distinguished Young Youths(Grant No.242300421013)the Innovative Scientific Research Team Project of Henan Polytechnic University(Grant No.T2024-1).
文摘Mitigating climate change demands innovative solutions,and carbon sequestration technologies are at the forefront.Among these,basalt,a mafic volcanic rock packed with calcium,magnesium,and iron,emerges as a powerful candidate for carbon dioxide(CO_(2))sequestration through mineral carbonation.This method transforms CO_(2)into stable carbonate minerals,ensuring a permanent and environmentally safe storage solution.While extensive research has explored into basalt’s potential under high hydration conditions,the untapped promise of low water content scenarios remains largely unexplored.Our ground-breaking study investigates the mineral carbonation of basalt powder under low water condi-tions using supercritical CO_(2)(sc-CO_(2)).Conducted at 50℃ and 15 MPa with a controlled moisture content of 30%,our experiment spans various time points(0,7,14,21,and 28 days).Utilising advanced X-ray diffraction(XRD)and scanning electron microscopy with energy-dispersive X-ray spectroscopy(SEM-EDS),we unveil the mineralogical and morphological transformations.The results are striking:even under low water conditions,basalt efficiently forms valuable carbonate minerals such as calcite,siderite,magnesite,and ankerite.The carbonation efficiency evolves over time,reflecting the dynamic transfor-mation of the basalt matrix.These findings offer pivotal insights into optimising CO_(2)sequestration in basalt under low hydration,marking a significant leap toward sustainable carbon capture and storage.
基金National Natural Science Foundation of China(grants 22072065,22178162,and 22222806)Distinguished Youth Foundation of Jiangsu Province(grant BK20220053)Six talent peaks project in Jiangsu Province(grant JNHB-035)。
文摘The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.
基金National Natural Science Foundation of China (Nos. 22371244 and 21573192)Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_3463)。
文摘Transition metal-carbonate interfaces often act as active sites in heterogeneous catalytic reactions.The interface between transition metal and metal carbonate exhibits a dynamic equilibrium during the CO_(2)hydrogenation reaction,involving surface carbonate hydrogenation and CO_(2)chemisorption.Nonetheless,there have been few reports on engineering the activity of the interface between transition metal and alkaline earth metal carbonate for catalytic CO_(2)conversion.This work demonstrated that the incorporation of CaH_(2)in Ni/CaCO_(3)enhances the CO_(2)methanation activity of the catalysts.The CO_(2)conversion for Ni/CaH_(2)-CaCO_(3)reached 68.5%at 400°C,which was much higher than that of the Ni/CaCO_(3)(31.6%) and Ni/CaH_(2)-CaO (42.4%) catalysts.Furthermore,the Ni/CaH_(2)-CaCO_(3)catalysts remained stable during the stability test for 24 h at 400°C and 8 bar.Our research revealed that CaH_(2)played a crucial role in promoting the activity of the Ni-carbonate interface for CO_(2)methanation.CaH_(2)could modify the electronic structure of Ni and tune the structural properties of CaCO_(3)to generate medium basic sites (OH groups),which are favorable for the activation of H2and CO_(2).In-situ Fourier transform infrared spectroscopy (FTIR) analysis combined with density functional theory calculations demonstrated that CO_(2)activation occurs at the hydroxyl group (OH) on the CaH_(2)-modified Ni-carbonate surface,leading to the formation of CO_(3)H*species.Furthermore,our study has confirmed that CO_(2)methanation over the Ni/CaH_(2)-CaCO_(3)catalysts proceeds via the formate pathway.
