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
Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent material...Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent materials were successfully synthesized by loading TEPA onto the pore MgO/ZrO_(2)carriers in the paper.The pore structure and surface characteristic of the samples were analyzed by using XRD,BET,FT-IR and SEM.The adsorbent materials exhibited microcrystalline state,and the crystallinity of all samples gradually decreased as the increase of TEPA content.The pore structure analysis indicated that the modification of MgO-ZrO_(2)adsorbents with TEPA led to the decrease of the specific surface areas,but the narrow micro-mesopore size distributions ranging from 1.8-12 nm in the adsorbents still were maintained.FT-IR spectrum results further verified the successful loading of TEPA.The adsorption capacity of the adsorbents for CO_(2)were tested by using an adsorption apparatus equipped with gas chromatography.The results indicated that when the TEPA loading reached 50%,the sample exhibited the maximum adsorption value for CO_(2),reaching 4.07 mmol/g under the operation condition of 75℃and atmospheric pressure.This result could be assigned to not only the base active sites but also the coexistence of both micropore and mesopore in the adsorbent.After three cycles tests for CO_(2)capture,the adsorption value of the sample for CO_(2)can also reached 95%of its original adsorption capacity,which verified the excellent cyclic operation stability.展开更多
To optimize the CO_(2) adsorption performance of carbon materials,this study proposed a preparation method for biomass-based porous carbon through hydrothermal carbonization coupled with nitrogen source optimization a...To optimize the CO_(2) adsorption performance of carbon materials,this study proposed a preparation method for biomass-based porous carbon through hydrothermal carbonization coupled with nitrogen source optimization and K_(2)CO_(3) activation.The effects of different nitrogen sources(urea,piperazine,melamine,and polyaniline)and activation temperatures on the physicochemical features and CO_(2) adsorption characteristics of the porous carbons were systematically investigated.The results indicated that different nitrogen sources showed varying impacts on the CO_(2) uptake of porous carbons,and not all nitrogen sources enhanced the adsorption performance.The urea and piperazine doped porous carbons exhibited relatively low nitrogen contents and specific surface areas.Whereas the melamine doped carbons showed higher nitrogen contents and specific surface areas,but lacked narrow micropores,limiting their CO_(2) adsorption performance.In contrast,PAC-700,prepared using polyaniline as nitrogen source,featured a well-developed pore structure,abundant narrow micropores and pyrrolic-N groups,endowing it with enhanced CO_(2) adsorption capability.At 0℃/1 bar and 25℃/1 bar,the CO_(2) uptake of PAC-700 reached 6.85 and 4.64 mmol/g,respectively.Additionally,PAC-700 maintained a CO_(2) uptake retention ratio of 99%after 5 adsorption-desorption cycles and exhibited good CO_(2)/N_(2) selectivity of 22.4−51.6.These findings highlighted the advantageous CO_(2) adsorption performance of PAC-700,indicating its substantial application potential in the domain of carbon capture.展开更多
Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have re...Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.展开更多
Perfluoroalkyl acids of different chain lengths,including trifluoroacetic acid,heptafluorobutyric acid,and nonafluoropentanoic acid,were used as second ligands to replace the formic acid on the Zr_(6)clusters in MOF-8...Perfluoroalkyl acids of different chain lengths,including trifluoroacetic acid,heptafluorobutyric acid,and nonafluoropentanoic acid,were used as second ligands to replace the formic acid on the Zr_(6)clusters in MOF-808.This led to the formation of a series of MOF-808-R materials(R=F_(3),F_(7),F_(9),corresponding to trifluoroacetic acid,hep-tafluorobutyric acid,and nonafluoropentanoic acid)with multiple ligands,and we investigated the impact of the sec-ond ligand modification on pore size and pore environment.The loading amount of the second ligand was deter-mined using NMR and other methods.We conducted adsorption tests for acetylene and carbon dioxide at different temperatures on both MOF-808 and MOF-808-R to explore the effects of the ligand diversification on acetylene sep-aration performance.It was found that MOF-808-F_(7)exhibited the best performance in acetylene-carbon dioxide sep-aration.展开更多
A new adsorbent was successfully prepared by hydrothermal treatment and chemical activation through coal gasification fine slag(CGFS)and blue algae(BA)as raw materials and used for CO_(2)capture.The CO_(2)chemisorptio...A new adsorbent was successfully prepared by hydrothermal treatment and chemical activation through coal gasification fine slag(CGFS)and blue algae(BA)as raw materials and used for CO_(2)capture.The CO_(2)chemisorption capacity of the adsorbent was further enhanced by taking advantage of the nitrogenous bases contained in the BA.In the hydrothermal process,the addition of BA significantly increased the content of pyrrole nitrogen in the adsorbent.In the activation process,pyrrole nitrogen gradually changed into pyridine nitrogen and graphite nitrogen.Increased BA addition result in a higher specific surface area and microporosity of the adsorbent.The CO_(2)adsorption performance test proved that the CGFS-50%-CA sample has the strongest CO_(2)adsorption capacity at low temperature,up to 15.59 cm^(3)/g,which is mainly through physical adsorption,and the CGFS-10%-CA sample has the strongest CO_(2)adsorption capacity at high temperature,up to 7.31 cm^(3)/g,which is mainly through chemical adsorption.CO_(2)uptake of the CGFS-10%-CA sample was well maintained after 10 cycles,with regeneration efficiencies above 99%.The results indicate that the novel adsorbents with coexistence of physical and chemical adsorption have great potential for CO_(2)adsorption applications.展开更多
气体分离膜技术凭借其运行能耗低、无相变过程及环境友好特性,已成为传统分离工艺的替代方案。特别是在“碳中和”战略背景下,开发高效碳捕集技术对减缓气候变化具有关键意义。金属有机框架(MOFs)材料因其独特的结构可设计性与功能多样...气体分离膜技术凭借其运行能耗低、无相变过程及环境友好特性,已成为传统分离工艺的替代方案。特别是在“碳中和”战略背景下,开发高效碳捕集技术对减缓气候变化具有关键意义。金属有机框架(MOFs)材料因其独特的结构可设计性与功能多样性,为构建高性能混合基质膜(Mixed Matrix Membranes,MMMs)提供了全新思路,展现出突破“Trade-off”限制的潜力。系统分析了MOFs基MMMs中研究进展,通过将MOFs材料(具有可调孔结构、超高比表面积及多功能性)与聚合物基质的互补结合,突破聚合物膜的性能极限。首先阐释气体分离膜的基本原理及MOFs的理化特性,继而深入解析MOFs基MMMs的设计思路。重点探讨其性能、精准可调的孔径分布及CO_(2)选择性吸附机制。针对碳捕集应用,对比评述了ZIF(Zeolitic Imidazolate Framework)、UiO(University of Oslo)和MIL(Materials of Institute Lavoisier)3类MOFs的结构-性能关系。通过对比溶液浇铸、原位生长和界面聚合等制备工艺,揭示了MOFs-MMMs构建过程中的关键工艺路径。结合CO_(2)渗透率、选择性系数等核心指标,剖析了界面缺陷形成、纳米粒子团聚等关键挑战。汇总整理了抗老化膜设计、规模化生产成本评估等最新突破,同时指出当前MOFs在规模化应用中面临合成成本高、长期运行稳定性不足、有机-无机界面的相容性较差等问题。最后提出未来需材料科学、化学工程与环境技术等多学科协同创新,推动MOFs-MMMs技术的工业化进程,提供应对气候变化的先进气体分离解决方案。展开更多
The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) ...The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.展开更多
Electrocatalytic carbon dioxide(CO_(2))reduction is an important way to achieve carbon neutrality by converting CO_(2)in-to high-value-added chemicals using electric energy.Carbon-based materials are widely used in va...Electrocatalytic carbon dioxide(CO_(2))reduction is an important way to achieve carbon neutrality by converting CO_(2)in-to high-value-added chemicals using electric energy.Carbon-based materials are widely used in various electrochemical reactions,including electrocatalytic CO_(2)reduction,due to their low cost and high activity.In recent years,defect engineering has attracted wide attention by constructing asymmetric defect centers in the materials,which can optimize the physicochemical properties of the mater-ial and improve its electrocatalytic activity.This review summarizes the types,methods of formation and defect characterization tech-niques of defective carbon-based materials.The advantages of defect engineering and the advantages and disadvantages of various defect formation methods and characterization techniques are also evaluated.Finally,the challenges of using defective carbon-based materials in electrocatalytic CO_(2)reduction are investigated and opportunities for their use are discussed.It is believed that this re-view will provide suggestions and guidance for developing defective carbon-based materials for CO_(2)reduction.展开更多
Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction us...Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction using H_(2)O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties.Metal-organic frameworks(MOFs)are promising candidates for overall CO_(2)photoreduction due to their large surface area,diverse active sites,and excellent tailorability.In this study,we designed a metal-organic framework photocatalyst,named PCN-224(Zn)-Bpy(Ru),by integrating photoactive Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties.In comparison,two isostructural MOFs just with either Zn(Ⅱ)-porphyrin or Ru(Ⅱ)-bipyridyl moiety,namely PCN-224-Bpy(Ru)and PCN-224(Zn)-Bpy were also synthesized.As a result,PCN-224(Zn)-Bpy(Ru)exhibited the highest photocatalytic conversion rate of CO_(2)to CO,with a production rate of 7.6μmol·g^(-1)·h^(-1)in a mixed solvent of CH_(3)CN and H_(2)O,without the need for co-catalysts,photosensitizers,or sacrificial agents.Mass spectrometer analysis detected the signals of^(13)CO(m/z=29),^(13)C^(18)O(m/z=31),^(16)O^(18)O(m/z=34),and^(18)O_(2)(m/z=36),confirming that CO_(2)and H_(2)O acted as the carbon and oxygen sources for CO and O_(2),respectively,thereby confirming the coupling of photocatalytic CO_(2)reduction with H_(2)O oxidation.In contrast,using PCN-224-Bpy(Ru)or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0μmol·g^(-1)·h^(-1),respectively.Mechanistic studies revealed that the lowest unoccupied molecular orbital(LUMO)potential of PCN-224(Zn)-Bpy(Ru)is more negative than the redox potentials of CO_(2)/CO,and the highest occupied molecular orbital(HOMO)potential is more positive than that of H_(2)O/O_(2),satisfying the thermodynamic requirements for overall photocatalytic CO_(2)reduction.In comparison,the HOMO potential of PCN-224(Zn)-Bpy without Ru(II)-bipyridyl moieties is less positive than that of H_(2)O/O_(2),indicating that the Ru(II)-bipyridyl moiety is thermodynamically necessary for CO_(2)reduction coupled with H_(2)O oxidation.Additionally,photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru)was almost completely quenched,and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru)was observed.These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru),which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru)compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru).In summary,the integrated Zn(II)-porphyrin and Ru(II)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru)play important roles of a photosensitizer and CO_(2)reduction as well as H_(2)O oxidation sites,and their efficient cooperation optimizes the band structure,thereby facilitating the coupling of CO_(2)reduction with H_(2)O oxidation and resulting in highperformance artificial photocatalytic CO_(2)reduction.展开更多
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 Shanxi Provincial Key Research and Development Project(202102090301026)Graduate Education Innovation Project of Taiyuan University of Science and Technology(SY2023024)。
文摘Currently,the solid adsorbents with porous structure have been widely applied in CO_(2)capture.However,the unmodified MgO-ZrO_(2)adsorbents appeared to be low adsorption capacity of CO_(2).The solid adsorbent materials were successfully synthesized by loading TEPA onto the pore MgO/ZrO_(2)carriers in the paper.The pore structure and surface characteristic of the samples were analyzed by using XRD,BET,FT-IR and SEM.The adsorbent materials exhibited microcrystalline state,and the crystallinity of all samples gradually decreased as the increase of TEPA content.The pore structure analysis indicated that the modification of MgO-ZrO_(2)adsorbents with TEPA led to the decrease of the specific surface areas,but the narrow micro-mesopore size distributions ranging from 1.8-12 nm in the adsorbents still were maintained.FT-IR spectrum results further verified the successful loading of TEPA.The adsorption capacity of the adsorbents for CO_(2)were tested by using an adsorption apparatus equipped with gas chromatography.The results indicated that when the TEPA loading reached 50%,the sample exhibited the maximum adsorption value for CO_(2),reaching 4.07 mmol/g under the operation condition of 75℃and atmospheric pressure.This result could be assigned to not only the base active sites but also the coexistence of both micropore and mesopore in the adsorbent.After three cycles tests for CO_(2)capture,the adsorption value of the sample for CO_(2)can also reached 95%of its original adsorption capacity,which verified the excellent cyclic operation stability.
基金supported by the National Key R&D Program(2022YFC3902403)Fundamental Research Funds for the Central Universities(2024JC001,2019JG002)Technology Innovation Special Fund of Jiangsu Province for Carbon Dioxide Emission Peaking and Carbon Neutrality(BE2022307)。
文摘To optimize the CO_(2) adsorption performance of carbon materials,this study proposed a preparation method for biomass-based porous carbon through hydrothermal carbonization coupled with nitrogen source optimization and K_(2)CO_(3) activation.The effects of different nitrogen sources(urea,piperazine,melamine,and polyaniline)and activation temperatures on the physicochemical features and CO_(2) adsorption characteristics of the porous carbons were systematically investigated.The results indicated that different nitrogen sources showed varying impacts on the CO_(2) uptake of porous carbons,and not all nitrogen sources enhanced the adsorption performance.The urea and piperazine doped porous carbons exhibited relatively low nitrogen contents and specific surface areas.Whereas the melamine doped carbons showed higher nitrogen contents and specific surface areas,but lacked narrow micropores,limiting their CO_(2) adsorption performance.In contrast,PAC-700,prepared using polyaniline as nitrogen source,featured a well-developed pore structure,abundant narrow micropores and pyrrolic-N groups,endowing it with enhanced CO_(2) adsorption capability.At 0℃/1 bar and 25℃/1 bar,the CO_(2) uptake of PAC-700 reached 6.85 and 4.64 mmol/g,respectively.Additionally,PAC-700 maintained a CO_(2) uptake retention ratio of 99%after 5 adsorption-desorption cycles and exhibited good CO_(2)/N_(2) selectivity of 22.4−51.6.These findings highlighted the advantageous CO_(2) adsorption performance of PAC-700,indicating its substantial application potential in the domain of carbon capture.
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
基金supported by the National Key R&D Program of China(2024YFB4106400)National Natural Science Foundation of China(22209200,52302331)。
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to carbon monoxide(CO)is an effective strategy to achieve carbon neutrality.High selective and low-cost catalysts for the electrocatalytic reduction of CO_(2)have received increasing attention.In contrast to the conventional tube furnace method,the high-temperature shock(HTS)method enables ultra-fast thermal processing,superior atomic efficiency,and a streamlined synthesis protocol,offering a simplified method for the preparation of high-performance single-atom catalysts(SACs).The reports have shown that nickel-based SACs can be synthesized quickly and conveniently using the HTS method,making their application in CO_(2)reduction reactions(CO_(2)RR)a viable and promising avenue for further exploration.In this study,the effect of heating temperature,metal loading and different nitrogen(N)sources on the catalyst morphology,coordination environment and electrocatalytic performance were investigated.Under optimal conditions,0.05Ni-DCD-C-1050 showed excellent performance in reducing CO_(2)to CO,with CO selectivity close to 100%(−0.7 to−1.0 V vs RHE)and current density as high as 130 mA/cm^(2)(−1.1 V vs RHE)in a flow cell under alkaline environment.
文摘Perfluoroalkyl acids of different chain lengths,including trifluoroacetic acid,heptafluorobutyric acid,and nonafluoropentanoic acid,were used as second ligands to replace the formic acid on the Zr_(6)clusters in MOF-808.This led to the formation of a series of MOF-808-R materials(R=F_(3),F_(7),F_(9),corresponding to trifluoroacetic acid,hep-tafluorobutyric acid,and nonafluoropentanoic acid)with multiple ligands,and we investigated the impact of the sec-ond ligand modification on pore size and pore environment.The loading amount of the second ligand was deter-mined using NMR and other methods.We conducted adsorption tests for acetylene and carbon dioxide at different temperatures on both MOF-808 and MOF-808-R to explore the effects of the ligand diversification on acetylene sep-aration performance.It was found that MOF-808-F_(7)exhibited the best performance in acetylene-carbon dioxide sep-aration.
基金supported by the National Natural Science Foundation of China(22168032)the National Key Research and Development Program of China(2023YFC3904302,2023YFB4103500)the Key Projects of Ning Dong Energy and Chemical Industry Base(2023NDKJXMLX022).
文摘A new adsorbent was successfully prepared by hydrothermal treatment and chemical activation through coal gasification fine slag(CGFS)and blue algae(BA)as raw materials and used for CO_(2)capture.The CO_(2)chemisorption capacity of the adsorbent was further enhanced by taking advantage of the nitrogenous bases contained in the BA.In the hydrothermal process,the addition of BA significantly increased the content of pyrrole nitrogen in the adsorbent.In the activation process,pyrrole nitrogen gradually changed into pyridine nitrogen and graphite nitrogen.Increased BA addition result in a higher specific surface area and microporosity of the adsorbent.The CO_(2)adsorption performance test proved that the CGFS-50%-CA sample has the strongest CO_(2)adsorption capacity at low temperature,up to 15.59 cm^(3)/g,which is mainly through physical adsorption,and the CGFS-10%-CA sample has the strongest CO_(2)adsorption capacity at high temperature,up to 7.31 cm^(3)/g,which is mainly through chemical adsorption.CO_(2)uptake of the CGFS-10%-CA sample was well maintained after 10 cycles,with regeneration efficiencies above 99%.The results indicate that the novel adsorbents with coexistence of physical and chemical adsorption have great potential for CO_(2)adsorption applications.
文摘气体分离膜技术凭借其运行能耗低、无相变过程及环境友好特性,已成为传统分离工艺的替代方案。特别是在“碳中和”战略背景下,开发高效碳捕集技术对减缓气候变化具有关键意义。金属有机框架(MOFs)材料因其独特的结构可设计性与功能多样性,为构建高性能混合基质膜(Mixed Matrix Membranes,MMMs)提供了全新思路,展现出突破“Trade-off”限制的潜力。系统分析了MOFs基MMMs中研究进展,通过将MOFs材料(具有可调孔结构、超高比表面积及多功能性)与聚合物基质的互补结合,突破聚合物膜的性能极限。首先阐释气体分离膜的基本原理及MOFs的理化特性,继而深入解析MOFs基MMMs的设计思路。重点探讨其性能、精准可调的孔径分布及CO_(2)选择性吸附机制。针对碳捕集应用,对比评述了ZIF(Zeolitic Imidazolate Framework)、UiO(University of Oslo)和MIL(Materials of Institute Lavoisier)3类MOFs的结构-性能关系。通过对比溶液浇铸、原位生长和界面聚合等制备工艺,揭示了MOFs-MMMs构建过程中的关键工艺路径。结合CO_(2)渗透率、选择性系数等核心指标,剖析了界面缺陷形成、纳米粒子团聚等关键挑战。汇总整理了抗老化膜设计、规模化生产成本评估等最新突破,同时指出当前MOFs在规模化应用中面临合成成本高、长期运行稳定性不足、有机-无机界面的相容性较差等问题。最后提出未来需材料科学、化学工程与环境技术等多学科协同创新,推动MOFs-MMMs技术的工业化进程,提供应对气候变化的先进气体分离解决方案。
基金Project(52204378)supported by the National Natural Science Foundation of China。
文摘The selective reduction of carbon dioxide(CO_(2))into high-value-added chemicals is one of the most effective means to solve the current energy and environmental problems,which could realize the utilization of CO_(2) and promote the balance of the carbon cycle.Formate is one of the most economical and practical products of all the electrochemical CO_(2) reduction products.Among the many metal-based electrocatalysts that can convert CO_(2) into formate,Sn-based catalysts have received a lot of attention because of their low-cost,non-toxic characteristics and high selectivity for formate.In this article,the most recent development of Sn-based electrocatalysts is comprehensively summarized by giving examples,which are mainly divided into monometallic Sn,alloyed Sn,Sn-based compounds and Sn composite catalysts.Finally,the current performance enhancement strategies and future directions of the field are summarized.
文摘Electrocatalytic carbon dioxide(CO_(2))reduction is an important way to achieve carbon neutrality by converting CO_(2)in-to high-value-added chemicals using electric energy.Carbon-based materials are widely used in various electrochemical reactions,including electrocatalytic CO_(2)reduction,due to their low cost and high activity.In recent years,defect engineering has attracted wide attention by constructing asymmetric defect centers in the materials,which can optimize the physicochemical properties of the mater-ial and improve its electrocatalytic activity.This review summarizes the types,methods of formation and defect characterization tech-niques of defective carbon-based materials.The advantages of defect engineering and the advantages and disadvantages of various defect formation methods and characterization techniques are also evaluated.Finally,the challenges of using defective carbon-based materials in electrocatalytic CO_(2)reduction are investigated and opportunities for their use are discussed.It is believed that this re-view will provide suggestions and guidance for developing defective carbon-based materials for CO_(2)reduction.
文摘Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction using H_(2)O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties.Metal-organic frameworks(MOFs)are promising candidates for overall CO_(2)photoreduction due to their large surface area,diverse active sites,and excellent tailorability.In this study,we designed a metal-organic framework photocatalyst,named PCN-224(Zn)-Bpy(Ru),by integrating photoactive Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties.In comparison,two isostructural MOFs just with either Zn(Ⅱ)-porphyrin or Ru(Ⅱ)-bipyridyl moiety,namely PCN-224-Bpy(Ru)and PCN-224(Zn)-Bpy were also synthesized.As a result,PCN-224(Zn)-Bpy(Ru)exhibited the highest photocatalytic conversion rate of CO_(2)to CO,with a production rate of 7.6μmol·g^(-1)·h^(-1)in a mixed solvent of CH_(3)CN and H_(2)O,without the need for co-catalysts,photosensitizers,or sacrificial agents.Mass spectrometer analysis detected the signals of^(13)CO(m/z=29),^(13)C^(18)O(m/z=31),^(16)O^(18)O(m/z=34),and^(18)O_(2)(m/z=36),confirming that CO_(2)and H_(2)O acted as the carbon and oxygen sources for CO and O_(2),respectively,thereby confirming the coupling of photocatalytic CO_(2)reduction with H_(2)O oxidation.In contrast,using PCN-224-Bpy(Ru)or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0μmol·g^(-1)·h^(-1),respectively.Mechanistic studies revealed that the lowest unoccupied molecular orbital(LUMO)potential of PCN-224(Zn)-Bpy(Ru)is more negative than the redox potentials of CO_(2)/CO,and the highest occupied molecular orbital(HOMO)potential is more positive than that of H_(2)O/O_(2),satisfying the thermodynamic requirements for overall photocatalytic CO_(2)reduction.In comparison,the HOMO potential of PCN-224(Zn)-Bpy without Ru(II)-bipyridyl moieties is less positive than that of H_(2)O/O_(2),indicating that the Ru(II)-bipyridyl moiety is thermodynamically necessary for CO_(2)reduction coupled with H_(2)O oxidation.Additionally,photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru)was almost completely quenched,and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru)was observed.These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru),which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru)compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru).In summary,the integrated Zn(II)-porphyrin and Ru(II)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru)play important roles of a photosensitizer and CO_(2)reduction as well as H_(2)O oxidation sites,and their efficient cooperation optimizes the band structure,thereby facilitating the coupling of CO_(2)reduction with H_(2)O oxidation and resulting in highperformance artificial photocatalytic CO_(2)reduction.
