Ethylene(C_(2)H_(4))is conventionally produced by a high energy-consumption process based on the steam cracking of ethane(C_(2)H_(6)).In contrast,we presented a novel symmetrical solid oxide fuel cell(SOFC)to coproduc...Ethylene(C_(2)H_(4))is conventionally produced by a high energy-consumption process based on the steam cracking of ethane(C_(2)H_(6)).In contrast,we presented a novel symmetrical solid oxide fuel cell(SOFC)to coproduce electricity and C_(2)H_(4)through C_(2)H_(6)dehydrogenation.The symmetrical cell contains a thin Ba Zr_(0.1)Ce_(0.7)Y_(0.2)O_(3)(BZCY)electrolyte sandwiched between two thicker(PrBa)_(0.95)(Fe_(0.7)Ni_(0.2)Cu_(0.1))_(1.8)Mo_(0.2)O_(6-δ)impregnated BZCY(PBFNCM-BZCY)electrodes.The as-synthesized reduced-PBFNCM(R-PBFNCM)contained Fe-Ni-Cu alloy particles embedded on a double-perovskite matrix uniformly,while the electrode showed high oxygen vacancy concentration,electronic conductivity,redox stability,and activity for C_(2)H_(6)dehydrogenation with improved ethylene selectivity.The symmetrical cell demonstrated a peak power density of 409 mW cm^(-2)using C_(2)H_(6)as fuel,accompanying with a C_(2)H_(6)conversion of 51.2%,a C_(2)H_(4)selectivity of 92.5%,and a C_(2)H_(4)yield of 47.4%at 750℃and 750 mA cm^(-2).Despite carbon deposition occurred slowly in the anode,the deposited carbon was removed by simply switching C_(2)H_(6)and air between electrodes.Consequently,the cell voltage and C_(2)H_(4)yield recover by 91.4%and 98.1%,respectively,after three switches with an interval of 48 h,suggesting that the symmetrical SOFC is a promising solution for long-term continuous electricity and C_(2)H_(4)co-production by C_(2)H_(6)dehydrogenation.展开更多
(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]是新型含能钙钛矿化合物的典型代表,需明确其热分解行为、热分解机制及感度特性,以推动其在配方中的应用。以差示扫描量热-热重分析方法实现了分解放热量、分解温度等参数的获取;以动力学模拟计算...(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]是新型含能钙钛矿化合物的典型代表,需明确其热分解行为、热分解机制及感度特性,以推动其在配方中的应用。以差示扫描量热-热重分析方法实现了分解放热量、分解温度等参数的获取;以动力学模拟计算解析了相关分解机理;以同步热分析-红外-质谱联用技术结合原位红外技术探索了(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]的分解产物及分解历程;以国军标法获得了热感度、摩擦感度与撞击感度参数。结果表明:在10℃·min^(-1)的升温速率下,(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]分解放热量为4227 J·g^(-1),分解温度则达到345℃,高于黑索今(RDX)、奥克托今(HMX)、六硝基六氮杂异伍兹烷(CL-20)等多数现役含能材料,显示了优异的热稳定性;分解产物研究表明其立方笼状骨架有效稳定了内部结合的有机物分子,使其热稳定性较高。此外,(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]在100℃下加热48 h的放气量约0.04 m L·g^(-1),撞击感度与机械感度分别为32%和80%,优于RDX和HMX。展开更多
Efficient recovery of ethane(C_(2)H_(6))from natural gas is of industrial importance,yet it poses considerable challenges.Herein,we report the two-step green preparation of asphalt-based carbon adsorbent Asphalt-based...Efficient recovery of ethane(C_(2)H_(6))from natural gas is of industrial importance,yet it poses considerable challenges.Herein,we report the two-step green preparation of asphalt-based carbon adsorbent Asphalt-based Carbon adsorbents(AsCs)with exceptional C_(2)H_(6)/CH_(4) selectivity and high capacity,where the KOH usage can be significantly reduced by 75% than conventional chemical activation processes.More importantly,the resulting AsC-0.75-900 exhibits exceptional C_(2)H_(6)/CH_(4) separation performance with the ideal adsorbed solution theory(IAST)selectivity of 30.74 and C_(2)H_(6) capacity of 4.53 mmol/g at 298 K and 100 kPa.Notably,even at the low pressure of 10 kPa,its C_(2)H_(6) uptake remains high at 2.25 mmol/g,comparable to many advanced metal-organic frameworks(MOFs).Molecular simulation was used to elucidate the adsorption mechanism.Fixed-bed experiments further demonstrate dynamic separation performance,achieving complete separation of a C_(2)H_(6)/CH_(4) binary mixture(10:90,v/v)at ambient condition.In addition to superior separation performance,AsC-0.75-900 offers inherent structural stability and cost-effectiveness,positioning it a highly promising candidate for C_(2)H_(6) recovery from natural gas.展开更多
Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic framewor...Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic frameworks(HOFs),NKM-HOF-6 and NKM-HOF-7,featuring permanent microporosity.Upon treatment with hot acetone,NKM-HOF-6 undergoes a structural transformation into NKM-HOF-7,characterized by a transition from a 3D polycatenated framework to a 2D parallel displacement-stacked structure.This transformation leads to a reduction in the maximum pore size of NKM-HOF-7 and a decrease in the density of-CF_(3)groups within its channels,thereby enhancing its preferential affinity for C_(2)H_(6)over C_(2)H_(4).The adsorption capacity difference between C_(2)H_(6)and C_(2)H_(4)in NKM-HOF-7 is 11.1 cm^(3)·g^(-1),with an IAST selectivity of 1.77,surpassing the corresponding values for NKM-HOF-6(9.6 cm^(3)·g^(-1)and 1.56,respectively).Breakthrough experiments further reveal that NKM-HOF-7 achieves nearly twice the separation efficiency of NKM-HOF-6 for C_(2)H_(6)/C_(2)H_(4)(10/90,V/V)mixtures.Theoretical calculations attribute this enhanced C_(2)H_(6)affinity to the synergistic effects of optimized pore dimensions and functionalized pore surfaces in NKM-HOF-7.These findings provide critical insights for the rational design of highly efficient C_(2)H_(6)-selective adsorbents.展开更多
Efficient CO_(2) photoreduction towards C_(2+)solar fuels has emerged as one of the most promising strategies for alleviating the current energy and environment problems.However,the C-C coupling barriers and complex m...Efficient CO_(2) photoreduction towards C_(2+)solar fuels has emerged as one of the most promising strategies for alleviating the current energy and environment problems.However,the C-C coupling barriers and complex multi-electron transfer steps still limit the activity and selectivity of CO_(2)-to-C_(2) photoreduction.Herein,Au nanoparticles(NPs)modified CeO_(2) with oxygen vacancies(Au/CeO_(2)-VO)were reported for enhancing the CO_(2)-to-C_(2)H_(6) photoreduction performance.Au/CeO_(2)-VO achieved the high C_(2)H_(6) activity of 51.7μmol·g^(-1)·h^(-1),accompanied with C_(2)H_(6) selectivity up to 80% in the absence of sacrificial agent.Experimental results combined with theoretical simulation indicated that VO strengthened CO_(2) adsorption and activated*CO production,and plasmon-induced hot electrons from Au NPs to CeO_(2)-VO facilitated the*CO-*CO dimerization.The synergistic modulation of VO and hot electrons further decreased the energy barriers of C-C coupling and subsequent hydrogenation,resulting in the superior photoreduction performance.This work opens an avenue of developing plasmonic photocatalysts for multi-carbon products from CO_(2) photoreduction.展开更多
BiOI mateials show significant potential forphotocatalytic CO_(2) reduction, but their limited CO_(2) activationand poor charge carrier properties hinder conversion efficiency.In this study, we engineered BiOI-based p...BiOI mateials show significant potential forphotocatalytic CO_(2) reduction, but their limited CO_(2) activationand poor charge carrier properties hinder conversion efficiency.In this study, we engineered BiOI-based photocatalystswith abundant crystal defects to enhance performance. X-raydiffraction (XRD), Raman spectroscopy, and high-resolutiontransmission electron microscopy (HRTEM) revealed latticedistortions and twin crystals in BiOI-LD and BiOI-TC. Ultraviolet-visible spectroscopy, micropore and chemisorptionanalyses, and photoluminescence spectroscopy demonstratedthat crystal defects improved light absorption, CO_(2) adsorption,charge transfer efficiency, and carrier lifetime. Electronparamagnetic resonance (EPR) spectroscopy showed increasedsuperoxide radical generation in BiOI-TC, suggesting higherreactivity. Consequently, BiOI achieved a CH_(3)CH_(2)OH generationrate of 6.2 μmol g.1 h.1 with 100% selectivity. Keyintermediates (*CO, *COCO, *CHO, *CH_(2)) for CH_(3)CH_(2)OHproduction were identified, and C_(2)H_(6) formation in BiOI-LDwas linked to the generation of *CH_(3).展开更多
The mechanism of the reaction of Ni^+ (~2D) with ethane in the gas-phase wasstudied by using density functional theory. Both the B3LYP and BLYP functionals with standardall-electron basis sets are used to give the det...The mechanism of the reaction of Ni^+ (~2D) with ethane in the gas-phase wasstudied by using density functional theory. Both the B3LYP and BLYP functionals with standardall-electron basis sets are used to give the detailed information of the potential energy surface(PES) of [Ni, C_2, H_6]^+. The mechanisms forming the products CH_4 and H_2 in the reaction of Ni^+with ethane are proposed. The reductive eliminations of CH_4 and H_2 are typicaladdition-elimination reactions. Each of the two reactions consists of two elementary steps; C―C orC―H bond activations to form inserted species followed by isomerizations to form product-likeintermediate. The rate determining steps for the elimination reactions of forming CH_4 and H_2 arethe isomerizations of the inserted species rather than C―C or C―H bond activations. Theelimination reaction of forming H_2 was found to be thermodynamically favored compared to that ofCH_4.展开更多
基金financially supported by the National Key R&D Program of China(No.2024YFF0506300)the National Natural Science Foundation of China(Nos.52472202 and 52272205)Hubei Province Science and Technology Program(Nos.2024EHA045,2024BCB073)
文摘Ethylene(C_(2)H_(4))is conventionally produced by a high energy-consumption process based on the steam cracking of ethane(C_(2)H_(6)).In contrast,we presented a novel symmetrical solid oxide fuel cell(SOFC)to coproduce electricity and C_(2)H_(4)through C_(2)H_(6)dehydrogenation.The symmetrical cell contains a thin Ba Zr_(0.1)Ce_(0.7)Y_(0.2)O_(3)(BZCY)electrolyte sandwiched between two thicker(PrBa)_(0.95)(Fe_(0.7)Ni_(0.2)Cu_(0.1))_(1.8)Mo_(0.2)O_(6-δ)impregnated BZCY(PBFNCM-BZCY)electrodes.The as-synthesized reduced-PBFNCM(R-PBFNCM)contained Fe-Ni-Cu alloy particles embedded on a double-perovskite matrix uniformly,while the electrode showed high oxygen vacancy concentration,electronic conductivity,redox stability,and activity for C_(2)H_(6)dehydrogenation with improved ethylene selectivity.The symmetrical cell demonstrated a peak power density of 409 mW cm^(-2)using C_(2)H_(6)as fuel,accompanying with a C_(2)H_(6)conversion of 51.2%,a C_(2)H_(4)selectivity of 92.5%,and a C_(2)H_(4)yield of 47.4%at 750℃and 750 mA cm^(-2).Despite carbon deposition occurred slowly in the anode,the deposited carbon was removed by simply switching C_(2)H_(6)and air between electrodes.Consequently,the cell voltage and C_(2)H_(4)yield recover by 91.4%and 98.1%,respectively,after three switches with an interval of 48 h,suggesting that the symmetrical SOFC is a promising solution for long-term continuous electricity and C_(2)H_(4)co-production by C_(2)H_(6)dehydrogenation.
文摘(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]是新型含能钙钛矿化合物的典型代表,需明确其热分解行为、热分解机制及感度特性,以推动其在配方中的应用。以差示扫描量热-热重分析方法实现了分解放热量、分解温度等参数的获取;以动力学模拟计算解析了相关分解机理;以同步热分析-红外-质谱联用技术结合原位红外技术探索了(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]的分解产物及分解历程;以国军标法获得了热感度、摩擦感度与撞击感度参数。结果表明:在10℃·min^(-1)的升温速率下,(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]分解放热量为4227 J·g^(-1),分解温度则达到345℃,高于黑索今(RDX)、奥克托今(HMX)、六硝基六氮杂异伍兹烷(CL-20)等多数现役含能材料,显示了优异的热稳定性;分解产物研究表明其立方笼状骨架有效稳定了内部结合的有机物分子,使其热稳定性较高。此外,(C_(6)H_(14)N_(2))[Na(ClO_(4))_(3)]在100℃下加热48 h的放气量约0.04 m L·g^(-1),撞击感度与机械感度分别为32%和80%,优于RDX和HMX。
基金the support from the National Natural Science Foundation of China(Nos.22378138,22278148,and 21978099).
文摘Efficient recovery of ethane(C_(2)H_(6))from natural gas is of industrial importance,yet it poses considerable challenges.Herein,we report the two-step green preparation of asphalt-based carbon adsorbent Asphalt-based Carbon adsorbents(AsCs)with exceptional C_(2)H_(6)/CH_(4) selectivity and high capacity,where the KOH usage can be significantly reduced by 75% than conventional chemical activation processes.More importantly,the resulting AsC-0.75-900 exhibits exceptional C_(2)H_(6)/CH_(4) separation performance with the ideal adsorbed solution theory(IAST)selectivity of 30.74 and C_(2)H_(6) capacity of 4.53 mmol/g at 298 K and 100 kPa.Notably,even at the low pressure of 10 kPa,its C_(2)H_(6) uptake remains high at 2.25 mmol/g,comparable to many advanced metal-organic frameworks(MOFs).Molecular simulation was used to elucidate the adsorption mechanism.Fixed-bed experiments further demonstrate dynamic separation performance,achieving complete separation of a C_(2)H_(6)/CH_(4) binary mixture(10:90,v/v)at ambient condition.In addition to superior separation performance,AsC-0.75-900 offers inherent structural stability and cost-effectiveness,positioning it a highly promising candidate for C_(2)H_(6) recovery from natural gas.
基金supported by the National Key Research and Development Program of China(2022YFA1502901)National Natural Science Foundation of China(22035003,22201137,and 22371137)Fundamental Research Funds for the Central Universities(63253171).
文摘Ethane-selective adsorbents enable the direct production of high-purity C_(2)H_(4)in a single step,showcasing substantial research potential.In this work,we report the synthesis of two hydrogen-bonded organic frameworks(HOFs),NKM-HOF-6 and NKM-HOF-7,featuring permanent microporosity.Upon treatment with hot acetone,NKM-HOF-6 undergoes a structural transformation into NKM-HOF-7,characterized by a transition from a 3D polycatenated framework to a 2D parallel displacement-stacked structure.This transformation leads to a reduction in the maximum pore size of NKM-HOF-7 and a decrease in the density of-CF_(3)groups within its channels,thereby enhancing its preferential affinity for C_(2)H_(6)over C_(2)H_(4).The adsorption capacity difference between C_(2)H_(6)and C_(2)H_(4)in NKM-HOF-7 is 11.1 cm^(3)·g^(-1),with an IAST selectivity of 1.77,surpassing the corresponding values for NKM-HOF-6(9.6 cm^(3)·g^(-1)and 1.56,respectively).Breakthrough experiments further reveal that NKM-HOF-7 achieves nearly twice the separation efficiency of NKM-HOF-6 for C_(2)H_(6)/C_(2)H_(4)(10/90,V/V)mixtures.Theoretical calculations attribute this enhanced C_(2)H_(6)affinity to the synergistic effects of optimized pore dimensions and functionalized pore surfaces in NKM-HOF-7.These findings provide critical insights for the rational design of highly efficient C_(2)H_(6)-selective adsorbents.
基金supported by the National Natural Science Foundation of China(Nos.22302002 and 22375006)the University Science Research Project of Anhui Province(Nos.2022AH050182 and 2022AH020020).
文摘Efficient CO_(2) photoreduction towards C_(2+)solar fuels has emerged as one of the most promising strategies for alleviating the current energy and environment problems.However,the C-C coupling barriers and complex multi-electron transfer steps still limit the activity and selectivity of CO_(2)-to-C_(2) photoreduction.Herein,Au nanoparticles(NPs)modified CeO_(2) with oxygen vacancies(Au/CeO_(2)-VO)were reported for enhancing the CO_(2)-to-C_(2)H_(6) photoreduction performance.Au/CeO_(2)-VO achieved the high C_(2)H_(6) activity of 51.7μmol·g^(-1)·h^(-1),accompanied with C_(2)H_(6) selectivity up to 80% in the absence of sacrificial agent.Experimental results combined with theoretical simulation indicated that VO strengthened CO_(2) adsorption and activated*CO production,and plasmon-induced hot electrons from Au NPs to CeO_(2)-VO facilitated the*CO-*CO dimerization.The synergistic modulation of VO and hot electrons further decreased the energy barriers of C-C coupling and subsequent hydrogenation,resulting in the superior photoreduction performance.This work opens an avenue of developing plasmonic photocatalysts for multi-carbon products from CO_(2) photoreduction.
基金supported by the Basic Science Center Program for Ordered Energy Conversion of the National Natural Science Foundation of China (52488201)the Sichuan Science and Technology Program (2024YFHZ0037)+2 种基金the Natural Science Basic Research Program of Shaanxi (2024JC-YBMS-284)the Key Research and Development Program of Shaanxi (2024GH-YBXM-02)the Fundamental Research Funds for the Central Universities。
文摘BiOI mateials show significant potential forphotocatalytic CO_(2) reduction, but their limited CO_(2) activationand poor charge carrier properties hinder conversion efficiency.In this study, we engineered BiOI-based photocatalystswith abundant crystal defects to enhance performance. X-raydiffraction (XRD), Raman spectroscopy, and high-resolutiontransmission electron microscopy (HRTEM) revealed latticedistortions and twin crystals in BiOI-LD and BiOI-TC. Ultraviolet-visible spectroscopy, micropore and chemisorptionanalyses, and photoluminescence spectroscopy demonstratedthat crystal defects improved light absorption, CO_(2) adsorption,charge transfer efficiency, and carrier lifetime. Electronparamagnetic resonance (EPR) spectroscopy showed increasedsuperoxide radical generation in BiOI-TC, suggesting higherreactivity. Consequently, BiOI achieved a CH_(3)CH_(2)OH generationrate of 6.2 μmol g.1 h.1 with 100% selectivity. Keyintermediates (*CO, *COCO, *CHO, *CH_(2)) for CH_(3)CH_(2)OHproduction were identified, and C_(2)H_(6) formation in BiOI-LDwas linked to the generation of *CH_(3).
文摘The mechanism of the reaction of Ni^+ (~2D) with ethane in the gas-phase wasstudied by using density functional theory. Both the B3LYP and BLYP functionals with standardall-electron basis sets are used to give the detailed information of the potential energy surface(PES) of [Ni, C_2, H_6]^+. The mechanisms forming the products CH_4 and H_2 in the reaction of Ni^+with ethane are proposed. The reductive eliminations of CH_4 and H_2 are typicaladdition-elimination reactions. Each of the two reactions consists of two elementary steps; C―C orC―H bond activations to form inserted species followed by isomerizations to form product-likeintermediate. The rate determining steps for the elimination reactions of forming CH_4 and H_2 arethe isomerizations of the inserted species rather than C―C or C―H bond activations. Theelimination reaction of forming H_2 was found to be thermodynamically favored compared to that ofCH_4.
