This study systematically investigates the cyclization reaction mechanisms between n-C_(4)H_(3)(1-buten-3-yn-1-yl)and i-C_(4)H_(3)(2-buten-3-yn-1-yl)radicals with acetylene(C_(2)H_(2))using density functional theory(D...This study systematically investigates the cyclization reaction mechanisms between n-C_(4)H_(3)(1-buten-3-yn-1-yl)and i-C_(4)H_(3)(2-buten-3-yn-1-yl)radicals with acetylene(C_(2)H_(2))using density functional theory(DFT)and transition state theory(TST).The results reveal that the reaction of n-C_(4)H_(3)with acetylene proceeds via a radical chain mechanism through an additioncyclization pathway,yielding phenyl(sixmembered ring),fulvenyl(five-membered ring),and four-membered ring intermediates.The product formation rates follow the order:fulvenyl(five-membered ring)>phenyl(six-membered ring)>four-membered ring.For i-C_(4)H_(3),the intermediate structures depend on the carbon position of i-C_(4)H_(3)where acetylene addition occurs:addition at the C2 position predominantly generates fulvenyl(five-membered ring)as the primary product,whereas addition at the C4 position may lead to phenyl(six-membered ring),fulvenyl(five-membered ring),or four-membered ring intermediates,with the four-membered ring forming most rapidly and the six-membered ring the slowest.Theoretical analyses demonstrate that the selectivity of reaction pathways is primarily governed by structural differences between the isomers.This work provides atomic-scale insights into the cyclization processes between acetylene and C_(4)H_(3)species,establishing a foundation for refining models of soot precursor formation.展开更多
Renewable electricity-driven production of value-added sulfur and H_(2)via electrocatalytic H_(2)S decomposition represents a sustainable route to conventional thermocatalysis.Both the electrocatalyst and electrolyte ...Renewable electricity-driven production of value-added sulfur and H_(2)via electrocatalytic H_(2)S decomposition represents a sustainable route to conventional thermocatalysis.Both the electrocatalyst and electrolyte solution strongly impact the H_(2)S decomposition performance.Despite significant progress in developing sophisticated electrocatalysts,a well-designed electrolyte solution in conjunction with industrial catalysts is an attractive strategy to advance the industrialization process of electrocatalytic H_(2)S decomposition,but remains unexplored.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of CS_(2)-N electrolyte solution and Ni-Mo_(2)C that can efficiently enable H_(2)S decomposition into valuable H_(2)and sulfur.Specifically,the solid-phase Ni-Mo_(2)C as a heterogeneous redox mediator presents excellent electrocatalytic efficiency for the H_(2)S removal efficiency of up to 99%,and the formation of liquid-phase sulfur product(CS_(2)-N electrolyte solution dissolves sulfur,yield up to 95%)with the generation of gas-phase H_(2)product(~1.32 mL min^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the scale-up production(~6 g in a batch experiment)of sulfur with continuous operation for 120 h without attenuation.This work may inaugurate a new electrocatalytic H_(2)S decomposition avenue to explore porous metal materials and electrolyte systems in simultaneous production of value-added sulfur and H_(2).展开更多
Inorganic materials can solve transportable and on-site hydrolytic hydrogen generation issues.CaH_(2)/(Al/Si)composites are preferable due to their notable chemical properties.However,these composites require pretreat...Inorganic materials can solve transportable and on-site hydrolytic hydrogen generation issues.CaH_(2)/(Al/Si)composites are preferable due to their notable chemical properties.However,these composites require pretreatments,an inert environment,and long hours of physical ball milling for high homogeneity and synergistic effects.CaH_(2)also inhibits the hydrolysis reaction by forming its products on the Al/Si surface,which hinders the direct utilization of composites.This work represents the first investigation of NaH-CaH_(2)(Al/Si)fuel composites,which greatly overcome these limitations and can be directly used for on-site hydrogen generation and proton exchange membrane(PEM)fuel cells.The NaH-CaH_(2)(Al/Si)fuel composites were prepared by using a straightforward mixing method with variable composition ratios,showing high H_(2)yield and fuel cell(FC)performance.NaH addition provides the bridge effect,which opens up a new way to enable efficient hydrolysis and greatly enhances the hydrolysis activity of CaH_(2)/(Al/Si)composites.The novel fuel composites(NaH-CaH_(2)/Al)have extraordinary FC performance and a 0.42 W/cm2 peak power density greater than commercial hydrogen generators.It provides high H_(2)yield 84.4%for NaH-CaH_(2)/Al and 82%for NaH-CaH_(2)/Si compared to NaOH-CaH_(2)(Al/Si),NaCl-CaH_(2)(Al/Si),and KCl-CaH_(2)(Al/Si)composites.The NaH bridge effect hinders the direct water contact and stops the formation of Ca(OH)2 around Al/Si,which provides adequate pathways for the CaH_(2)(Al/Si)hydrolysis.The impressive capabilities of novel fuel composites are anticipated to offer practical uses in fuel cells,automobile applications,and portable/on-board H_(2)generation.展开更多
Developing advanced electrocatalysts to convert CO_(2) into liquid fuels such as C_(2)H_(5)OH is critical for utilizing intermittent renewable energy.The formation of C_(2)H_(5)OH,however,is generally less favored com...Developing advanced electrocatalysts to convert CO_(2) into liquid fuels such as C_(2)H_(5)OH is critical for utilizing intermittent renewable energy.The formation of C_(2)H_(5)OH,however,is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts.In this work,an alkanethiolmodified Cu_(2)O nanowire array(OTT-Cu_(2)O) was constructed with asymmetric Cu sites consisting of paired Cu-O and Cu-S motifs to overcome previous limitations of C_(2)H_(5)OH electrosynthesis via CO_(2)RR pathway.This catalyst achieves a high Faradaic efficiency of 45 % for CO_(2)-to-C_(2)H_(5)OH conversion at 300 m A/cm^(2),representing a more than two-fold enhancement over the Cu_(2)O electrode.Mechanistic investigations reveal that the Cu-S site exhibits distinct C-binding capability that stabilizes key intermediates(^(*)OCH_(2) and ^(*)CO),in contrast to the O-affinitive Cu-O site.The asymmetric S-Cu-O configuration promotes thermodynamically favorable asymmetric C-C coupling between ^(*)CO and ^(*)OCH_(2),forming the critical CO-OCH_(2) intermediate and facilitating C_(2)H_(5)OH production,as opposed to symmetric O-Cu-O sites that mainly generate HCOOH.This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO_(2) reduction to C_(2)H_(5)OH and provides fundamental insight into the reaction mechanism.展开更多
基金Supported by the National Key Research and Development Program of China(2022YFB4301400)the Basic Science(Natural Science)Research Project for Higher Education Institutions in Jiangsu Province(24KJD580001)。
文摘This study systematically investigates the cyclization reaction mechanisms between n-C_(4)H_(3)(1-buten-3-yn-1-yl)and i-C_(4)H_(3)(2-buten-3-yn-1-yl)radicals with acetylene(C_(2)H_(2))using density functional theory(DFT)and transition state theory(TST).The results reveal that the reaction of n-C_(4)H_(3)with acetylene proceeds via a radical chain mechanism through an additioncyclization pathway,yielding phenyl(sixmembered ring),fulvenyl(five-membered ring),and four-membered ring intermediates.The product formation rates follow the order:fulvenyl(five-membered ring)>phenyl(six-membered ring)>four-membered ring.For i-C_(4)H_(3),the intermediate structures depend on the carbon position of i-C_(4)H_(3)where acetylene addition occurs:addition at the C2 position predominantly generates fulvenyl(five-membered ring)as the primary product,whereas addition at the C4 position may lead to phenyl(six-membered ring),fulvenyl(five-membered ring),or four-membered ring intermediates,with the four-membered ring forming most rapidly and the six-membered ring the slowest.Theoretical analyses demonstrate that the selectivity of reaction pathways is primarily governed by structural differences between the isomers.This work provides atomic-scale insights into the cyclization processes between acetylene and C_(4)H_(3)species,establishing a foundation for refining models of soot precursor formation.
基金supported by the National Natural Science Foundation of China(No.22278439 and 21776313).
文摘Renewable electricity-driven production of value-added sulfur and H_(2)via electrocatalytic H_(2)S decomposition represents a sustainable route to conventional thermocatalysis.Both the electrocatalyst and electrolyte solution strongly impact the H_(2)S decomposition performance.Despite significant progress in developing sophisticated electrocatalysts,a well-designed electrolyte solution in conjunction with industrial catalysts is an attractive strategy to advance the industrialization process of electrocatalytic H_(2)S decomposition,but remains unexplored.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of CS_(2)-N electrolyte solution and Ni-Mo_(2)C that can efficiently enable H_(2)S decomposition into valuable H_(2)and sulfur.Specifically,the solid-phase Ni-Mo_(2)C as a heterogeneous redox mediator presents excellent electrocatalytic efficiency for the H_(2)S removal efficiency of up to 99%,and the formation of liquid-phase sulfur product(CS_(2)-N electrolyte solution dissolves sulfur,yield up to 95%)with the generation of gas-phase H_(2)product(~1.32 mL min^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the scale-up production(~6 g in a batch experiment)of sulfur with continuous operation for 120 h without attenuation.This work may inaugurate a new electrocatalytic H_(2)S decomposition avenue to explore porous metal materials and electrolyte systems in simultaneous production of value-added sulfur and H_(2).
基金financial support granted by the National Natural Science Foundation of China (No. 22402225)the Gusu Innovation and Entrepreneurship Leading Talent Plan(No. ZXL2023193)+2 种基金the Sinano Talents Plan (No. 2022000175)the Guangdong Basic and Applied Basic Research Foundation (No.2023A1515111133)the ANSO Scholarship for Young Talents
文摘Inorganic materials can solve transportable and on-site hydrolytic hydrogen generation issues.CaH_(2)/(Al/Si)composites are preferable due to their notable chemical properties.However,these composites require pretreatments,an inert environment,and long hours of physical ball milling for high homogeneity and synergistic effects.CaH_(2)also inhibits the hydrolysis reaction by forming its products on the Al/Si surface,which hinders the direct utilization of composites.This work represents the first investigation of NaH-CaH_(2)(Al/Si)fuel composites,which greatly overcome these limitations and can be directly used for on-site hydrogen generation and proton exchange membrane(PEM)fuel cells.The NaH-CaH_(2)(Al/Si)fuel composites were prepared by using a straightforward mixing method with variable composition ratios,showing high H_(2)yield and fuel cell(FC)performance.NaH addition provides the bridge effect,which opens up a new way to enable efficient hydrolysis and greatly enhances the hydrolysis activity of CaH_(2)/(Al/Si)composites.The novel fuel composites(NaH-CaH_(2)/Al)have extraordinary FC performance and a 0.42 W/cm2 peak power density greater than commercial hydrogen generators.It provides high H_(2)yield 84.4%for NaH-CaH_(2)/Al and 82%for NaH-CaH_(2)/Si compared to NaOH-CaH_(2)(Al/Si),NaCl-CaH_(2)(Al/Si),and KCl-CaH_(2)(Al/Si)composites.The NaH bridge effect hinders the direct water contact and stops the formation of Ca(OH)2 around Al/Si,which provides adequate pathways for the CaH_(2)(Al/Si)hydrolysis.The impressive capabilities of novel fuel composites are anticipated to offer practical uses in fuel cells,automobile applications,and portable/on-board H_(2)generation.
基金financial supports of the National Natural Science Foundation of China (NSFC,Nos.52394202,52476056,and 52301232)the Natural Science Foundation of Chongqing Province (No.2024NSCQ-MSX1109)。
文摘Developing advanced electrocatalysts to convert CO_(2) into liquid fuels such as C_(2)H_(5)OH is critical for utilizing intermittent renewable energy.The formation of C_(2)H_(5)OH,however,is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts.In this work,an alkanethiolmodified Cu_(2)O nanowire array(OTT-Cu_(2)O) was constructed with asymmetric Cu sites consisting of paired Cu-O and Cu-S motifs to overcome previous limitations of C_(2)H_(5)OH electrosynthesis via CO_(2)RR pathway.This catalyst achieves a high Faradaic efficiency of 45 % for CO_(2)-to-C_(2)H_(5)OH conversion at 300 m A/cm^(2),representing a more than two-fold enhancement over the Cu_(2)O electrode.Mechanistic investigations reveal that the Cu-S site exhibits distinct C-binding capability that stabilizes key intermediates(^(*)OCH_(2) and ^(*)CO),in contrast to the O-affinitive Cu-O site.The asymmetric S-Cu-O configuration promotes thermodynamically favorable asymmetric C-C coupling between ^(*)CO and ^(*)OCH_(2),forming the critical CO-OCH_(2) intermediate and facilitating C_(2)H_(5)OH production,as opposed to symmetric O-Cu-O sites that mainly generate HCOOH.This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO_(2) reduction to C_(2)H_(5)OH and provides fundamental insight into the reaction mechanism.
