Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O cr...Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.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the financial support from the National Natural Science Foundation of China (Nos.U23A20677,22022610 and 52400137)"Pioneer" and "Leading Goose" R&D Program of Zhejiang (Nos.2022C03146 and 2023C03017)+2 种基金China Postdoctoral Science Foundation (No.2024T170805)Zhejiang Provincial Natural Science Foundation of China (No.LDT23E06015B06)the support of the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University for assistance with the calculations。
文摘Cuprous oxide(Cu_(2)O) is one of the most promising catalysts for electrochemical conversion of CO_(2) into value-added C_(2) products.The efficiency of CO_(2)-to-C_(2) conversion is highly dependent on the Cu_(2)O crystal plane orientation and the corresponding adsorbed ^(*)CO species.Herein,we constructed high-index crystal planes(311) in Cu_(2)O(CO-Cu_(2)O) via a facile self-selective CO-induced strategy under a CO atmosphere,which was verified by high-resolution transmission electron microscopy(HR-TEM) and atomic force microscopy(AFM) results.By exploiting the high surface energy of the high index crystal planes,^(*)CO species are stabilized in CO-Cu_(2)O during CO_(2)RR,resulting in exceptional catalytic performance for CO_(2)-to-C_(2)products.In situ infrared spectroscopy revealed that both atop-type(^(*)CO_(atop)) and hollow-type(^(*)CO_(hollow)) adsorption of ^(*)CO species occurred on the CO-Cu_(2)O.The asymmetric C-C coupling energy barrier between ^(*)CO_(atop) and ^(*)CO_(hollow) in(311) crystal plane decreases by 47.8 % compared to the symmetric coupling of ^(*)CO_(atop) in conventional(100) crystal planes.Consequently,the Faradaic efficiency of C_(2) products generated with CO-Cu_(2)O was increased by as high as 100 % compared to that with pristine Cu_(2)O.
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.
