{"id":131726,"date":"2023-09-15T07:29:00","date_gmt":"2023-09-15T05:29:00","guid":{"rendered":"https:\/\/renewable-carbon.eu\/news\/?p=131726"},"modified":"2023-09-12T13:56:48","modified_gmt":"2023-09-12T11:56:48","slug":"researchers-reveal-photocoupled-electroreduction-of-co2-over-photosensitizer-decorated-covalent-organic-frameworks","status":"publish","type":"post","link":"https:\/\/renewable-carbon.eu\/news\/researchers-reveal-photocoupled-electroreduction-of-co2-over-photosensitizer-decorated-covalent-organic-frameworks\/","title":{"rendered":"Researchers Reveal Photocoupled Electroreduction of CO2\u00a0over Photosensitizer Decorated Covalent Organic Frameworks"},"content":{"rendered":"\n\n
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\u00a9 American Chemical Society<\/figcaption><\/figure><\/div>\n\n\n

Electrocatalytic CO2<\/sub>\u00a0reduction reaction (CO2<\/sub>RR) is thought to be an ecologically favorable technique to use CO2<\/sub>\u00a0as a cheap and abundant C1 feedstock for the production of value-added chemicals such as CO. However, the thermodynamically stable nature of CO2<\/sub>\u00a0molecule featuring high C=O bond energy frequently leads to sluggish kinetics of CO2<\/sub>\u2192CO and high energy inputs.<\/strong><\/p>\n\n\n\n

Introducing an additional visible-light field will be a potential way to explore the optimized reaction conditions and develop effective catalysts for the efficient CO2<\/sub>RR towards CO, as the highly energetic photo-induced excited state of light-sensitive electrocatalysts can effectively optimize the formation barrier of reactive intermediates and lower the energy of the rate determining steps (RDS) of electrocatalytic CO2<\/sub>RR. The efficient excited state lifetime of the active site is an important influencing factor in visible photocoupled electrocatalysis.<\/p>\n\n\n\n

In a study published in Journal of the American Chemical Society<\/em><\/a>, a group led by Prof. CAO Rong and Prof. HUANG Yuanbiao from Fujian Institute of Research on the Structure of Matter of the Chinese Academy of Sciences incorporated the Ru(bpy)3<\/sub>Cl2<\/sub> photosensitive donors into a 2,2\u2019-bipyridine functionalized Co-porphyrin-based COF (Co-Bpy-COF) by a post-synthetic method (PSM), providing Co-Bpy-COF-Rux<\/sub> (X is the molar ratio of Ru and Co speices, X = 1\/2 and 2\/3) with longer excited state lifetime for CO2<\/sub> reduction under photo-electric conditions. Donor\u2013acceptor characteristic and giant built-in electric field in Co-Bpy-COF-Rux<\/sub> efficiently accelerate the photo-induced electron transfer from Ru(bpy)3<\/sub>Cl2<\/sub> to the cobalt porphyrin under the external light.<\/p>\n\n\n\n

The researchers found that compared with the unmodified counterpart Co-Bpy-COF, the optimal Co-Bpy-COF-Ru1\/2<\/sub>displays high CO Faradaic efficiency of 96.7% at -0.7 V vs reversible hydrogen electrode (RHE) and CO partial current density of 16.27 mA cm-2<\/sup> at -1.1 V vs RHE under the assistance of light, both of which were far surpassing the values observed in the dark. Nonetheless, for Co-Bpy-COF, the values of FECO<\/sub> and j<\/em>CO<\/sub> tested in the light displayed no significant improvement than those recorded in the dark, which could be attributed to the rapid relaxation of the excited state in the mono-photosensitive unit system.<\/p>\n\n\n\n

Besides, the researchers revealed the trend of excited-electron transfer from Ru(bpy)3<\/sub>Cl2 <\/sub>to cobalt porphyrin by highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the building units. The fluorescence quenching experiment and X-ray photoelectron spectroscopy (XPS) under the visible light further confirmed the real existence of excited-electron transfer from Ru(bpy)3<\/sub>Cl2<\/sub> to cobalt porphyrin.<\/p>\n\n\n\n

Furthermore, the researchers verified the formation of giant built-in electric field in Co-Bpy-COF-Rux<\/sub> by electrochemical impedance spectroscopy (EIS) and conductivity measurements. Ultrafast transient absorption (TA) spectra indicated that powerful donor (Ru(bpy)3<\/sub>Cl2<\/sub>) and giant built-in electric field dramatically extend the excited state lifetime of cobalt-porphyrins up to 3.4 times higher than the unmodified counterpart Co-Bpy-COF. The effect of external light irradiation lowering the energy barrier to the formation of CO was verified by the Tafel slopes and density function theory (DFT) calculations.<\/p>\n\n\n\n

This study focuses on extending long excited state lifetime of photo-coupled electrocatalysts for efficient CO2<\/sub>RR to CO products, and provides a guideline for the development of efficient photocoupled electrocatalysts.<\/p>\n","protected":false},"excerpt":{"rendered":"

Electrocatalytic CO2\u00a0reduction reaction (CO2RR) is thought to be an ecologically favorable technique to use CO2\u00a0as a cheap and abundant C1 feedstock for the production of value-added chemicals such as CO. However, the thermodynamically stable nature of CO2\u00a0molecule featuring high C=O bond energy frequently leads to sluggish kinetics of CO2\u2192CO and high energy inputs. Introducing an […]<\/p>\n","protected":false},"author":59,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"_seopress_robots_primary_cat":"none","nova_meta_subtitle":"New study focuses on extending long excited state lifetime of photo-coupled electrocatalysts for efficient CO2RR to CO products, and provides a guideline for the development of efficient photocoupled electrocatalysts","footnotes":""},"categories":[5571],"tags":[10744,20596,10630,10743],"supplier":[7471],"class_list":["post-131726","post","type-post","status-publish","format-standard","hentry","category-co2-based","tag-carboncapture","tag-electrocatalysis","tag-hydrogen","tag-useco2","supplier-chinese-academy-sciences"],"_links":{"self":[{"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/posts\/131726","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/users\/59"}],"replies":[{"embeddable":true,"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/comments?post=131726"}],"version-history":[{"count":0,"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/posts\/131726\/revisions"}],"wp:attachment":[{"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/media?parent=131726"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/categories?post=131726"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/tags?post=131726"},{"taxonomy":"supplier","embeddable":true,"href":"https:\/\/renewable-carbon.eu\/news\/wp-json\/wp\/v2\/supplier?post=131726"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}