Constructing cuprous oxide-modified zinc tetraphenylporphyrin ultrathin nanosheets heterojunction for enhanced photocatalytic carbon dioxide reduction to methane

Zhuoyue Wang; Shihao Min; Renfu Li; Wenlie Lin; Kang Li; Shoufeng Wang; Longtian Kang

doi:10.1016/j.jcis.2024.04.076

Constructing cuprous oxide-modified zinc tetraphenylporphyrin ultrathin nanosheets heterojunction for enhanced photocatalytic carbon dioxide reduction to methane

J Colloid Interface Sci. 2024 Aug:667:212-222. doi: 10.1016/j.jcis.2024.04.076. Epub 2024 Apr 15.

Authors

Zhuoyue Wang¹, Shihao Min¹, Renfu Li², Wenlie Lin², Kang Li², Shoufeng Wang¹, Longtian Kang³

Affiliations

¹ Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China; Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108, PR China; College of Chemistry, Fuzhou University, Fuzhou 350116, PR China; University Chinese Academy of Science, Fujian College, Fuzhou 350002, PR China.
² Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China; Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108, PR China; University Chinese Academy of Science, Fujian College, Fuzhou 350002, PR China.
³ Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China; Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, Fujian 350108, PR China; University Chinese Academy of Science, Fujian College, Fuzhou 350002, PR China. Electronic address: longtiank@fjirsm.ac.cn.

PMID: 38636223
DOI: 10.1016/j.jcis.2024.04.076

Abstract

The application of supermolecular naonostructures in the photocatalytic carbon dioxide reduction reaction (CO₂RR) has attracted increasing attentions. However, it still faces significant challenges, such as low selectivity for multi-electron products and poor stability. Here, the cuprous oxide (Cu₂O)-modified zinc tetraphenylporphyrin ultrathin nanosheets (ZnTPP NSs) are successfully constructed through the aqueous chemical reaction. Comprehensive characterizations confirm the formation of type-II heterojunction between Cu₂O and ZnTPP in Cu₂O@ZnTPP, and the electron transfer from Cu₂O to ZnTPP through the Zn-O-Cu bond under the static contact. Under the visible-light irradiation (λ > 420 nm), the optimized Cu₂O@ZnTPP sample as catalyst for photocatalytic CO₂RR exhibits the methane (CH₄) evolution rate of 120.9 μmol/g/h, which is ∼ 4 and ∼ 10 times those of individual ZnTPP NSs (28.0 μmol/g/h) and Cu₂O (12.8 μmol/g/h), respectively. Meanwhile, the CH₄ selectivity of ∼ 98.7 % and excellent stability can be achieved. Further experiments reveal that Cu₂O@ZnTPP has higher photocatalytic conversion efficiency than Cu₂O and ZnTPP NSs, and the photoinduced electron transfer from ZnTPP to Cu₂O can be identified via the path of ZnTPP→ (ZnTPP•ZnTPP)*→ ZnTPP^-→ Zn-O-Cu → Cu₂O. Consequently, Cu₂O@ZnTPP exhibits a shorter electron-hole separation lifetime (3.3 vs. 9.3 ps) and a longer recombination lifetime (23.1 vs. 13.4 ps) than individual ZnTPP NSs. This work provides a strategy to construct the organic nanostructures for photocatalytic CO₂RR to multi-electron products.

Keywords: Cu(2)O; Heterojunction; Methane; Photocatalytic CO(2) reduction; Zinc tetraphenylporphyrin.