Core-Shell Covalently Linked Graphitic Carbon Nitride-Melamine-Resorcinol-Formaldehyde Microsphere Polymers for Efficient Photocatalytic CO2 Reduction to Methanol

被引:115
作者
Ding, Jie [1 ,2 ,3 ]
Tang, Qingli [4 ]
Fu, Yanghe [5 ]
Zhang, Yulong [6 ]
Hu, Juanmin [1 ]
Li, Tong [1 ]
Zhong, Qin [1 ]
Fan, Maohong [2 ,3 ,7 ]
Kung, Harold H. [8 ]
机构
[1] Nanjing Univ Sci & Technol, Sch Chem & Chem Engn, Nanjing 210094, Jiangsu, Peoples R China
[2] Univ Wyoming, Dept Chem Engn, Laramie, WY 82071 USA
[3] Univ Wyoming, Dept Petr Engn, Laramie, WY 82071 USA
[4] Shanghai Jiao Tong Univ, Univ Michigan Shanghai Jiao Tong Univ Joint Inst, Shanghai 200240, Peoples R China
[5] Zhejiang Normal Univ, Key Lab, Minist Educ Adv Catalysis Mat, Inst Phys Chem, Jinhua 321004, Zhejiang, Peoples R China
[6] Henan Polytech Univ, Coll Chem & Chem Engn, Jiaozuo 454000, Henan, Peoples R China
[7] Georgia Inst Technol, Sch Civil & Environm Engn, Atlanta, GA 30332 USA
[8] Northwestern Univ, Dept Chem & Biol Engn, Evanston, IL 60208 USA
基金
中国国家自然科学基金;
关键词
CONVERSION; HYDROGEN; ACID; COMPOSITE; GRAPHENE; WATER; AU; PD;
D O I
10.1021/jacs.1c13301
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Photocatalytic reduction of CO2 with light and H2O to form CH3OH is a promising route to mitigate carbon emissions and climate changes. Although semiconducting metal oxides are potential photocatalysts for this reaction, low photon efficiency and leaching of environmentally unfriendly toxic metals limit their applicability. Here, we report metal-free, core-shell photocatalysts consisting of graphitic carbon nitride (g-C3N4, CN) covalently linked to melamine-resorcinol-formaldehyde (MRF) microsphere polymers for this reaction. Covalent linkage enabled efficient separation of photogenerated carriers and photocatalysis. Using 100 mg of a photocatalyst containing 15 wt % CN, a CH3OH yield of 0.99 mu mol.h(-1) was achieved at a reaction temperature of 80 degrees C and 0.5 MPa with external quantum efficiencies ranging from 5.5% at 380 nm to 1.7% at 550 nm. The yield was about 20 and 10 times higher than that of its components CN and MRF, respectively. Characterization with X-ray photoelectron spectroscopy, transmission electron microscopy, and bulk and surface elemental analyses supported the formation of a core-shell structure and the charge transfer in the C-N bond at the CN-MRF interface between the methoxy group in the 2,4-dihydroxylmethyl-1,3-diphenol part of MRF and the terminal amino groups in CN. This enhanced ligand-to-ligand charge transfer resulted in 67% of the photo-excited internal charge transferred from CN to the hydroxymethylamino group in MRF, whose amino group was the catalytic site for the CO2 photocatalytic reduction to CH3OH. This study provides a series of new metal-free photocatalyst designs and insights into the molecular-level structure-mediated photocatalytic response.Y
引用
收藏
页码:9576 / 9585
页数:10
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