基于氨基化煤基碳点的复合光催化剂的制备及对CO2还原的催化性能

doi:10.7503/cjcu20180597

摘要/Abstract

摘要：

采用过氧化氢氧化法剥离出煤炭结构中的晶体碳[煤基碳点(CDs)], 并通过亚硫酰氯氯化及乙二胺钝化等步骤对其进行氨基化修饰, 制得N, S共掺杂的氨基化煤基碳点(NH₂-CDs), 再利用其表面的氨基和含氧基等官能团的配位及分散作用, 将由氯化铜原位还原得到的氧化亚铜(Cu₂O)纳米粒子包覆于其中, 制备了复合催化剂Cu₂O/NH₂-CDs, 表征了其结构和形貌, 并考察了其可见光催化还原CO₂/H₂O的性能. 结果发现, NH₂-CDs的存在使复合催化剂不仅具备了较强的CO₂吸附性能, 而且还具有了高效的电子-空穴对分离和电子转移能力, 从而表现出优异的光催化还原CO₂制备HCOOH的性能. 反应6 h时, 产物HCOOH的量为2582.4 μmol/g cat, 约为同条件下纯Cu₂O作为光催化剂时产物HCOOH产率的7.3倍.

关键词: 煤炭, 氨基化碳点, 氧化亚铜, 光催化还原二氧化碳

Abstract:

The crystalline carbon in the coal structure[coal-based carbon dots(CDs)] was stripped by hydrogen peroxide oxidation method, and then the surface of the synthesized carbon dots was modified by thionyl chloride chlorination, ethylenediamine passivation steps to obtain N, S co-doped aminated coal-based carbon dots(NH₂-CDs). After that, using the coordination and dispersing function of amino groups and oxygen-containing functional groups on the surface, a kind of composite photocatalyst, Cu₂O/NH₂-CDs, was prepared by coating cuprous oxide(Cu₂O) nanoparticles, which were obtained by in situ reduction of copper chloride(CuCl₂∙2H₂O), on the NH₂-CDs. The structures of the Cu₂O/NH₂-CDs were characterized and the photocatalytic performance toward CO₂ reduction under visible light was tested. The results show that the presence of NH₂-CDs not only makes the composite catalyst possess excellent CO₂ adsorption performance, but also improve the efficient electron-hole pair separation and electron transfer ability of the composite catalysts, so that Cu₂O/NH₂-CDs show excellent CO₂ photocatalytic reduction to HCOOH performance. After reaction for 6 h, the amount of HCOOH was up to 2582.4 μmol/g cat, about 7.3 times of that on Cu₂O photocatalyst under the same conditions.

Key words: Coal, Aminated carbon dots, Cu₂O, Photocatalytic reduction of CO₂

中图分类号:

O644

TrendMD:

阿卜杜黑热木∙阿瓦提, 张得栋, 哈丽丹∙买买提. 基于氨基化煤基碳点的复合光催化剂的制备及对CO₂还原的催化性能. 高等学校化学学报, 2019, 40(2): 306.

ABUDUHEIREMU Awati,ZHANG Dedong,HALIDAN Maimaiti. Preparation and CO₂ Reduction Performance of Composite Photocatalyst Based on Aminated Coal-based Carbon Dots^†. Chem. J. Chinese Universities, 2019, 40(2): 306.

图/表 13

Scheme 1 Schematic illustration of the synthesis of Cu2O/NH2-CDs

Scheme 2 Schematic of experimental setup for photoreduction of CO2 with H2O

Fig.1 XRD pattern(A), EDS(B) and TG-DTG curves(C) of Cu2O/NH2-CDs

Fig.2 TEM(A) and HRTEM(B) images and particle distribution(C) of Cu2O/NH2-CDsThe insets in (A): TEM images of Cu2O(lower left corner) and NH2-CDs(upper right corner).

Fig.3 SEM image(A) and mapping results(B—F) of Cu2O/NH2-CDs(B) Cu; (C) C; (D) O; (E) N; (F) S.

Fig.4 FTIR(A) and Raman spectra(B) of Cu2O(a), NH2-CDs(b) and Cu2O/NH2-CDs(c)

Fig.5 XPS spectra of Cu2O/NH2-CDs and NH2-CDs[the insets in (B)—(F)](A) Survey; (B) C1s; (C) N1s; (D) O1s; (E) S2p; (F) Cu2p;

Fig.6 N2 adsorption-desorption isotherms and corresponding BJH pore size distributions(inset)(A) and CO2-TPD profiles(B) of Cu2O(a) and Cu2O/NH2-CDs(b)

Fig.7 1H NMR spectrum of the aqueous samples after 6 h of irradiation

Fig.8 Influence of NH2-CDs in Cu2O/NH2-CDs on HCOOH and CH3OH yield within 6 h

Fig.9 HCOOH yield changed with irradiation time with sample CP3 as catalystInset is the long-term time curve of recovered sample CP3 for photocatalysis of CO2(with solution being replaced and photocatalyst being recovered every 4 h).

Fig.10 DR UV-Vis spectra and the calculation of band gap(inset)(A), FL spectra(B), Nyquist plots(C) and transient photocurrent responses(D) of Cu2O(a) and Cu2O/NH2-CDs(b)

Scheme 3 Schematic of the mechanism of the photocatalytic CO2/H2O reduction on Cu2O/NH2-CDs

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基于氨基化煤基碳点的复合光催化剂的制备及对CO₂还原的催化性能

Preparation and CO₂ Reduction Performance of Composite Photocatalyst Based on Aminated Coal-based Carbon Dots^†

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