二维非金属的石墨相氮化碳/共价三嗪骨架异质结构材料用于高效和高选择性光催化二氧化碳还原

doi:10.1016/S1872-2067(21)63936-0

催化学报 ›› 2022, Vol. 43 ›› Issue (5): 1306-1315.DOI: 10.1016/S1872-2067(21)63936-0

二维非金属的石墨相氮化碳/共价三嗪骨架异质结构材料用于高效和高选择性光催化二氧化碳还原

何杰^a, 王选东^a^,^d(), 金尚彬^b, 刘兆清^c, 朱明山^a()

^a暨南大学环境学院, 广东广州511443
^b西安交通大学化学工程与技术学院, 陕西西安710049
^c广州大学化学与化学工程学院/广州大学清洁能源材料研究所/广州市清洁能源材料重点实验室, 广东广州510006
^d佛山科学技术学院环境与化学工程学院, 广东佛山528225

收稿日期:2021-05-27 接受日期:2021-06-27 出版日期:2022-05-18 发布日期:2022-03-23
通讯作者: 王选东,朱明山
基金资助:
广东省自然科学杰出青年基金项目(2020B1515020038);广东省自然科学杰出青年基金项目(2020A1515011424);广东省“珠江人才计划”青年拔尖人才项目(2019QN01L148)

2D metal-free heterostructure of covalent triazine framework/g-C₃N₄ for enhanced photocatalytic CO₂ reduction with high selectivity

Jie He^a, Xuandong Wang^a^,^d(), Shangbin Jin^b, Zhao-Qing Liu^c, Mingshan Zhu^a()

^aSchool of Environment, Jinan University, Guangzhou 511443, Guangdong, China
^bSchool of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710049, Shannxi, China
^cSchool of Chemistry and Chemical Engineering/Institute of Clean Energy and Materials/Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou 510006, Guangdong, China
^dSchool of Environmental and Chemical Engineering, Foshan University, Foshan 528225, Guangdong, China

Received:2021-05-27 Accepted:2021-06-27 Online:2022-05-18 Published:2022-03-23
Contact: Xuandong Wang, Mingshan Zhu
Supported by:
the Guangdong Basic and Applied Basic Research Foundation(2020B1515020038);the Guangdong Basic and Applied Basic Research Foundation(2020A1515011424);Pearl River Talent Recruitment Program of Guangdong Province(2019QN01L148)

摘要/Abstract

摘要：

利用太阳光驱动CO₂转化成为有价值的化工品是一种极具前景的降低大气中CO₂含量和生产可再生能源的方法, 而这种方法主要依赖于具有高效分离载流子能力的光催化剂. 本文将石墨相氮化碳(g-C₃N₄, 简写为CN)和共价三嗪骨架(CTF)结合的非金属异质结构(CN/CTF)应用于CO₂的光催化还原反应中.

材料的zeta电位和X射线光电子能谱结果表明, CN和CTF在超声自组装过程中通过静电作用力相结合, 并进一步通过共价键作用增强其界面反应形成CN/CTF异质结构. 紫外可见漫反射光谱、光致发光光谱和时间分辨荧光衰变光谱等结果表明, CN/CTF异质结构具有较好的可见光吸收性质, 同时具备高效分离光生载流子的能力, 其电子转移速率达2.04 × 10⁸ s^‒1, 有助于提高光催化CO₂还原效率.

CTF的引入可以极大提高CN的光催化活性, 当CTF含量为2.5 wt%时CN/CTF异质结构还原CO₂生成CO的产率达到151.1 μmol/(g·h), 可稳定保持30 h, 且反应过程中几乎没有CH₄的生成, CO生成选择性达99.9%. 与单纯的CTF和CN相比, 最优条件的CN/CTF异质结构在可见光照射下能更有效地分离载流子, 且载流子复合率更低, 其光催化CO₂还原成CO的产率分别为CTF和CN的25.5倍和2.5倍. 与已报道的基于CN和CTF的光催化剂相比, CN/CTF异质结构具有更好的光催化活性、稳定性和还原CO₂选择性. 莫特肖特基曲线测试等实验结果表明, CN的导带电位和价带电位分别为-1.20和1.73 V, 而CTF的分别为-0.78和1.71 V, 该能带结构使得CN和CTF形成Ⅰ型异质结, 有利于进行CO₂/CO的还原反应(氧化还原电位为-0.52 V). 在反应动力学上, CN/CTF异质结构光催化CO₂还原生成CO仅需两对H⁺/e^-, 提高了生成CO的选择性, 同时助剂2,2’-联吡啶配合物的加入可加快电子传输效率, 实现CO₂的吸附断键和光催化还原的动态循环. 综上, 本文有望为基于太阳光驱动的光催化还原CO₂研究领域提供新的高效非金属催化剂.

关键词: 二氧化碳还原, 共价三嗪骨架, 石墨相氮化碳, 非金属异质结构, 光催化

Abstract:

Solar-driven CO₂ conversion to precious fossil fuels has been proved to become a potential way to decrease CO₂ with producing renewable fuels, which mainly relies on photocatalysts with efficient charge separation. In this work, a metal free heterostructure of covalent triazine framework (CTF) and graphite carbon nitride (g-C₃N₄, abbreviated as CN) is applied in the CO₂ photoreduction for the first time. Detailed characterization methods such as photoluminescence (PL) and time-resolved PL (TR-PL) decay are utilized to reveal the photo-induced carries separating process on g-C₃N₄/CTF (CN/CTF) heterostructure. The introduced CTF demonstrated a great boosting photocatalytic activity for CN, bringing about the transform rates of CO₂ to CO reaching 151.1 μmol/(g·h) with a 30 h stabilization time, while negligible CH₄ was detected. The optimal CN/CTF heterostructure could more efficiently separate charges with a lower probability of recombination under visible light irradiation, which made the photoreduction efficiency of CO₂ to CO be 25.5 and 2.5 times higher than that of CTF and CN, respectively. This investigation is expected to offer a new thought for fabricating high-efficiency photocatalyst without metal in solar-energy-driven CO₂ reduction.

Key words: CO₂ reduction, Covalent triazine framework, Graphite carbon nitride, Metal-free heterostructure, Photocatalysis

何杰, 王选东, 金尚彬, 刘兆清, 朱明山. 二维非金属的石墨相氮化碳/共价三嗪骨架异质结构材料用于高效和高选择性光催化二氧化碳还原[J]. 催化学报, 2022, 43(5): 1306-1315.

Jie He, Xuandong Wang, Shangbin Jin, Zhao-Qing Liu, Mingshan Zhu. 2D metal-free heterostructure of covalent triazine framework/g-C₃N₄ for enhanced photocatalytic CO₂ reduction with high selectivity[J]. Chinese Journal of Catalysis, 2022, 43(5): 1306-1315.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63936-0

https://www.cjcatal.com/CN/Y2022/V43/I5/1306

图/表 9

Fig. 1. The schematic diagram of synthesis and photocatalytic procedure of CN/CTF heterostructure.

Fig. 2. TEM patterns of CN (a), CTF (b) and CN/CTF heterostructure (c); (d) Enlarged TEM image of CN/CTF heterostructure; (e) XRD patterns of CN, CTF and CN/CTF.

Fig. 3. XPS spectra of C 1s (a) and N 1s (b); Raman spectra (c) and UV-Vis DRS (d) of CTF, CN and CN/CTF heterostructure.

Fig. 4. (a) Instantaneous photocurrent of CN and CN/CTF under light on/off; (b) EIS signals of CN and CN/CTF with/without light illumination; PL (c) and TR-PL decay curve (d) of CN and CN/CTF at the excitation light of 360 nm.

Table 1 TR-PL decay parameters of CN and CN/CTF at 360 nm stimulation wavelength.

Sample	τ₁ (ns)	A₁ (%)	τ₂ (ns)	A₂ (%)	τ_av (ns)	k_ET (/s)
CN	2.71	88.94	16.61	11.06	4.25	—
CN/CTF	0.77	70.31	5.85	29.69	2.28	2.04 × 10⁸

Fig. 5. (a) Yield of reduced products with reaction time via CN/CTF (2.5%) heterostructure; (b) The comparison of CO yield for CO2 reduction under 200 mW/cm2 visible light within 3 h with blank, CTF, CN, CN/CTF (1.0%), CN/CTF (2.5%), CN/CTF (5.0%) in acetonitrile/Co(bpy)3Cl2 TEOA system; (c) Cycle runs of photo-catalytic CO2 reduction by CN/CTF (2.5%) heterostructure.

Fig. 6. The GC-MS spectrum (a) and total ion chromatographic spectrum (b) of the isotope experiment using 12CO2 or 13CO2 as gas source with CN/CTF.

Fig. 7. Mott-Schottky plots of CN (a) and CTF (b); (c) Tauc’s plots of CN and CTF based on UV-Vis DRS spectrum; (d) Energy band structure of the as-synthesized CN/CTF heterostructure.

Fig. 8. The mechanism scheme of CN/CTF heterostructure for photocatalytic CO2 reduction.

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二维非金属的石墨相氮化碳/共价三嗪骨架异质结构材料用于高效和高选择性光催化二氧化碳还原

2D metal-free heterostructure of covalent triazine framework/g-C₃N₄ for enhanced photocatalytic CO₂ reduction with high selectivity

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二维非金属的石墨相氮化碳/共价三嗪骨架异质结构材料用于高效和高选择性光催化二氧化碳还原

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2D metal-free heterostructure of covalent triazine framework/g-C₃N₄ for enhanced photocatalytic CO₂ reduction with high selectivity