Cr2O3/C@TiO2核壳型复合材料的设计合成及其光催化产氢性能

doi:10.1016/S1872-2067(20)63615-4

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 225-234.DOI: 10.1016/S1872-2067(20)63615-4

Cr₂O₃/C@TiO₂核壳型复合材料的设计合成及其光催化产氢性能

陈洋^a, 冒国兵^a, 唐亚文^a, 武恒^a, 王刚^a, 张力^b^,^*(), 刘琪^a^,^#()

^a安徽工程大学机械与汽车工程学院, 安徽芜湖241000
^b南开大学电子信息与光学工程学院, 天津300071

收稿日期:2020-03-19 接受日期:2020-05-04 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 张力,刘琪
基金资助:
安徽省对外科技合作项目(1704e1002212);安徽省高校自然科学研究项目重点项目(KJ2019A0157);安徽省人才工程(Z175050020001);天津市自然科学基金.(15JCYBJC21200)

Synthesis of core-shell nanostructured Cr₂O₃/C@TiO₂ for photocatalytic hydrogen production

Yang Chen^a, Guobing Mao^a, Yawen Tang^a, Heng Wu^a, Gang Wang^a, Li Zhang^b^,^*(), Qi Liu^a^,^#()

^aDepartment of materials science and Engineering, Anhui Polytechnic University, Wuhu 241000, Anhui, China
^bInstitute of Photoelectronics Thin Film Devices and Technique of Nankai University, Nankai University, Tianjin 300071, China

Received:2020-03-19 Accepted:2020-05-04 Online:2021-01-18 Published:2021-01-18
Contact: Li Zhang,Qi Liu
About author:^#Tel: +86-553-2871738; E-mail: modieer_67@ahpu.edu.cn
^*Tel: +86-22-23500197; E-mail: lzhang@nankai.edu.cn;
Supported by:
International Science and Technology Cooperation Project of Anhui Province(1704e1002212);the Key Project of Anhui Provincial Department of Education(KJ2019A0157);Talent Project of Anhui Province(Z175050020001);Tianjin Natural Science Foundation(15JCYBJC21200)

摘要/Abstract

摘要：

随着社会经济的快速发展, 能源危机和环境污染问题成为世界各国关注的焦点. 通过光催化剂将太阳能用于污染物降解、分解水产氢、CO₂还原及有机物合成等领域, 是解决上述问题的理想途径. 过渡金属氧化物TiO₂因其稳定性高、催化活性好、制备简单等优点, 被认为是最理想的光催化材料. 然而, TiO₂带隙较宽、光响应范围窄、光量子效率低等缺点限制了其实际应用. 将碳或Cr₂O₃与TiO₂结合形成复合结构已被证明可以有效提升其光催化性能. 另一方面, 金属离子的掺杂可以有效提高氧化钛的可见光响应.
本文利用具有高比表面积的金属有机骨架材料MIL-101(Cr)纳米材料作为模板、镉源和碳源, 首先在MIL-101(Cr)表面可控生长TiO₂纳米颗粒, 获得MIL-101(Cr)@TiO₂复合结构;然后在氮气保护下碳化形成Cr₂O₃/C@TiO₂核壳型复合材料. 碳化后, 制备的复合材料具有模板的八面体形貌和高比表面积, MIL-101(Cr)中的Cr元素一部分会形成Cr₂O₃, 一部分会掺杂到TiO₂中, 使得TiO₂的吸收边红移. 此外, Cr₂O₃/C@TiO₂中的C有利于光的吸收和载流子的分离. 这种独特的纳米结构赋予Cr₂O₃/C@TiO₂复合材料优异的光催化性能. 在300 W氙灯照射下, 该复合材料光解水产氢的速率为446 μmol h^-1 g^-1, 约为纯TiO₂的4倍. 在可见光照射下, Cr₂O₃/C@TiO₂分解水产氢的速率为25.5 μmol h^-1 g^-1. 将获得的粉体催化剂制备成光电极发现, Cr₂O₃/C@TiO₂在全幅光照射下的光电流密度在0.4 V (vs.Ag/AgCl)下达到2.3 mA/cm², 约为纯TiO₂的3.5倍. Cr₂O₃/C@TiO₂光催化产氢活性的提高一方面是由于Cr掺杂到TiO₂中使得其具有可见光响应, 另一方面MIL-101碳化获得的Cr₂O₃/C有效促进了光生载流子的分离.

关键词: 核壳结构, Cr₂O₃, 二氧化钛, 产氢, 光催化剂

Abstract:

In this study, the Cr₂O₃/C@TiO₂composite was synthesized via the calcination of yolk-shell MIL-101@TiO₂. The composite presented core-shell structure, where Cr-doped TiO₂ and Cr₂O₃/C were the shell and core, respectively. The introduction of Cr³⁺ and Cr₂O₃/C, which were derived from the calcination of MIL-101, in the composite enhanced its visible light absorbing ability and lowered the recombination rate of the photogenerated electrons and holes. The large surface area of the Cr₂O₃/C@TiO₂composite provided numerous active sites for the photoreduction reaction. Consequently, the photocatalytic performance of the composite for the production of H₂ was better than that of pure TiO₂. Under the irradiation of a 300 W Xe arc lamp, the H₂ production rate of the Cr₂O₃/C@TiO₂ composite that was calcined at 500 °C was 446 μmol h^-1 g^-1, which was approximately four times higher than that of pristine TiO₂ nanoparticles. Moreover, the composite exhibited the high H₂ production rate of 25.5 μmol h^-1 g^-1 under visible light irradiation (λ > 420 nm). The high photocatalytic performance of Cr₂O₃/C@TiO₂ could be attributed to its wide visible light photoresponse range and efficient separation of photogenerated electrons and holes. This paper offers some insights into the design of a novel efficient photocatalyst for water-splitting applications.

Key words: Core-shell structure, Cr₂O₃, TiO₂, Hydrogen generation, Photocatalyst

陈洋, 冒国兵, 唐亚文, 武恒, 王刚, 张力, 刘琪. Cr₂O₃/C@TiO₂核壳型复合材料的设计合成及其光催化产氢性能[J]. 催化学报, 2021, 42(1): 225-234.

Yang Chen, Guobing Mao, Yawen Tang, Heng Wu, Gang Wang, Li Zhang, Qi Liu. Synthesis of core-shell nanostructured Cr₂O₃/C@TiO₂ for photocatalytic hydrogen production[J]. Chinese Journal of Catalysis, 2021, 42(1): 225-234.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63615-4

https://www.cjcatal.com/CN/Y2021/V42/I1/225

图/表 10

Scheme 1. Schematic illustration of synthesis of Cr2O3/C@TiO2.

Fig. 1. Scanning electron micrographs of (a) MIL-101(Cr) and (b and c) MIL-101@TiO2. (d) Transmission electron micrograph of MIL-101@TiO2.

Fig. 2. (a) Fourier-transform infrared spectra of MIL-101(Cr), MT (MIL-101@TiO2) and MT500 (Cr2O3/C@TiO2) and (b) Raman spectra of MT500.

Fig. 3. (a) X-ray diffraction patterns of prepared samples: diffraction peak positions of (b) (101) plane of TiO2 in the 2θ range of 24.5°-26° and (c) Cr2O3 in the 2θ range of 33°-37°.

Fig. 4. (a and b) Scanning and (c) transmission electron micrographs of MT500; inset of (c) high-resolution transmission electron micrograph of MT500. (d) Scanning transmission electron micrograph and (e, f, g, and h) Cr, Ti, O, and C energy-dispersive X-ray spectroscopy mappings, respectively, of MT500.

Fig. 5. (a) Ultraviolet-visible absorption spectra and corresponding Kubelka-Munk function vs. the photon energy of prepared samples (b).

Fig. 6. X-ray photoelectron spectroscopy profiles of MT500: (a) survey, (b) Cr 2p, (c) Ti 2p, and (d) O 1s.

Fig. 7. (a) Rate of H2 production and (b) time evolution of photocatalytic H2 production over synthesized photocatalyst samples under the irradiation of a 300 W Xe arc lamp. (c) Cyclic H2 production over MT500 photocatalyst. (d) Time evolution of H2 production over prepared photocatalyst samples under visible light (λ > 420 nm) irradiation.

Fig. 8. (a) Photocurrent density at 0.4 V vs. Ag/AgCl under 300 W Xe arc lamp irradiation. (b) Electrochemical impendence spectra Nyquist plots and (c) photoluminescence spectra of pristine TiO2, MT, and MT500.

Fig. 9. Proposed mechanism for photocatalytic H2 production via water splitting over Cr2O3/C@TiO2 composite. Here NHE denotes the normal hydrogen electrode.

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Cr₂O₃/C@TiO₂核壳型复合材料的设计合成及其光催化产氢性能

Synthesis of core-shell nanostructured Cr₂O₃/C@TiO₂ for photocatalytic hydrogen production

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