Metal–Organic Framework‐Based Hetero‐Phase Nanostructure Photocatalysts with Molecular‐Scale Tunable Energy Levels

Author:

Yuan Kuo123ORCID,Liu Zongyang1,Yan Zhuang45,Yun Qinbai6,Song Tianqun123,Guo Jun7,Zhang Xiaotao2,Zhong Dichang1,Tang Zhiyong45,Lu Tongbu1,Hu Wenping2

Affiliation:

1. Institute for New Energy Materials and Low Carbon Technologies School of Materials Science & Engineering Tianjin University of Technology 300384 Tianjin China

2. Department of Chemistry School of Science & Key Laboratory of Organic Integrated Circuits Ministry of Education Tianjin University 300072 Tianjin China

3. Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Nankai University 300071 Tianjin China

4. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication National Center for Nanoscience and Technology 100190 Beijing China

5. University of Chinese Academy of Sciences 100049 Beijing China

6. Department of Chemical and Biological Engineering & Energy Institute The Hong Kong University of Science and Technology Kowloon Hong Kong China This address is complete. There is no official postal code for Hong Kong.

7. State Key Laboratory of Separation Membranes and Membrane Processes School of Chemistry Tiangong University 300387 Tianjin China

Abstract

AbstractAs an effective method to modulate the physicochemical properties of materials, crystal phase engineering, especially hetero‐phase, plays an important role in developing high‐performance photocatalysts. However, it is still a huge challenge but significant to construct porous hetero‐phase nanostructures with adjustable band structures. As a kind of unique porous crystalline materials, metal–organic frameworks (MOFs) might be the appropriate candidate, but the MOF‐based hetero‐phase is rarely reported. Herein, we developed a secondary building unit (SBU) regulating strategy to prepare two crystal phases of Ti‐MOFs constructed by titanium and 1,4‐dicarboxybenzene, i.e., COK and MIL‐125. Besides, COK/MIL‐125 hetero‐phase was further constructed. In the photocatalytic hydrogen evolution reaction, COK/MIL‐125 possessed the highest H2 yield compared to COK and MIL‐125, ascribing to the Z‐Scheme homojunction at hetero‐phase interface. Furthermore, by decorating with amino groups (i.e., NH2‐COK/NH2‐MIL‐125), the light absorbing capacity was broadened to visible‐light region, and the visible‐light‐driven H2 yield was greatly improved. Briefly, the MOF‐based hetero‐phase possesses periodic channel structures and molecularly adjustable band structures, which is scarce in traditional organic or inorganic materials. As a proof of concept, our work not only highlights the development of MOF‐based hetero‐phase nanostructures, but also paves a novel avenue for designing high‐performance photocatalysts.

Funder

National Key Research and Development Program of China

National Natural Science Foundation of China

Tianjin Research Innovation Project for Postgraduate Students

Publisher

Wiley

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