Abstract
The development of efficient oxygen evolution reaction (OER) photocatalysts to enable solar-driven photocatalytic water splitting into oxygen has been tremendously challenging, primarily due to the low oxygen evolution efficiency caused by intrinsically sluggish kinetics. Herein, we report the design of a novel “host-guest” photocatalytic system that incorporates the molecular ruthenium (Ru) catalyst into covalent triazine framework (CTF) channels through a facile immersion treatment. The CTF acts as the photosensitizer and support material, while the mononuclear Ru-based complex Ru-bda-Isoq acts as a molecular water-oxidation catalyst. Remarkably, Ru-bda-Isoq@CTF-Bph achieves an excellent oxygen evolution rate of up to 2308 µmol g−1 h−1 under visible light irradiation for 5 h. The structural matching between the porous photosensitizer and molecular catalyst is found to play a very critical role in achieving the high performance, and the specificity and universality of this system are also highlighted. This strategy provides valuable insights into the design of efficient water oxidation photocatalytic systems.
摘要
由于析氧反应的内在动力学缓慢, 开发高效的光催化析氧反应催化剂, 以利用太阳能进行光催化分解水产氧, 面临着巨大的挑战. 本研究设计了一种新型的“主-客体”光催化系统, 通过简单的预负载将单位点钌(Ru)分子催化剂引入共价三嗪框架(CTFs)的孔道内. 其中, CTFs作为光敏剂和光催化载体, 单核钌配合物Ru-bda-Isoq作为分子水氧化催化剂. 在可见光照射下, Ru-bda-Isoq@CTF-Bph 在5 h内**均析氧速率达到2308 µmol g−1 h−1, 其性能超过了大多数有机光催化剂. 同时, 研究还发现多孔光敏剂与分子催化剂之间的结构匹配起着非常关键的作用. 该体系具有广泛的适用性, 这一策略有助于高效水氧化光催化系统的设计.
References
Wang Q, Domen K. Particulate photocatalysts for light-driven water splitting: Mechanisms, challenges, and design strategies. Chem Rev, 2020, 120: 919–985
Hisatomi T, Kubota J, Domen K. Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev, 2014, 43: 7520–7535
Yue M, He X, Sun S, et al. Co-doped Ni3S2 nanosheet array: A high-efficiency electrocatalyst for alkaline seawater oxidation. Nano Res, 2023, doi: https://doi.org/10.1007/s12274-023-6002-6
Shi S, Sun S, He X, et al. Improved electrochemical alkaline seawater oxidation over cobalt carbonate hydroxide nanowire array by iron do**. Inorg Chem, 2023, 62: 11746–11750
Kudo A, Miseki Y. Heterogeneous photocatalyst materials for water splitting. Chem Soc Rev, 2009, 38: 253–278
Zhang G, Lan ZA, Wang X. Surface engineering of graphitic carbon nitride polymers with cocatalysts for photocatalytic overall water splitting. Chem Sci, 2017, 8: 5261–5274
Fang Y, Hou Y, Fu X, et al. Semiconducting polymers for oxygen evolution reaction under light illumination. Chem Rev, 2022, 122: 4204–4256
Wang X, Maeda K, Thomas A, et al. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater, 2009, 8: 76–80
Lin L, Lin Z, Zhang J, et al. Molecular-level insights on the reactive facet of carbon nitride single crystals photocatalysing overall water splitting. Nat Catal, 2020, 3: 649–655
Sheng Y, Li W, Xu L, et al. High photocatalytic oxygen evolution via strong built-in electric field induced by high crystallinity of perylene imide supramolecule. Adv Mater, 2022, 34: e2102354
Liu D, Yang X, Chen P, et al. Rational design of PDI-based linear conjugated polymers for highly effective and long-term photocatalytic oxygen evolution. Adv Mater, 2023, 35: e2300655
Zhang J, Wang Z, Shi J, et al. Bay-monosubstitution with electron-donating group as an efficiently strategy to functionalize perylene imide polymer for enhancing photocatalytic oxygen evolution activity. Adv Funct Mater, 2022, 32: 2205895
Bai Y, Li C, Liu L, et al. Photocatalytic overall water splitting under visible light enabled by a particulate conjugated polymer loaded with palladium and iridium. Angew Chem Int Ed, 2022, 61: e202201299
Sprick RS, Chen Z, Cowan AJ, et al. Water oxidation with cobalt-loaded linear conjugated polymer photocatalysts. Angew Chem Int Ed, 2020, 59: 18695–18700
Ma X, Wang H, Cheng J, et al. Fully conjugated ladder polymers as metal-free photocatalysts for visible-light-driven water oxidation. Chin J Chem, 2021, 39: 1079–1084
Li C, Liu J, Li H, et al. Covalent organic frameworks with high quantum efficiency in sacrificial photocatalytic hydrogen evolution. Nat Commun, 2022, 13: 2357
Yang Y, Chu X, Zhang HY, et al. Engineering β-ketoamine covalent organic frameworks for photocatalytic overall water splitting. Nat Commun, 2023, 14: 593
Wang C, Lyu P, Chen Z, et al. Green and scalable synthesis of atomic-thin crystalline two-dimensional triazine polymers with ultrahigh photocatalytic properties. J Am Chem Soc, 2023, 145: 12745–12754
Wang K, Yang LM, Wang X, et al. Covalent triazine frameworks via a low-temperature polycondensation approach. Angew Chem Int Ed, 2017, 56: 14149–14153
Kong D, Han X, **e J, et al. Tunable covalent triazine-based frameworks (CTF-0) for visible-light-driven hydrogen and oxygen generation from water splitting. ACS Catal, 2019, 9: 7697–7707
**e J, Shevlin SA, Ruan Q, et al. Efficient visible light-driven water oxidation and proton reduction by an ordered covalent triazine-based framework. Energy Environ Sci, 2018, 11: 1617–1624
Sun R, Tan B. Covalent triazine frameworks (CTFs): Synthesis, crystallization, and photocatalytic water splitting. Chem Eur J, 2023, 29: e202203077
Lan ZA, Fang Y, Zhang Y, et al. Photocatalytic oxygen evolution from functional triazine-based polymers with tunable band structures. Angew Chem Int Ed, 2018, 57: 470–474
Wang C, Zhang H, Luo W, et al. Ultrathin crystalline covalent-triazine-framework nanosheets with electron donor groups for synergistically enhanced photocatalytic water splitting. Angew Chem Int Ed, 2021, 60: 25381–25390
Zhang W, Fu Q, Luo Q, et al. Understanding single-atom catalysis in view of theory. JACS Au, 2021, 1: 2130–2145
Chen H, Gardner AM, Lin G, et al. Covalent triazine-based frameworks with cobalt-loading for visible light-driven photocatalytic water oxidation. Catal Sci Technol, 2022, 12: 5442–5452
Duan L, Wang L, Li F, et al. Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands. Acc Chem Res, 2015, 48: 2084–2096
Zhang B, Sun L. Ru-bda: Unique molecular water-oxidation catalysts with distortion induced open site and negatively charged ligands. J Am Chem Soc, 2019, 141: 5565–5580
Duan L, Bozoglian F, Mandal S, et al. A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II. Nat Chem, 2012, 4: 418–423
Wang L, Mirmohades M, Brown A, et al. Sensitizer-catalyst assemblies for water oxidation. Inorg Chem, 2015, 54: 2742–2751
Li F, Jiang Y, Zhang B, et al. Towards a solar fuel device: Light-driven water oxidation catalyzed by a supramolecular assembly. Angew Chem Int Ed, 2012, 51: 2417–2420
Liu M, Jiang K, Ding X, et al. Controlling monomer feeding rate to achieve highly crystalline covalent triazine frameworks. Adv Mater, 2019, 31: e1807865
Sun R, Wang X, Wang X, et al. Three-dimensional crystalline covalent triazine frameworks via a polycondensation approach. Angew Chem Int Ed, 2022, 61: e202117668
Hu X, Guo Y, Sun R, et al. Crystalline covalent triazine frameworks manipulated by aliphatic amine modulator. Sci China Chem, 2023, 66: 2676–2682
Chen J, Tao X, Li C, et al. Synthesis of bipyridine-based covalent organic frameworks for visible-light-driven photocatalytic water oxidation. Appl Catal B-Environ, 2020, 262: 118271
Karak S, Stepanenko V, Addicoat MA, et al. A covalent organic framework for cooperative water oxidation. J Am Chem Soc, 2022, 144: 17661–17670
Acknowledgements
The authors thank the Analysis and Testing Center, Huazhong University of Science and Technology for the assistance in the characterization of materials. This work was financially supported by the National Natural Science Foundation of China (22161142005 and 21975086), and the Science and Technology Department of Hubei Province (2019CFA008).
Author information
Authors and Affiliations
Contributions
Author contributions Tan B and Hu X conceived the project and designed the experiments. Sun R performed the experiments and analyzed the data. Sun R, Hu X, Wang X and Tan B co-wrote the manuscript. Shu C and Guo Y helped in collecting the optical and electronic data.
Corresponding author
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Supplementary information Experimental details and supporting data are available in the online version of the paper.
Bien Tan is a professor at the School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology (HUST). He received his PhD degree in 1999 from the College of Materials at South China University of Technology. He then joined Bei**g Institute of Aeronautical Materials for postdoctoral research at the National Laboratory of Advanced Composites (1999–2001). He worked as a post-doc research associate at the University of Liverpool (2001–2007). He then returned to China and joined HUST in September 2007 as a professor. His main research interests include polymeric materials, microporous materials, hydrogen storage, metal nano-particles, and high throughput materials methodology.
Ruixue Sun received her Bachelor’s degree in materials chemistry from Ludong University in 2016. She then received her Master’s degree in materials physics and chemistry from Shandong University in 2019. She is currently studying for her PhD degree in the group of Professor Bien Tan in polymer chemistry and physics at HUST. Her current research interests focus on the synthesis and applications of covalent triazine frameworks.
Xunliang Hu received his Bachelor’s degree in applied chemistry from Huazhong Agricultural University in 2013. He then received his Master’s degree in chemical engineering from Hubei University of Technology in 2017. He then received PhD degree in materials chemistry from HUST in 2022. His current research interests focus on the synthesis and applications of covalent triazine frameworks.
Rights and permissions
About this article
Cite this article
Sun, R., Hu, X., Shu, C. et al. Covalent triazine frameworks with Ru molecular catalyst for efficient photocatalytic oxygen evolution reaction. Sci. China Mater. 67, 642–649 (2024). https://doi.org/10.1007/s40843-023-2714-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-023-2714-x