Rhodium complex-anchored and supramolecular polymer-grafted CdS nanoflower for enhanced photosynthesis of H₂O₂ and photobiocatalytic C–H bond oxyfunctionalization

Abstract

Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp³)–H bonds using only H₂O₂ as a clean oxidant, while also exhibiting sensitivity to H₂O₂ concentration. CdS-based semiconductors are promising for the photosynthesis of H₂O₂ owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process, however, they suffer from fast H₂O₂ decomposition on the surface of pristine CdS. Therefore, [Cp*Rh(bpy)H₂O]²⁺, a highly selective proton-coupled electron transfer catalyst, was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H₂O₂, mitigating the surface issue of pristine CdS, increasing light absorption, accelerating photonic carrier separation, and enhancing oxygen reduction reaction selectivity to H₂O₂. This photocatalyst promoted the light driven H₂O₂ generation rate up to 1345 μmol·L^–1·g^–1·h^–1, which was 2.4 times that of pristine CdS. The constructed heterojunction photocatalyst could supply H₂O₂ in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene, achieving a yield of 81% and an ee value of 99% under optimum conditions. A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system, achieving the corresponding chiral alcohols in good yield (51%–88%) and excellent enantioselectivity (90%–99% ee).

Graphical abstract

Keywords

cadmium sulfide / unspecific peroxygenases / photobiocatalysis / hydrogen peroxide / oxyfunctionalization

References

[1] Yamaguchi J , Yamaguchi A D , Itami K . Itami K. C–H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals. Angewandte Chemie International Edition, 2012, 51(36): 8960–9009

[2] Guillemard L , Kaplaneris N , Ackermann L , Johansson M J . Late-stage C–H functionalization offers new opportunities in drug discovery. Nature Reviews. Chemistry, 2021, 5(8): 522–545

[3] Sinha S K , Guin S , Maiti S , Biswas J P , Porey S , Maiti D . Toolbox for distal C–H bond functionalizations in organic molecules. Chemical Reviews, 2022, 122(6): 5682–5841

[4] Holmberg-Douglas N , Nicewicz D A . Photoredox-catalyzed C–H functionalization reactions. Chemical Reviews, 2022, 122(2): 1925–2016

[5] Zhang L , Ritter T . A perspective on late-stage aromatic C–H bond functionalization. Journal of the American Chemical Society, 2022, 144(6): 2399–2414

[6] Lam N Y S , Wu K , Yu J Q . Advancing the logic of chemical synthesis: C−H activation as strategic and tactical disconnections for C−C bond construction. Angewandte Chemie International Edition, 2021, 60(29): 15767–15790

[7] Heath R S , Turner N J . Recent advances in oxidase biocatalysts: enzyme discovery, cascade reactions and scale up. Current Opinion in Green and Sustainable Chemistry, 2022, 38: 100693

[8] Hobisch M , Holtmann D , Gomez de Santos P , Alcalde M , Hollmann F , Kara S . Recent developments in the use of peroxygenases—exploring their high potential in selective oxyfunctionalisations. Biotechnology Advances, 2021, 51: 107615

[9] Beltrán-Nogal A , Sánchez-Moreno I , Méndez-Sánchez D , Gómez de Santos P , Hollmann F , Alcalde M . Surfing the wave of oxyfunctionalization chemistry by engineering fungal unspecific peroxygenases. Current Opinion in Structural Biology, 2022, 73: 102342

[10] MonterreyD TMenés-RubioAKeserMGonzalez-PerezDAlcaldeM. Unspecific peroxygenases: the pot of gold at the end of the oxyfunctionalization rainbow? Current Opinion in Green and Sustainable Chemistry, 2023, 41: 100786

[11] Grogan G . Hemoprotein catalyzed oxygenations: P450s, UPOs, and progress toward scalable reactions. JACS Au, 2021, 1(9): 1312–1329

[12] Schmermund L , Reischauer S , Bierbaumer S , Winkler C K , Diaz-Rodriguez A , Edwards L J , Kara S , Mielke T , Cartwright J , Grogan G . . Chromoselective photocatalysis enables stereocomplementary biocatalytic pathways*. Angewandte Chemie International Edition, 2021, 60(13): 6965–6969

[13] YuWHuCBaiLTianNZhangYHuangH. Photocatalytic hydrogen peroxide evolution: what is the most effective strategy? Nano Energy, 2022, 104: 107906

[14] Lee J H , Cho H , Park S O , Hwang J M , Hong Y , Sharma P , Jeon W C , Cho Y , Yang C , Kwak S K . . High performance H₂O₂ production achieved by sulfur-doped carbon on CdS photocatalyst via inhibiting reverse H₂O₂ decomposition. Applied Catalysis B: Environment and Energy, 2021, 284: 119690

[15] Thakur S , Kshetri T , Kim N H , Lee J H . Sunlight-driven sustainable production of hydrogen peroxide using a CdS-graphene hybrid photocatalyst. Journal of Catalysis, 2017, 345: 78–86

[16] Zhang E , Zhu Q , Huang J , Liu J , Tan G , Sun C , Li T , Liu S , Li Y , Wang H . . Visually resolving the direct Z-scheme heterojunction in CdS@ZnIn₂S₄ hollow cubes for photocatalytic evolution of H₂ and H₂O₂ from pure water. Applied Catalysis B. Applied Catalysis B: Environment and Energy, 2021, 293: 120213

[17] Lai C , Xu M , Xu F , Li B , Ma D , Li Y , Li L , Zhang M , Huang D , Tang L . . An S-scheme CdS/K₂Ta₂O₆ heterojunction photocatalyst for production of H₂O₂ from water and air. Chemical Engineering Journal, 2023, 452: 139070

[18] Zhu B , Liu J , Sun J , Xie F , Tan H , Cheng B , Zhang J . CdS decorated resorcinol-formaldehyde spheres as an inorganic/organic S-scheme photocatalyst for enhanced H₂O₂ production. Journal of Materials Science and Technology, 2023, 162: 90–98

[19] Wei Z , Zhao S , Li W , Zhao X , Chen C , Phillips D L , Zhu Y , Choi W . Artificial photosynthesis of H₂O₂ through reversible photoredox transformation between catechol and o-benzoquinone on polydopamine-coated CdS. ACS Catalysis, 2022, 12(18): 11436–11443

[20] Zhang G , Li X , Chen D , Li N , Xu Q , Li H , Lu J . Internal electric field and adsorption effect synergistically boost carbon dioxide conversion on cadmium sulfide@covalent triazine frameworks core-shell photocatalyst. Advanced Functional Materials, 2023, 33(51): 2308553

[21] Mengele A K , Rau S . Product selectivity in homogeneous artificial photosynthesis using [(bpy)Rh(Cp*)X]ⁿ⁺-based catalysts. Inorganics, 2017, 5(2): 35

[22] Ogo S , Yatabe T , Tome T , Takenaka R , Shiota Y , Kato K . Safe, one-pot, homogeneous direct synthesis of H₂O₂. Journal of the American Chemical Society, 2023, 145(8): 4384–4388

[23] Lee C H , Kim J , Park C B . Park C B. Z-Schematic artificial leaf structure for biosolar oxyfunctionalization of hydrocarbons. ACS Energy Letters, 2023, 8(6): 2513–2521

[24] Deng X , Zheng X , Jia F , Cao C , Song H , Jiang Y , Liu Y , Liu G , Li S , Wang L . Unspecific peroxygenases immobilized on Pd-loaded three-dimensional ordered macroporous (3DOM) titania photocatalyst for photo-enzyme integrated catalysis. Applied Catalysis B: Environment and Energy, 2023, 330: 122622

[25] Jia F , Liu Y , Deng X , Cao X , Zheng X , Zhou L , Gao J , Jiang Y . Immobilization of enzymes on cyclodextrin-anchored dehiscent mesoporous TiO₂ for efficient photoenzymatic hydroxylation. ACS Applied Materials & Interfaces, 2023, 15(6): 7928–7938

[26] Zhang L , Ran J , Qiao S Z , Jaroniec M . Characterization of semiconductor photocatalysts. Chemical Society Reviews, 2019, 48(20): 5184–5206

[27] Xiang Q , Yu J , Jaroniec M . Synergetic effect of MoS₂ and graphene as cocatalysts for enhanced photocatalytic H₂ production activity of TiO₂ nanoparticles. Journal of the American Chemical Society, 2012, 134(15): 6575–6578

[28] Xiang Q , Cheng B , Yu J . Hierarchical porous CdS nanosheet-assembled flowers with enhanced visible-light photocatalytic H₂-production performance. Applied Catalysis B: Environment and Energy, 2013, 138: 299–303

[29] Chen Y , Zhong W , Chen F , Wang P , Fan J , Yu H . Photoinduced self-stability mechanism of CdS photocatalyst: the dependence of photocorrosion and H₂-evolution performance. Journal of Materials Science and Technology, 2022, 121: 19–27

[30] Xue X , Dong W , Luan Q , Gao H , Wang G . Novel interfacial lateral electron migration pathway formed by constructing metallized CoP₂/CdS interface for excellent photocatalytic hydrogen production. Applied Catalysis B: Environment and Energy, 2023, 334: 122860

[31] Xie L , Huang X , Huang Y , Yang K , Jiang P . Core-shell structured hyperbranched aromatic polyamide/BaTiO₃ hybrid filler for poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) nanocomposites with the dielectric constant comparable to that of percolative composites. ACS Applied Materials & Interfaces, 2013, 5(5): 1747–1756

[32] Xia M , Zhang W , Xu Y , Lin H , Jiao Y , Shen L , Li R , Zhang M , Hong H . Polyamide membranes with a ZIF-8@Tannic acid core-shell nanoparticles interlayer to enhance nanofiltration performance. Desalination, 2022, 541: 116042

[33] Li C Q , Du X , Jiang S , Liu Y , Niu Z L , Liu Z Y , Yi S S , Yue X Z . Constructing direct Z-scheme heterostructure by enwrapping ZnIn₂S₄ on CdS hollow cube for efficient photocatalytic H₂ generation. Advanced Science, 2022, 9(24): 2201773

[34] Mu Q , Su Y , Wei Z , Sun H , Lian Y , Dong Y , Qi P , Deng Z , Peng Y . Dissecting the interfaces of MOF-coated CdS on synergized charge transfer for enhanced photocatalytic CO₂ reduction. Journal of Catalysis, 2021, 397: 128–136

[35] Liu J , Ren X , Li C , Wang M , Li H , Yang Q . Assembly of COFs layer and electron mediator on silica for visible light driven photocatalytic NADH regeneration. Applied Catalysis B: Environment and Energy, 2022, 310: 121314

[36] Wang D , Zeng H , Xiong X , Wu M F , Xia M , Xie M , Zou J , Luo S L . Highly efficient charge transfer in CdS-covalent organic framework nanocomposites for stable photocatalytic hydrogen evolution under visible light. Science Bulletin, 2020, 65(2): 113–122

[37] Sun L , Li L , Yang J , Fan J , Xu Q . Fabricating covalent organic framework/CdS S-scheme heterojunctions for improved solar hydrogen generation. Chinese Journal of Catalysis, 2022, 43(2): 350–358

[38] Zou L , Sa R , Zhong H , Lv H , Wang X , Wang R . Photoelectron transfer mediated by the interfacial electron effects for boosting visible-light-driven CO₂ reduction. ACS Catalysis, 2022, 12(6): 3550–3557

[39] Gao R , Bai J , Shen R , Hao L , Huang C , Wang L , Liang G , Zhang P , Li X . 2D/2D covalent organic framework/CdS Z-scheme heterojunction for enhanced photocatalytic H₂ evolution: insights into interfacial charge transfer mechanism. Journal of Materials Science and Technology, 2023, 137: 223–231

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