自然光合系统需要时空组织来优化光敏反应并保持整体效率，这涉及光合成分的分层自组装及其通过协同相互作用的稳定。然而，复制这种水平的组织是具有挑战性的，由于超分子纳米组件与纳米颗粒或生物结构的动态不稳定性，它们很难有效地沟通。作者证明了通过金属-酚配合物处理自组装的两亲罗丹明B纳米球（RN）的超分子重建导致了稳定的杂化结构的形成。这种重构的结构提高了电子传递效率，从而改善了光催化性能。由于RN的光致发光猝灭特性及其与单宁酸(T)和锆(Z)的电子协同作用，杂化纳米球（RNTxZy）与Pt纳米粒子或生物主体希瓦氏菌MR-1的超分子配合物在光催化制氢方面表现出明显的改善。Pt （Pt/RNTxZy）和MR-1 （M/RNTxZy）的析氢效率分别提高了5.6倍和4.0倍。这些结果突出了用于能量收集和生物混合系统的超分子纳米材料的结构和光化学控制的进一步发展潜力。
Figure 1. Supramolecular reconstruction and optical properties of RNTxZy hybrid structure. (a) Schematic illustration depicting the self-assembly of RhBC18 followed by metal phenolic coating with TA (T) and Zr (Z). (b) Zeta potential distribution comparison among RN, RNT20Z20, and T20Z20. (c) EDX mapping image of RNT20Z20 showing elemental distribution of C, Zr, and N. In the notation RNTxZy, ‘x’ and ‘y’ denote the molar concentrations of the corresponding components in the solution ([RN] = 100 μM, [Tx] = x μM, and [Zy] = y μM).
Figure 2. Time-resolved morphological analysis of RNT20Z20 during its supramolecular reconstruction process. (a) Time-resolved DLS showing average diameter size and zeta potential of RN, RNT20 and RNT20Z20 supramolecular complexes. Schematic representations illustrate the average diameter size of the supramolecular complexes derived from DLS data, with the size of each nanoparticle aggregated in the cluster. (b) SEM and TEM (inner) images of RN, RNT20 and RNT20Z20. In the notation RNTxZy, ‘x’ and ‘y’ denote the molar concentrations of the corresponding components in the solution ([RN] = 100 μM, [Tx] = x μM, and [Zy] = y μM).
Figure 3. Comparison of the optical properties of RN and RNTxZy at different assembly state in aqueous solution. (a) UV-vis spectrum of RhB, RN and RNT20Z20 hybrid system. The symbol ‘D’ indicates that the solvent was replaced with DMSO. (b) PL emission spectrum of RhB and RNTxZy hybrid system at various compositions. The symbol ‘D’ indicates that the solvent was replaced with DMSO. (c) Comparison of PL emission intensity and DLS size distribution data of RhB and RNTxZy hybrid system at various compositions. (d) Time-resolved PL decay lifetime measurement of RhB, RNT20 and RNT20Z20 at 580 nm emission wavelength with coefficient table of each fitted equation model. In the notation RNTxZy, ‘x’ and ‘y’ denote the molar concentrations of the corresponding components in the solution ([RN] = 100 μM, [Tx] = x μM, and [Zy] = y μM).
Figure 4. Comparison of hydrogen production properties of RhB, RN and RNTxZy hybrid structure. (a) Schematic illustration of the light-driven hydrogen production process of RhB and RNTxZy in Pt nanoparticle hybrid system. (b) Photocatalytic hydrogen production of RhB, RN, and RNTnZn with Pt at various composition ratio. (c) Individual effects of TA and ZrOCl2 as well as their combined effect, on the photocatalytic hydrogen production of RN. (d) Cyclic hydrogen production test of RNT20, and RNT20Z20 with schematic images of each hybrid structure. Each cycle was treated with 1 hour of light irradiation. In the notation RNTnZn and RNTxZy, ‘n’, ‘x’ and ‘y’ denote the molar concentrations of the corresponding components in the solution ([RN] = 100 μM, [Tn] = n μM, and [Zn] = n μM, [Tx] = x μM, and [Zy] = y μM).
Figure 5. Supramolecular reconstruction process and light-driven hydrogen production of M/RNTxZy. (a) Schematic illustration and SEM image of the fusion of RN onto MR-1 (M/RN). (b) CLSM and optical images of M/RN. Inset vial shows fluorescent image of M/RN solution under UV lamp irradiation. (c) Schematic illustration and SEM image of the anchoring of RNT20Z20 onto MR-1 (M/RNT20Z20). (d) CLSM and optical images of M/RNT20Z20. Inset vial shows fluorescent image of M/RNT20Z20 solution under UV lamp irradiation. (e) Hydrogen evolution of M/Lactate, M/RN, M/RNT20, and M/RNT20Z20. (f) Mechanistic illustration of solar-driven and metabolic hydrogen evolution of MR-1 and M/RNTxZy. In the notation RNTxZy, ‘x’ and ‘y’ denote the molar concentrations of the corresponding components in the solution ([RN] = 100 μM, [Tx] = x μM, and [Zy] = y μM).
Figure 6. Demonstration of a plant-inspired design for SED-circulation hydrogen photosynthesis systems. (a) Schematic illustration of a dialysis membrane-based SED-circulation bio-hybrid photocatalysis system, detailing holdable and diffusive component groups within the dialysis-based membrane pack. (b) Penetration ratio of RhB, H2PtCl6, Ascorbic acid (AA), RNT20Z20, and MR-1 through the dialysis membrane pack. The photo images of the dialysis membrane pack with RNT20Z20. The penetration ratio was calculated by comparing the absorbance intensity between the experimental molar concentration and the molar concentration at 100% diffused state (The scale ‘100 %’ indicates that the molar concentration inside and outside of the dialysis tube is in perfect equilibrium state). (c) M/RNT20Z20 in the dialysis membrane is a sustainable system without significant release of components, while (d) Pt/RB100 and (e) Pt/RNT20Z20 systems are unstable in the dialysis membrane, leading to the release of components from the membrane. (f) Cyclic hydrogen evolution tests of Pt/RNT20Z20, M/RNT20Z20 (SED-circulatory mode and isolated mode) and Pt/RB100. In the notation RNTxZy, ‘x’ and ‘y’ denote the molar concentrations of the corresponding components in the solution ([RN] = 100 μM, [Tx] = x μM, and [Zy] = y μM).
Supramolecular Reconstruction of Self-Assembling Photosensitizers for Enhanced Photocatalytic Hydrogen Evolution
https://doi.org/10.1002/anie.202416114
