Silver nanoparticle enhanced metal-organic matrix with interface-engineering for efficient photocatalytic hydrogen evolution

Abstract

Integrating plasmonic nanoparticles into the photoactive metal-organic matrix is highly desirable due to the plasmonic near field enhancement, complementary light absorption, and accelerated separation of photogenerated charge carriers at the junction interface. The construction of a well-defined, intimate interface is vital for efficient charge carrier separation, however, it remains a challenge in synthesis. Here we synthesize a junction bearing intimate interface, composed of plasmonic Ag nanoparticles and matrix with silver node via a facile one-step approach. The plasmonic effect of Ag nanoparticles on the matrix is visualized through electron energy loss mapping. Moreover, charge carrier transfer from the plasmonic nanoparticles to the matrix is verified through ultrafast transient absorption spectroscopy and in-situ photoelectron spectroscopy. The system delivers highly efficient visible-light photocatalytic H2 generation, surpassing most reported metal-organic framework-based photocatalytic systems. This work sheds light on effective electronic and energy bridging between plasmonic nanoparticles and organic semiconductors.

Glutathione-Capped Hollow Silver Nanoparticles: Optimization of Surface Plasmon Resonance, Photothermal Effect, and In Vitro and In Vivo Biocompatibility

“…The capping of the stabilizer on the surface of HAgNPs was confirmed using Fourier transform infrared (FTIR) spectroscopy (Figure a,b). FTIR spectra of pure glutathione and trisodium citrate are similar to the reported ones. , Pure glutathione has functional groups of −NH 2 , −COOH, −HN–CO–, and −SH with stretching at (3200–3300), (1700, 3500), (1650, 1540), and 2520 cm –1 , respectively. − However, in the case of NBG-HAgNPs, the peak intensity corresponding to −COOH is almost negligible and agrees with the reported literature. − Instead, the peaks appearing at 1450 and 1550 cm –1 indicate the bond Ag–OOC formation (Figure a). Moreover, the peak corresponding to −SH is almost negligible, indicating the formation of −S – Ag + …”

Advances in organic semiconductors for photocatalytic hydrogen evolution reaction

“…The Ag(I) cluster-based nodes can allow efficient LMCT or MLCT/CLCT and help improve photocatalytic performance, while the plasmonic effect of silver-containing materials produces a synergistic effect. For example, Ag-AgMOM has been developed 92 , with the highest occupied valence band (HOVB) rotating upward and located on the AgO 4 junction, while the lowest unoccupied conduction band (LUCB) rotates downward and is distributed in the porphyrin of TCPP (Figure 5f). The strong interaction between the plasmonic AgNPs and excited AgMOM promotes the photocatalytic HER (Figure 5g), exhibiting a hydrogen production rate of up to 1025 μmol h −1 g −1 in visible light photocatalysis and further increasing to 3153 μmol h −1 g −1 under full-spectrum irradiation (Figure 5h).…”

Advanced Nanomaterials and Characterization Techniques for Photovoltaic and Photocatalysis Applications

“…32 The importance of the intimate interface was also confirmed in another system composed of in situ synthesized plasmonic Ag NPs and a metal−organic matrix, which allowed highly efficient visiblelight photocatalytic H 2 generation. 19 To further improve the light absorption efficiency, we designed a porous hollow TiO 2 microsphere as the support for plasmonic Au NPs. 18 Based on the theoretical calculations, the "nanojet effect" of the unique hollow structure facilitated the SPR excitation of the Au NPs situated at the shadow-side of the hollow TiO 2 spheres and largely enhanced the UV−vis light absorption.…”