Hot Carriers and Photothermal Effects of Monolayer MoO_x for Promoting Sulfite Oxidase Mimetic Activity

Abstract

Local surface plasmon resonance (LSPR)-enhanced catalysis has brought a substantial amount of opportunities across various disciplines such as photocatalysis, photodetection, and photothermal therapeutics. Plasmon-induced photothermal and hot carriers effects have also been utilized to activate the enzyme-like reactions. Compared with natural enzymes, the relatively low catalytic performance of nanozymes severely hampered the potential applications in the field of biomedicine. For these issues mentioned above, herein, we demonstrate a highly efficient sulfite oxidase (SuO x ) mimetic performance of plasmonic monolayer MoO x (ML-MoO x ) upon LSPR excitation. We also established that the considerable photothermal effect and the injection of hot carriers induced by LSPR are responsible for promoting the SuO x activity of ML-MoO x . The high transient local temperature on the surface of ML-MoO x generated by the photothermal effect facilitates to impact the reaction velocity and feed the SuO x -like activity, while the generation of hot carriers which are suggested as predominant effects catalyzes the oxidation of sulfite to sulfate through significantly decreasing the activation energy for the SuO x -like reaction. These investigations present a contribution to the basic understanding of plasmon-enhanced enzyme-like reaction and provided an insight into the optimization of the SuO x mimetic performance of nanomaterials.

Guest Molecule Insertion-Optimized d-Band Center Position in MoS2 with Improved Sulfite Activation Ability Inspired by Sulfite Oxidase

“…The lower K m and higher V max imply that MoS 2 /BPE possesses more superior SuO x mimic activity over MoS 2 . 55,56 The activity of MoS 2 /BPE is comparable to that of the recently reported artificial SuO x (Table S3). As for MoS 2 / BPE, the stability of SuO x mimic catalysis is also significant for future applications.…”

“…In SuO x mimic catalysis, SO 3 2– is absorbed by MoS 2 and forms *SO 3 2– at first, which is oxidized to *SO 4 2– in turn. Finally, • SO 4 – desorbs from the MoS 2 surface . For MoS 2 /BPE and MoS 2 , SO 3 2– absorption and *SO 3 2– oxidation are both thermodynamically favorable downhill processes (Figure a and Scheme S2).…”

Plasmonic Nanozymes: Leveraging Localized Surface Plasmon Resonance to Boost the Enzyme‐Mimicking Activity of Nanomaterials

“…greatly enhanced upon LSPR excitation [130] due to the hot carriers and photothermal effects. The results confirmed the existence of oxygen vacancies, which boosted the carrier intensity of ML-MoO x .…”

“…Similarly, Wan et al reported that the CAT-like activity of Pt could be enhanced by the photothermal effect from plasmonic hollow AuAg nanocages (Figure 5C). [127] Moreover, Yang et al reported that the photothermal effect of monolayer MoO x promoted the sulfite oxidase (SuO x ) mimetic activity, [130] and Zhang et al proposed that platinum-doped prussian blue (PB) nanozyme exhibited the tunable LSPR frequency with significantly improved photothermal conversion efficiency, which could be used for enhancing the antioxidative catalytic activity of nanozyme. [53] Noteworthy, when leveraging the photothermal effect of a PNP to regulate the enzyme-mimicking activity, the morphological changes of PNzymes upon continuous laser irradiation are rarely explored.…”

“…[ 127 ] Moreover, Yang et al. reported that the photothermal effect of monolayer MoO x promoted the sulfite oxidase (SuO x ) mimetic activity, [ 130 ] and Zhang et al. proposed that platinum‐doped prussian blue (PB) nanozyme exhibited the tunable LSPR frequency with significantly improved photothermal conversion efficiency, which could be used for enhancing the antioxidative catalytic activity of nanozyme.…”