Full-spectrum nonmetallic plasmonic carriers for efficient isopropanol dehydration

Abstract

Plasmonic hot carriers have the advantage of focusing, amplifying, and manipulating optical signals via electron oscillations which offers a feasible pathway to influence catalytic reactions. However, the contribution of nonmetallic hot carriers and thermal effects on the overall reactions are still unclear, and developing methods to enhance the efficiency of the catalysis is critical. Herein, we proposed a new strategy for flexibly modulating the hot electrons using a nonmetallic plasmonic heterostructure (named W18O49-nanowires/reduced-graphene-oxides) for isopropanol dehydration where the reaction rate was 180-fold greater than the corresponding thermocatalytic pathway. The key detail to this strategy lies in the synergetic utilization of ultraviolet light and visible-near-infrared light to enhance the hot electron generation and promote electron transfer for C-O bond cleavage during isopropanol dehydration reaction. This, in turn, results in a reduced reaction activation barrier down to 0.37 eV (compared to 1.0 eV of thermocatalysis) and a significantly improved conversion efficiency of 100% propylene from isopropanol. This work provides an additional strategy to modulate hot carrier of plasmonic semiconductors and helps guide the design of better catalytic materials and chemistries.

W18O49 Nanowire Arrays for Plasmonic Photodetector with Electromediated Broadband Photoresponse

“…As observed in Figure e, the W 18 O 49 NWA exhibits two distinct absorption bands: One absorption band appears at a wavelength below ∼400 nm, which can be attributed to the semiconducting intrinsic absorption of W 18 O 49 , and the absorption band of ∼400–550 nm can be attributed to semiconducting defects in the material. Similar to localized surface plasmon resonance (LSPR) observed in noble metals such as Ag, Au, and Pt, − an additional absorption band ranging from 550 nm to the near-infrared (NIR) light region can be attributed to the LSPR arising from the collective oscillations of excess electrons in W 18 O 49 caused by the oxygen vacancies . Furthermore, Figure S3 shows the simulated calculation results of dielectric permittivity variation of W 18 O 49 with wavelength and its corresponding electric distribution, which provide further evidence for the plasmonic absorption of W 18 O 49 and highlight the significance of the LSPR in determining its optical properties.…”

“…Similar to localized surface plasmon resonance (LSPR) observed in noble metals such as Ag, Au, and Pt, 27−31 an additional absorption band ranging from 550 nm to the near-infrared (NIR) light region can be attributed to the LSPR arising from the collective oscillations of excess electrons in W 18 O 49 caused by the oxygen vacancies. 32 Furthermore, Figure S3 shows the simulated calculation results of dielectric permittivity variation of W 18 O 49 with wavelength and its corresponding electric distribution, which provide further evidence for the plasmonic absorption of W 18 O 49 and highlight the significance of the LSPR in determining its optical properties.…”

In Situ Photodeposition of Cobalt Phosphate (CoHxPOy) on CdIn2S4 Photocatalyst for Accelerated Hole Extraction and Improved Hydrogen Evolution

“…The ternary metal sulfide CdIn 2 S 4 (CIS), as a member of AB 2 X 4 family, is considered a promising photocatalyst due to its superior physicochemical stability, narrow bandgap, and suitable band position for hydrogen evolution reaction (HER) [ 24 , 25 , 26 , 27 ]. However, the practical application of CIS is extremely confined by lack of catalytic active sites and difficulty of hole extraction [ 28 , 29 , 30 , 31 ].…”

Atomically Dispersed Pt on CdS Nanosheets for Photocatalytic Evolution of H2 and 1,1-Diethoxyethane from Ethanol

“…As a zero-emission carrier with energy density of 142 MJ kg –1 , H 2 is believed to be an effective chemical energy carrier that could be produced from renewable sources, for example, via photo/electro-catalysis H 2 evolution reaction. – Ethanol, derived from biomass fermentation, contains 13.04 wt % of hydrogen, making it an ideal chemical hydrogen source. Furthermore, it is also a versatile precursor for producing numerous chemicals and fuels, including acetaldehyde, acetic acid, esters, and acetals. – Among them, 1,1-diethoxyethane (DEE) is a significant ethanol product owing to its wide applications in fuel additives, pharmaceuticals, chemical synthesis, and so on. – Hence, ethanol is an appropriate platform for H 2 production concurrently with high value-added conversion.…”