Embedding Plasmonic Metal into Heterointerface of MOFs‐Encapsulated Semiconductor Hollow Architecture for Boosting CO₂ Photoreduction

Abstract

Coupling hollow semiconductor with metal–organic frameworks (MOFs) holds great promise for constructing high‐efficient CO2 photoreduction systems. However, energy band mismatch between them makes it difficult to exert their advantages to maximize the overall photocatalytic efficiency, since that the blockage of desirable interfacial charge transfer gives rise to the enrichment of photoelectrons and CO2 molecules on the different locations. Herein, an interfacial engineering is presented to overcome this impediment, based on the insertion of plasmonic metal into the heterointerfaces between them, forming a stacked semiconductor/metal@MOF photocatalyst. Experimental observations and theoretical simulations validate the critical roles of embedded Au in maneuvering the charge separation/transfer and surface reaction: (i) bridges the photoelectron transfer from hollow CdS (H‐CdS) to ZIF‐8; (ii) produces hot electrons and shifts them to ZIF‐8; (iii) induces the formation of ZIF‐8 defects in promoting the CO2 adsorption/activation and transformation to CO with low energy barriers. Consequently, the as‐prepared H‐CdS/Au@ZIF‐8 with optimal ZIF‐8 thickness exhibits distinctly boosted activity and superb selectivity in CO production as compared with H‐CdS@ZIF‐8 and other counterparts. This work provides protocols to take full advantages of components involved for enhanced solar‐to‐chemical energy conversion efficiency of hybrid artificial photosynthetic systems through rationally harnessing the charge transfer between them.

Enhancing CO2 photoreduction through unique 2D MOF-based heterostructures with metalloid doping

“…The analysis reveals that the morphology and crystal properties remain largely unchanged compared to the original sample, confirming the commendable stability of the CuS@CuO@ZIF-8NS photocatalyst. To evaluate the photocatalytic CO 2 reduction performance of the as-prepared CuS@CuO@ZIF-8NS, the CO 2 photoreduction performances of reported MOF-based photocatalysts and our work were compared as shown in Table S7 † 51–59 . It is notable that the CuS@CuO@ZIF-8NS catalyst possesses much higher yield rates of CO and selectivity of CH 4 , indicating its superiority for CO 2 photoreduction.…”

“…To evaluate the photocatalytic CO 2 reduction performance of the as-prepared CuS@CuO@ZIF-8NS, the CO 2 photoreduction performances of reported MOF-based photocatalysts and our work were compared as shown in Table S7. † [51][52][53][54][55][56][57][58][59] It is notable that the CuS@CuO@ZIF-8NS catalyst possesses much higher yield rates of CO and selectivity of CH 4 , indicating its superiority for CO 2 photoreduction.…”

Metal– and covalent organic frameworks for photocatalytic CO2 reduction coupled with H2O oxidation

“…Furthermore, the introduction of Au induced the formation of defects in ZIF-8, promoted the adsorption of CO 2 , and lowered the energy barrier for the conversion of CO 2 -to-CO, thereby enhancing the reactivity and selectivity. 140 According to the article, H-CdS/Au@ZIF-8 demonstrated a peak production rate of 233.8 µmol g cat −1 h −1…”

Crystal phase of nickel sulfide dictates hydrogen evolution activity of various semiconducting photocatalysts

“…With the fast development in the field of nanomaterials, serious research results have shown that the micro-nano structure of nanomaterials plays a vital role in determining the physio-chemical properties and functions of catalysts. [1][2][3] In addition to the widely studied structural parameters, including shape, 4 size, 5 defect, 6 and facet, 7 it has been recently investigated that different crystal phases can modulate the catalytic properties and functions toward enhanced performance. [8][9][10] Generally, nanomaterials can exist in more than one crystal phase, in which the thermodynamically stable phases are the parts that have attracted the most attention.…”