Water‐Tolerant Lead Halide Perovskite Nanocrystals as Efficient Photocatalysts for Visible‐Light‐Driven CO₂ Reduction in Pure Water

Abstract

Lead halide perovskite (LHP) nanocrystals have recently been actively investigated for photocatalysis, owing to their inexpensive fabrication and excellent optoelectronic properties. However, LHP nanocrystals have not been used for artificial photosynthesis in aqueous solution, owing to their high sensitivity to water. In this study, water‐tolerant cobalt‐doped CsPbBr3/Cs4PbBr6 nanocrystals have been prepared with the protection of hexafluorobutyl methacrylate. The resultant materials are employed as efficient photocatalysts for visible‐light‐driven CO2 reduction in pure water. The perovskite nanocrystals with 2 % cobalt doping afford an impressive overall yield of 247 μmol g−1 for photocatalytic CO2 conversion into CO and CH4, using water as an electron source. This study represents a significant step for practical artificial photosynthesis by using LHP nanocrystals as photocatalysts in aqueous solution.

Glycine‐Functionalized CsPbBr3 Nanocrystals for Efficient Visible‐Light Photocatalysis of CO2 Reduction

“…In the field of the photocatalysis of CO 2 conversion with MHP NCs‐based photocatalysts, continuous efforts have focused on surface/interface modification [16, 18–24] and heterojunction engineering [25–32] to increase the active sites and improve the separation efficiency of photogenerated carriers, achieving a great improvement in photocatalytic performance over the past few years. However, the long alkyl‐chain capping ligands in conventional MHP NCs will be unfavorable for the CO 2 adsorption and hinder the efficient carrier transport in MHP NCs‐based heterojunctions, [26, 27] which has not yet been recognized extensively.…”

“…[9] TheseM HP NCs have attracted ever-increasing attention recently in the photocatalytic field, [10][11][12][13] for applications such as photocatalysis of H 2 evolution, [14] photodegradation of organic pollutants, [15] photocatalysis of CO 2 reduction, [16] and photocatalytic organic synthesis. [17] In the field of the photocatalysiso fC O 2 conversion with MHP NCs-based photocatalysts, continuouse ffortsh ave focused on surface/interface modification [16,[18][19][20][21][22][23][24] and heterojunction engineering [25][26][27][28][29][30][31][32] to increase the active sites and improve the separatione fficiencyo fp hotogenerated carriers,a chieving ag reat improvementi np hotocatalytic performanceo ver the past few years. However,t he long alkyl-chain capping ligands in conventional MHP NCs will be unfavorable for the CO 2 adsorptiona nd hinder the efficient carriert ransport in MHP NCsbasedh eterojunctions, [26,27] which has not yet been recognized extensively.C onsidering that capping ligandsa re indispensable for the preparation of MHP NCs with good stabilitya nd low surface defect density, the employment of small functional organic molecules as capping ligandsc ould be an ideal solution to maintain colloidals tability andi mprove the photocatalytic CO 2 activity of MHP NCs-based photocatalysts.…”

Recent Progress in Engineering Metal Halide Perovskites for Efficient Visible‐Light‐Driven Photocatalysis

“…Recently, Mu et al. reported a cobalt‐doped dual‐phase CsPbBr 3 /Cs 4 PbBr 6 heterojunction (Co@CsPbBr 3 /Cs 4 PbBr 6 ), which exhibited an impressive photocatalytic CO 2 reduction activity of 12.35 μmol g −1 h −1 in pure water. This work presents a significant step towards implementing this unique composite in artificial photocatalysis.…”

Perovskite Nanocrystals‐Based Heterostructures: Synthesis Strategies, Interfacial Effects, and Photocatalytic Applications

“…For example, a water‐proof shell of highly hydrophobic hexafluorobutyl methacrylate (HFBMA) ligand was created on the CsPbBr 3 /Cs 4 PbBr 6 PNCs exterior by Lu and co‐workers for improving the PNC stability. [ 47 ] However, notably, for practical photocatalytic application, the selected shell material should not block the light absorption or restrict the interfacial electron transfer of PNCs. So despite many attempts made to encapsulate the PNC and obtain a satisfying stability enhancement relying on the traditional coating materials, such as silica or polymer matrices, etc., the light penetration or interfacial electron transfer between the PNC and outer media was still interdicted due to the insulating encapsulation material.…”

“…Some of these modified PNCs‐based photocatalysts have achieved remarkable stability improvement and even realized the CO 2 photoreduction in pure water. [ 47 ] Also, the enhanced photocatalytic degradation of organic impurities and organic selectivity synthesis indicates the superiority of the heterostructure construction strategy in boosting the performance of PNCs‐based photocatalysts.…”