Photocatalytic CO2 reduction is an appealing approach to convert solar energy into high value-added chemicals. All-inorganic CsPbBr3 quantum dots (QDs) have emerged as a promising photocatalyst for reducing CO2. However, pristine CsPbBr3 has a low catalytic performance, mainly due to severe charge recombination. Herein, a 0D/2D heterojunction of CsPbBr3 QDs/Bi2WO6 nanosheet (CPB/BWO) photocatalysts is fabricated for photocatalytic CO2 reduction. The CPB/BWO photocatalyst achieves excellent photocatalytic performance: the total yield of CH4/CO is 503 μmol g–1, nearly 9.5 times higher than the pristine CsPbBr3. The CPB/BWO heterojunction also exhibits much-improved stability during photocatalytic reactions. On the basis of various characterization techniques, our investigations verified a direct Z-scheme charge migration mechanism between CsPbBr3 QDs and Bi2WO6 nanosheets. The improved photocatalytic performance is originated from the high spatial separation of photoexcited charge carriers in CPB/BWO, which can also preserve strong individual redox abilities of two components. This work reports an efficient direct Z-scheme heterojunction photocatalytic system based on metal halide perovskites. The novel strategy we proposed may bring up new opportunities for the development of metal halide perovskite photocatalysts with greatly enhanced activities.

Converting CO2 into chemical fuels with a photocatalyst and sunlight is an appealing approach to address climate deterioration and energy crisis. Metal complexes are superb candidates for CO2 reduction due to their tunable catalytic sites with high activity. The coupling of metal complexes with organic photosensitizers is regarded as a common strategy for establishing photocatalytic systems for visible-light-driven CO2 reduction. While most of the organic photosensitizers generally contain precious metals and are available through onerous synthetic routes, their large-scale application in the photocatalysis is limited. Halide perovskite nanocrystals (NCs) have been considered as one of the most promising light-harvesting materials to replace the organic photosensitizers due to their tunable light absorption range, low cost, abundant surface sites, and high molar extinction coefficient. Herein, we demonstrate a facile strategy to immobilize [Ni­(terpy)2]2+ (Ni­(tpy)) on inorganic ligand-capped CsPbBr3 NCs and to apply this hybrid as a catalyst for visible-light-driven CO2 reduction. In this hybrid photocatalytic system, the Ni­(tpy) can provide specific catalytic sites and serve as electron sinks to suppress electron–hole recombination in the CsPbBr3 NCs. The CsPbBr3-Ni­(tpy) catalytic system achieves a high yield (1724 μmol/g) in the reduction of CO2 to CO/CH4, which is approximately 26-fold higher than that achieved with the pristine CsPbBr3 NCs. This work has developed a method for enhancing the performance of photocatalytic CO2 reduction by immobilizing metal complexes on perovskite NCs. The methodology we present here provides a new platform for utilizing halide perovskite NCs for photocatalytic applications.

Utilizing sunlight to convert CO 2 into chemical fuels could simultaneously address the greenhouse effect and fossil fuel crisis. ZnSe nanocrystals are promising candidates for photocatalysis because of their low toxicity and excellent photoelectric properties. However, pristine ZnSe generally has low catalytic activities due to serious charge recombination and the lack of efficient catalytic sites for CO 2 reduction. Herein, a ZnSe nanorods−CsSnCl 3 perovskite (ZnSe−CsSnCl 3 ) type II heterojunction composite is designed and prepared for photocatalytic CO 2 reduction. The ZnSe−CsSnCl 3 type II heterojunction composite exhibits enhanced photocatalytic activity for CO 2 reduction with respect to pristine ZnSe nanorods. The experimental characterizations and theoretical calculations reveal that the efficient charge separation and lowered free energy of CO 2 reduction facilitate the CO 2 conversion on the ZnSe−CsSnCl 3 heterojunction composite. This work presents a type II heterojunction composite photocatalyst based on ecofriendly metal chalcogenides and metal halide perovskites. Our study has also promoted the understanding of the CO 2 reduction mechanisms on perovskite nanocrystals, which could be valuable for the development of metal halide perovskite photocatalysts.

All inorganic lead halide perovskite nanocrystals (PNCs) typically suffer from poor stability against moisture and UV radiation as well as degradation during thermal treatment. The stability of PNCs can be significantly enhanced through polymer encapsulation, often accompanied by a decrease of photoluminescence quantum yield (PLQY) due to the loss of highly dynamic oleylamine/oleic acid (OLA/OA) ligands. Herein, we propose a solution for this problem by utilizing partially hydrolyzed poly(methyl methacrylate) (h-PMMA) and highly branched poly(ethylenimine) (b-PEI) as double ligands stabilizing the PNCs already during the mechanochemical synthesis (grinding). The hydrophobic polymer of h-PMMA imparts excellent film-forming properties and water stability to the resulting NC−polymer composite. In its own turn, the b-PEI forms an amino-rich, strongly binding ligand layer on the surface of the PNCs being responsible for the significant improvement of the PLQY and the stability of the resulting material. Moreover, the introduction of b-PEI promotes a partial phase conversion from CsPbBr 3 to CsPb 2 Br 5 to obtain CsPbBr 3 /CsPb 2 Br 5 nanocrystals with a core− shell-like structure. As-prepared PNCs solutions are directly processable as inks, while their PLQY drops only slightly from 75% in colloidal solution to 65% in films. Moreover, the final PNC−polymer film exhibits excellent stability against water, heat, and ultraviolet light irradiation. These superior properties allowed us to fabricate a proof of concept thin film OLED with h-PMMA/b-PEI-stabilized PNCs as an easily processable, narrowly emitting color conversion composite material. KEYWORDS: CsPbBr 3 −CsPb 2 Br 5 , partially hydrolyzed PMMA, highly branched PEI, high photoluminescence quantum yield, stability B ecause of their excellent photophysical properties, such as adjustable band gaps, high molar extinction coefficients, and excellent charge−transfer performance, all-inorganic cesium lead halide perovskite nanomaterials CsPbX 3 (X = Cl, Br, or I) have been perfect candidates for many optoelectronic applications, such as solar cells, 1 LEDs, 2,3 lasers, 4 photodetectors, 5 field effect transistors (FETs), 6 and Xray scintillators. 7 However, moisture, heat, and oxygen make perovskite nanomaterials suffering from poor stability. 8,9 For example, they dissolve in polar solvents, such as water, due to the ionic nature of the material itself. Additionally, perovskite nanomaterials easily undergo phase transitions and decompose

Metal halide perovskite nanocrystals (MHP NCs) have attracted much scientific interest in photocatalysis. Various types of MHP photocatalysts have been intensively explored in photocatalytic CO 2 reduction in the past few years. However, some key issues, such as severe charge recombination, low stability, and the origin of products, have created bottlenecks in developing MHP photocatalysts. Therefore, the rational design of MHPs is worthwhile to deepen our understanding of the above issues and develop efficient photocatalysts. This Focus Review highlights the recent advances in MHP photocatalysts regarding design principles toward photocatalytic CO 2 reduction. Various modification strategies are clarified, and an outlook on future challenges and prospects is also provided to point out the possible research directions in MHP photocatalysts. It is anticipated that this Focus Review can provide guidance on the design of MHP-based photocatalysts and help uncover some common issues encountered by the scientific community when studying MHP photocatalysts.