Regulating the Active Sites of Cs2 AgBiCl6 by Doping for Efficient Coupling of Photocatalytic CO2 Reduction and Benzyl Alcohol Oxidation.

Halide perovskites exhibit outstanding optoelectronic properties, which make them an ideal choice for photocatalytic CO2 reduction and benzyl alcohol (BA) oxidation. Nevertheless, the simultaneous realization of the above redox coupling reactions on halide perovskites remains a great challenge, as it requires distinct catalytic sites for different target reactions. Herein, the catalytic sites of Cs2 AgBiCl6 (CABC) are regulated by doping Fe for efficient coupling of photocatalytic CO2 reduction and BA oxidation. The Fe-doped CABC (Fe: CABC) exhibits an enhanced visible-light response and effective charge separation. Experimental results and theoretical calculations reveal a synergistic interplay between Bi and Fe sites, where the Bi and Fe sites have lower activation energies toward CO2 reduction and BA oxidation. Further investigations demonstrate that electrons and holes prefer to accumulate at the Bi site and Fe site under light irradiation, respectively, which creates favorable conditions for facilitating CO2 reduction and BA oxidation. The resultant Fe: CABC achieves a high photocatalytic performance toward CO (18.5 µmol g-1  h-1 ) and BD (1.1 mmol g-1  h-1 ) generation, which surpasses most of the state-of-the-art halide photocatalysts. This work demonstrates a facile strategy for regulating the catalytic site for redox coupling reactions, which will pave a new way for designing halide perovskites for photocatalysis.

Rubidium Doped Cs2AgBiBr6 Hierarchical Microsphere for Enhanced Photocatalytic CO2 Reduction.

Halide perovskites have garnered significant attention for their unique optoelectronic properties in solar-to-fuel conversions. However, the efficiency of halide perovskites in the field of photocatalytic CO2 reduction is largely limited by serious charge recombination and a lack of efficient active sites. In this work, a rubidium (Rb) doped Cs2AgBiBr6 (Rb:CABB) hierarchical microsphere is developed for photocatalytic CO2 reduction. Experimental and theoretical analysis discloses that partially substituting Rb+ for Ag+ can effectively modulate the electronic structure of CABB, favoring charge separation and making adjacent Bi atoms an electron-rich active site. Further investigations indicated that Rb doping also reduces the energy barriers of the rate-determining step in CO2 reduction. As a result, Rb:CABB demonstrated an enhanced CO yield compared to its undoped counterpart. This work presents a promising approach to optimizing the electronic structures of photocatalysts and paving a new way for exploring halide perovskites for photocatalytic CO2 reduction.

Boosting Photocatalytic CO2 Methanation through Interface Fusion over CdS Quantum Dot Aerogels.

In the field of photocatalytic CO2 reduction, quantum dot (QD) assemblies have emerged as promising candidate photocatalysts due to their superior light absorption and better substrate adsorption. However, the poor contacts within QD assemblies lead to low interfacial charge transfer efficiency, making QD assemblies suffer from unsatisfactory photocatalytic performance. Herein, a novel approach is presented involving the construction of strongly interfacial fused CdS QD assemblies (CdS QD gel) for CO2 reduction. The novel CdS QD gel demonstrates outstanding photocatalytic performance for CO2 methanation, achieving a CH4 generation rate of ≈296 µmol g-1 h-1, with a selectivity surpassing 76% and an apparent quantum yield (AQY) of 1.4%. Further investigations reveal that the robust interfacial fusion in these CdS QDs not only boosts their ability to absorb visible light but also significantly promotes charge separation. The present work paves the way for utilizing QD gel photocatalysts in realizing efficient CO2 reduction and highlights the critical role of interfacial engineering in photocatalysts.

Generating Long-Lived Charge Carriers in CdS Quantum Dots by Cu-Doping for Photocatalytic CO2 Reduction.

Converting CO2 into high-value-added chemicals has been recognized as a promising way to tackle the fossil fuel crisis. Quantum dots (QDs) have been extensively studied for photocatalytic CO2 reduction due to their excellent optoelectronic properties. However, most of the photogenerated charge carriers recombine before they participate in the photocatalytic reaction. It is crucial to regulate the charge carriers to minimize undesired charge recombination, thus, promoting surface photocatalysis. Herein, we report a copper-doped CdS (Cu:CdS) QD photocatalyst for CO2 reduction. Density functional theory simulations and experimental results demonstrate that Cu dopants create intermediate energy levels in CdS QDs that can extend the lifetime of exciton charge carriers. Furthermore, the long-lived charge carriers can be harnessed for the photocatalytic reaction on Cu:CdS QDs. The resultant Cu:CdS QDs exhibited a significantly enhanced photocatalytic activity toward CO2 reduction compared to the pristine CdS QDs. This work highlights the importance of charge regulation in photocatalysts and opens new pathways for the exploration of efficient QD photocatalysts.

Passivating Defects and Constructing Catalytic Sites on CsPbBr3 with ZnBr2 for Photocatalytic CO2 Reduction.

In recent years, halide perovskites have attracted considerable attention for photocatalytic CO2 reduction. However, the presence of surface defects and the lack of specific catalytic sites for CO2 reduction lead to low photocatalytic performance. In this study, we demonstrate a facile method that post-treats CsPbBr3 with ZnBr2 for photocatalytic CO2 reduction. Our experimental and characterization results show that ZnBr2 has a dual role: the Br- ions in ZnBr2 passivate Br vacancies (VBr) on the CsPbBr3 surface, while Zn2+ cations act as catalytic sites for CO2 reduction. The ZnBr2-CsPbBr3 achieves a photocatalytic CO evolution rate of 57 µmol g-1 h-1, which is nearly three times higher than that of the pristine CsPbBr3. The enhanced performance over ZnBr2-CsPbBr3 is mainly due to the decreased VBr and lower reaction energy barrier for CO2 reduction. This work presents an effective method to simultaneously passivate surface defects and introduce catalytic sites, providing useful guidance for the regulation of perovskite photoelectric properties and the design of efficient photocatalysts.

In Situ Constructed Perovskite-Chalcogenide Heterojunction for Photocatalytic CO2 Reduction.

Perovskite nanocrystals (PNCs) are promising candidates for solar-to-fuel conversions yet exhibit low photocatalytic activities mainly due to serious recombination of photogenerated charge carriers. Constructing heterojunction is regarded as an effective method to promote the separation of charge carriers in PNCs. However, the low interfacial quality and non-directional charge transfer in heterojunction lead to low charge transfer efficiency. Herein, a CsPbBr3 -CdZnS heterojunction is designed and prepared via an in situ hot-injection method for photocatalytic CO2 reduction. It is found that the high-quality interface in heterojunction and anisotropic charge transfer of CdZnS nanorods (NRs) enable efficient spatial separation of charge carriers in CsPbBr3 -CdZnS heterojunction. The CsPbBr3 -CdZnS heterojunction achieves a higher CO yield (55.8 µmol g-1  h-1 ) than that of the pristine CsPbBr3 NCs (13.9 µmol g-1  h-1 ). Furthermore, spectroscopic experiments and density functional theory (DFT) simulations further confirm that the suppressed recombination of charge carriers and lowered energy barrier for CO2 reduction contribute to the improved photocatalytic activity of the CsPbBr3 -CdZnS heterojunction. This work demonstrates a valid method to construct high-quality heterojunction with directional charge transfer for photocatalytic CO2 reduction. This study is expected to pave a new avenue to design perovskite-chalcogenide heterojunction.

Interparticle Charge-Transport-Enhanced Electrochemiluminescence of Quantum-Dot Aerogels.

Electrochemiluminescence (ECL) represents a widely explored technique to generate light, in which the emission intensity relies critically on the charge-transfer reactions between electrogenerated radicals. Two types of charge-transfer mechanisms have been postulated for ECL generation, but the manipulation and effective probing of these routes remain a fundamental challenge. Here, we demonstrate the design of quantum dot (QD) aerogels as novel ECL luminophores via a versatile water-induced gelation strategy. The strong electronic coupling between adjacent QDs enables efficient charge transport within the aerogel network, leading to the generation of highly efficient ECL based on the selectively improved interparticle charge-transfer route. This mechanism is further verified by designing CdSe-CdTe mixed QD aerogels, where the two mechanistic routes are clearly decoupled for ECL generation. We anticipate our work will advance the fundamental understanding of ECL and prove useful for designing next-generation QD-based devices.

Promoting the Electrocatalytic Performance of Noble Metal Aerogels by Ligand-Directed Modulation.

Noble metal aerogels (NMAs) are an emerging class of porous materials. Embracing nano-sized highly-active noble metals and porous structures, they display unprecedented performance in diverse electrocatalytic processes. However, various impurities, particularly organic ligands, are often involved in the synthesis and remain in the corresponding products, hindering the investigation of the intrinsic electrocatalytic properties of NMAs. Here, starting from laser-generated inorganic-salt-stabilized metal nanoparticles, various impurity-free NMAs (Au, Pd, and Au-Pd aerogels) were fabricated. In this light, we demonstrate not only the intrinsic electrocatalytic properties of NMAs, but also the prominent roles played by ligands in tuning electrocatalysis through modulating the electron density of catalysts. These findings may offer a new dimension to engineer and optimize the electrocatalytic performance for various NMAs and beyond.

Organosilicon-Based Ligand Design for High-Performance Perovskite Nanocrystal Films for Color Conversion and X-ray Imaging.

Perovskite nanocrystals (PNCs) bear a huge potential for widespread applications, such as color conversion, X-ray scintillators, and active laser media. However, the poor intrinsic stability and high susceptibility to environmental stimuli including moisture and oxygen have become bottlenecks of PNC materials for commercialization. Appropriate barrier material design can efficiently improve the stability of the PNCs. Particularly, the strategy for packaging PNCs in organosilicon matrixes can integrate the advantages of inorganic-oxide-based and polymer-based encapsulation routes. However, the inert long-carbon-chain ligands (e.g., oleic acid, oleylamine) used in the current ligand systems for silicon-based encapsulation are detrimental to the cross-linking of the organosilicon matrix, resulting in performance deficiencies in the nanocrystal films, such as low transparency and large surface roughness. Herein, we propose a dual-organosilicon ligand system consisting of (3-aminopropyl)triethoxysilane (APTES) and (3-aminopropyl)triethoxysilane with pentanedioic anhydride (APTES-PA), to replace the inert long-carbon-chain ligands for improving the performance of organosilicon-coated PNC films. As a result, strongly fluorescent PNC films prepared by a facile solution-casting method demonstrate high transparency and reduced surface roughness while maintaining high stability in various harsh environments. The optimized PNC films were eventually applied in an X-ray imaging system as scintillators, showing a high spatial resolution above 20 lp/mm. By designing this promising dual organosilicon ligand system for PNC films, our work highlights the crucial influence of the molecular structure of the capping ligands on the optical performance of the PNC film.

Self-supported CsPbBr3/Ti3C2Tx MXene aerogels towards efficient photocatalytic CO2 reduction.

Aerogels, especially MXene aerogels, are an ideal multifunctional platform for developing efficient photocatalysts for CO2 reduction because they are featured by abundant catalytic sites, high electrical conductivity, high gas absorption ability and self-supported structure. However, the pristine MXene aerogel has almost no ability to utilize light, which requires additional photosensitizers to assist it in achieving efficient light harvesting. Herein, we immobilized colloidal CsPbBr3 nanocrystals (NCs) onto the self-supported Ti3C2Tx (where Tx represents surface terminations such as fluorine, oxygen, and hydroxyl groups) MXene aerogels for photocatalytic CO2 reduction. The resultant CsPbBr3/Ti3C2Tx MXene aerogels exhibit a remarkable photocatalytic activity toward CO2 reduction with total electron consumption rate of 112.6 µmol g-1h-1, which is 6.6-fold higher than that of the pristine CsPbBr3 NC powders. The improvement of the photocatalytic performance is presumably attributed to the strong light absorption, effective charge separation and CO2 adsorption in the CsPbBr3/Ti3C2Tx MXene aerogels. This work presents an effective perovskite-based photocatalyst in aerogel form and opens a new avenue for their solar-to-fuel conversions.

In-situ producing CsPbBr3 nanocrystals on (001)-faceted TiO2 nanosheets as S­scheme heterostructure for bifunctional photocatalysis.

Fabricating a cost-effective yet highly active photocatalyst to reduce CO2 to CO and oxidize benzyl alcohol to benzaldehyde simultaneously, is challenging. Herein, we construct an S-scheme 0D/2D CsPbBr3/TiO2 heterostructure for bifunctional photocatalysis. An in-situ synthetic route is used, which enables the precise integration between CsPbBr3 nanocrystals and ultrathin TiO2 nanosheets exposed with (001) facets (termed as TiO2-001), resulting in a tightly coupled heterointerface and desirable band offsets. The as-prepared CsPbBr3/TiO2-001heterojunctions exhibit boosted charge carrier kinetics, particularly, quick carrier separation/transfer and efficient utilization. Experimental results and theoretical calculations validate the S-scheme route in CsPbBr3/TiO2-001, which allows the enrichment of strongly conserved electrons-holes at conduction and valence bands of CsPbBr3 and TiO2-001, respectively. Consequently, compared to its counterparts, an excellent bifunctional activity (with 24 h reusability) is realized over CsPbBr3/TiO2-001, where the production rate of CO and benzaldehyde reach up to 78.06 µmol g-1h-1 and 1.77 mmol g-1h-1 respectively, without employing any sacrificial agents. This work highlights the development of perovskite-based heterostructures and describes the efficient harnessing of redox potentials and charge carriers towards combined photocatalytic systems.

Highly Luminescent and Water-Resistant CsPbBr3-CsPb2Br5 Perovskite Nanocrystals Coordinated with Partially Hydrolyzed Poly(methyl methacrylate) and Polyethylenimine.

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 CsPbBr3 to CsPb2Br5 to obtain CsPbBr3/CsPb2Br5 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.

Origin of the effects of PEG additives in electrolytes on the performance of quantum dot sensitized solar cells.

It has been well established that polymer additives in electrolyte can impede the charge recombination processes at the photoanode/electrolyte interface, and improve performance, especially V oc, of the resulting sensitized solar cells. However, there are few reports about the effect of electrolyte additives on counter electrode (CE) performance. Herein, we systematically investigated the effect of polyethylene glycol (PEG) additives with various molecular weights (M w from 300 to 20 000) in polysulfide electrolyte on the performance of two representative CdSe and Zn-Cu-In-Se (ZCISe) quantum dot sensitized solar cells (QDSCs), and explored the mechanism of the observed effects. Electrochemical impedance spectroscopy measurements indicate that all PEG additives can improve the charge recombination resistance at the photoanode/electrolyte interface, therefore suppressing the unwanted charge recombination process, and enhancing the V oc of the resulting cell devices accordingly. On the CE side, with the increase of M w of PEG additives, the initial effect of reducing the charge transfer resistance at the CE/electrolyte interface evolves into an increasing resistance; accordingly the initial positive effect on FF turns into negative one. Accordingly, low M w PEG can improve efficiency for both CdSe (increasing from 6.81% to 7.60%) and ZCISe QDSCs (increasing from 9.26% to 10.20%). High M w PEG is still effective for CdSe QDSCs with an efficiency of 7.38%, but falls flat on ZCISe QDSCs (with an efficiency of 9.11%).

High Efficiency Quantum Dot Sensitized Solar Cells Based on Direct Adsorption of Quantum Dots on Photoanodes.

Unambiguously direct adsorption (DA) of initial oil-soluble quantum dots (QDs) on TiO2 film electrode is a convenient and simple approach in the construction of quantum dot sensitized solar cells (QDSCs). Regrettably, low QD loading amount and poor reproducibility shadow the advantages of DA route and constrain its practical application. Herein, the influence of experimental variables in DA process on QD loading amount as well as on the photovoltaic performance of the resultant QDSCs was investigated and optimized systematically, including the choice of solvent, purification of QDs, and sensitization time, as well as QD concentration. Experimental results demonstrated that it is essential to choose appropriate solvent as well as control purification cycles of original QD suspensions so as to realize satisfactory QD loading amount and ensure the high reproducibility. In addition, DA mode renders efficient electron injection from QD to TiO2, yet low QD loading amount and adverse QD agglomeration in comparison with the well-developed capping ligand induced self-assembly (CLIS) deposition approach. Mg2+ treatment on TiO2 photoanodes can promote the QD loading amount in DA mode. The optimized QDSCs based on DA mode exhibited efficiencies of 6.90% and 9.02% for CdSe and Zn-Cu-In-Se QDSCs, respectively, which were comparable to the best results based on CLIS mode (6.88% and 9.56%, respectively).