Self-Trapped Exciton Emission in Highly Polar 0D Hybrid Ammonium/Hydronium-Based Perovskites Triggered by Antimony Doping.

Various monovalent cations are employed to construct metal halide perovskites with various structures and functionalities. However, perovskites based on highly polar A-site cations have seldom been reported. Here, a novel hybrid 0D (NH4)x(OH3)3-xInCl6 perovskite with highly polar hydronium OH3+ cations is introduced in this study. Upon doping with Sb3+, hybrid 0D (NH4)x(OH3)3-xInCl6 single crystals exhibited highly efficient broadband yellowish-green (550 nm) and red (630 nm) dual emissions with a PLQY of 86%. The dual emission arises due to Sb3+ occupying two sites within the crystal lattice that possess different polarization environments, leading to distinct Stokes shift energies. The study revealed that lattice polarity plays a significant role in the self-trapped exciton emission of Sb3+-doped perovskites, contributing up to 25% of the Stokes shift energy for hybrid 0D (NH4)x(OH3)3-xInCl6:Sb3+ as a secondary source, in addition to the Jahn-Teller deformation. These findings highlight the potential of Sb3+-doped perovskites for achieving tunable broadband emission and underscore the importance of lattice polarity in determining the emission properties of perovskite materials.

Selective Photoelectrochemical Oxidation of Glycerol to Glyceric Acid on (002) Facets Exposed WO3 Nanosheets.

Glycerol is a byproduct of biodiesel production. Selective photoelectrochemical oxidation of glycerol to high value-added chemicals offers an economical and sustainable approach to transform renewable feedstock as well as store green energy at the same time. In this work, we synthesized monoclinic WO3 nanosheets with exposed (002) facets, which could selectively oxidize glycerol to glyceric acid (GLYA) with a photocurrent density of 1.7 mA cm-2 , a 73 % GLYA selectivity and a 39 % GLYA Faradaic efficiency at 0.9 V vs. reversible hydrogen electrode (RHE) under AM 1.5G illumination (100 mW cm-2 ). Compared to (200) facets exposed WO3 , a combination of experiments and theoretical calculations indicates that the superior performance of selective glycerol oxidation mainly originates from the better charge separation and prolonged carrier lifetime resulted from the plenty of surface trapping states, lower energy barrier of the glycerol-to-GLYA reaction pathway, more abundant active sites and stronger oxidative ability of photogenerated holes on the (002) facets exposed WO3 . Our findings show great potential to significantly contribute to the sustainable and environmentally friendly chemical processes via designing high performance photoelectrochemical cell via facet engineering for renewable feedstock transformation.

Zero-Dimensional Organic-Inorganic Hybrid Copper-Based Halides with Highly Efficient Orange-Red Emission.

Lead-free metal halides are promising luminescent materials with low non-toxicity, tunable emission, and high luminescence quantum yield (PLQY). The development of red light-emitting materials with high PLQY to meet the color coordinate requirements for light-emitting diode (LED) lighting and wide color gamut displays remains a major scientific challenge. Herein, novel lead-free copper-based halide materials are reported. PEA4 Cu4 I4 is an efficient orange-red broad emission with a highest PLQY of 73.6%. All three materials, namely, those of ((R)-(+)-α-PEA)4 Cu4 I4 , ((S)-(-)-α-PEA)4 Cu4 I4 , and (ß-PEA)4 Cu4 I4 with zero-dimensional structures have large exciton binding energies and Huang-Rhys factors, thus causing efficient self-trapped exciton emissions. A prototypical orange-red LED device is fabricated successfully that demonstrates the potential of copper-based halide materials in lighting and display applications.

Highly Luminescent CsPbX3 (X=Cl, Br, I) Nanocrystals Achieved by a Rapid Anion Exchange at Room Temperature.

Cesium lead halide perovskite (CsPbX3 ) nanocrystals (NCs) exhibit an excellent photoelectric performance, which is directly governed by fine-tuning of the composition and preparation of materials with a special phase structure and morphology. However, it is still facing challenges to achieve highly stable and luminescent CsPbX3 NCs at room temperature. Herein, we report on a novel exchange reaction, in which metal halides MX2 (M=Zn, Mg, Cu, or Ca; X=Cl, Br, or I) solids act as anion source to directly prepare CsPbX3 NCs at room temperature without any pretreatment. Introducing small amount of oleic acid or oleylamine speed up the exchange reaction through different promotion mechanisms. Oleic acid coordinates to the surface of the NCs, which increases the reaction activity, and oleylamine greatly enhances the dissolution of ZnCl2 . XRD and TEM tests demonstrate that the cubic phase structure and the morphology of the parent CsPbX3 were well preserved. Moreover, the band-gap energies and photoluminescence (PL) spectra were readily tunable over the entire visible spectral region of λ=406-685 nm. Our findings could open up the possibilities of using metal halide solids as new anion sources to prepare high-quality CsPbX3 NCs at room temperature.

Modulation of the Excitation States in All-Inorganic Halide Perovskites via Sb3+ and Bi3+ Codoping.

Sb3+-doped halide perovskites are promising candidates for solid-state lighting due to their diverse fluorescent colors and high efficiency. However, the mismatched high excitation energy with commercial UV chips is one of the critical issues to be addressed. Herein, a Bi3+ codoping strategy was established as a general and efficient approach to modulate the excitation spectrum from the Sb3+-doping center in all-inorganic perovskites of Cs2InCl5·H2O, Cs2NaInCl6, and Rb3InCl6. The incorporated Bi3+ greatly enhanced the splitting of the A band (1S0-3P1 transition) and boosts the enormous redshift of the low-energy branch in all these systems. The interactions persist strongly even at extremely low doping concentrations, suggesting a dipole-based long-range interaction. The results provide an in-depth insight into the contribution mechanism of Bi3+ to Sb3+ in all-inorganic perovskites, which throws light upon tuning the excitation spectrum of broadband emission from the extrinsic self-trapped exciton (STE).

Enhanced light harvesting and charge separation of carbon and oxygen co-doped carbon nitride as excellent photocatalyst for hydrogen evolution reaction.

Solar-driven water splitting has been regarded as a promising strategy for renewable hydrogen production. Among many semiconductor photocatalysts, graphitic carbon nitride (g-C3N4) has received tremendous attention due to its two-dimensional structure, appropriate band gap and decent photocatalytic activity. However, it suffers severe charge recombination problems, affecting its practical performance. In this work, we demonstrated that dual heteroatoms (C and O) doped g-C3N4 can exhibit about 3 times higher catalytic performance for hydrogen evolution than that of the normal g-C3N4 with a hydrogen evolution rate reaching 2595.4 umol g-1h-1 and an apparent quantum efficiency at 420 nm of 16.6%. The heteroatoms (C and O) doped g-C3N4 photocatalyst also exhibited superior removal performance when removing Rhodamine B (RhB) . X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (ssNMR) and X-ray absorption near-edge structure (XANES) spectroscopy reveal that the carbon and oxygen dopants replace the sp2 nitrogen and bridging N atom, respectively. DFT calculations demonstrate the codoping of carbon and oxygen- induced the generation of mid-gap state, leading to the improvement of light harvesting and charge separation.

Emission Mechanism of Self-Trapped Excitons in Sb3+-Doped All-Inorganic Metal-Halide Perovskites.

Sb3+ doping confers highly efficient and color-diverse broadband light emission to all-inorganic metal-halide perovskites. However, the emission mechanism is still under debate. Herein, a trace amount of Sb3+ ions (<0.1% atomic percentage) doping in the typical all-inorganic perovskites Cs2NaInCl6, Rb3InCl6, and Cs2InCl5·H2O allows universal observation of the fine structure in the photoluminescence excitation spectrum of the ns2 electron. A lifetime mapping method was utilized to reveal the origin of broadband emission triggered by Sb3+ doping, by which various fluorescence components can be differentiated. In particular, free-exciton emission was identified at the high-energy end of the broadband emission for all three doped systems. The excitation-energy- and temperature-dependent fluorescence decay further indicates the existence and origin of self-trapped states. The observed structural and vibrational symmetry-dependent emission behaviors suggest dipole interactions can dramatically alter Stokes-shift energy and modulate the light-emitting wavelength.

Semi-heterogeneous photo-Cu-dual-catalytic cross-coupling reactions using polymeric carbon nitrides.

A merger of copper catalysis and semiconductor photocatalysis using polymeric carbon nitride (PCN) for multi-type cross-coupling reactions was developed. This dual-catalytic system enables mild C-H arylation, chalcogenation, and C-N cross-coupling reactions under visible light irradiation with a broad substrate scope. Good-to-excellent yields were obtained with appreciable site selectivity and functional group tolerance. Metal-free and low-cost PCN photocatalyst can easily be recovered and reused several times.

Two-Dimensional Cs2AgBiBr6/WS2 Heterostructure-Based Photodetector with Boosted Detectivity via Interfacial Engineering.

Two-dimensional (2D) transition metal dichalcogenide (TMDC) monolayers have been widely used for optoelectronic devices because of their ultrasensitivity to light detection acquired from their direct gap properties. However, the small cross-section of photon absorption in the atomically thin layer thickness significantly limits the generation of photocarriers, restricting their performance. Here, we integrate monolayer WS2 with 2D perovskites Cs2AgBiBr6, which serve as the light absorption layer, to greatly enhance the photosensitivity of WS2. The efficient charge transfer at the Cs2AgBiBr6/WS2 heterojunction is evidenced by the shortened photoluminescence (PL) decay time of Cs2AgBiBr6. Scanning photocurrent microscopy of Cs2AgBiBr6/WS2/graphene reveals that improved charge extraction from graphene leads to an enhanced photoresponse. The 2D Cs2AgBiBr6/WS2/graphene vertical heterostructure photodetector exhibits a high detectivity (D*) of 1.5 × 1013 Jones with a fast response time of 52.3 µs/53.6 µs and an on/off ratio of 1.02 × 104. It is worth noting that this 2D heterostructure photodetector can realize self-powered light detection behavior with an open-circuit voltage of ∼0.75 V. The results suggest that the 2D perovskites can effectively improve the TMDC layer-based photodetectors for low-power consumption photoelectrical applications.

CsCu2I3 Nanocrystals: Growth and Structural Evolution for Tunable Light Emission.

CsCu2I3 mixed with Cs3Cu2I5 has shown potential applications as white-light-emitting materials, while their growth, structural evolution behaviors, and their impact on photoluminescence of CsCu2I3 nanocrystals (NCs) are still not known. In this work, we investigated the growth and structural evolution of CsCu2I3 nanocrystals with increasing reaction temperature. At low temperature and in the presence of a high dosage of oleic acid and oleylamine, Cs3Cu2I5 nanoparticles, rather than CsCu2I3 NCs, preferred to form in the hot-injection reaction system. Increasing the reaction temperature promoted the formation of CsCu2I3 nanorods. Phase-pure CsCu2I3 nanorods were steadily obtained at 180 °C. Structural evolution from less copper-containing NCs to copper-rich ones in the low-temperature reaction condition is highly related to the coordination of copper ions with OAm. More importantly, accompanying the growth of nanorods and structural evolution from Cu3Cs2I5 to CsCu2I3, the color of photoluminescence emission of NCs changed from blue to nearly white and to yellow, but their photoluminescence quantum yield decreased from 36.00 to 9.86%. The finding in this work would give a view to the structural evolution of copper-containing perovskite-like halides, being helpful for adjusting their photoluminescence in white LEDs.

Organic titanates: a model for activating rapid room-temperature synthesis of shape-controlled CsPbBr3 nanocrystals and their derivatives.

The application of lead halide perovskite nanocrystals is challenged by the lack of strategies in rapid room-temperature synthesis with controlled morphologies. Here, we report on an initial study of adopting organic titanates as a model activator that promotes rapid room-temperature synthesis of shape-controlled, highly luminescent CsPbBr3 nanocrystals and their derivatives.

Optimum Preferential Oxidation Performance of CeO2-CuO x-RGO Composites through Interfacial Regulation.

Interfacial regulation offers a promising route to rationally and effectively design advanced materials for CO preferential oxidation. Herein, we initiated an interfacial regulation of CeO2-CuO x-RGO composites by adjusting the addition sequence of the components during the support formation. The presence of RGO along with the sequence tuning of the components is confirmed to survey the changes of the oxidation state of copper species, the content and distribution of the Cu+ site, and the synergistic interactions between Cu-Ce mixed oxides and reduced graphene oxide (RGO) over the catalysts. These catalysts were systematically characterized by inductively coupled plasma, X-ray diffraction, transmission electron microscopy/high-resolution transmission electron microscopy, hydrogen temperature-programmed reduction, X-ray photoelectron spectra, thermal gravimetric analysis, Raman spectra, and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements. The results show that RGO is favorable for the generation of Cu+ and the dispersion of copper-cerium species in the as-prepared catalysts. Furthermore, by multi-interfacial regulation of the CeO2-CuO x-RGO composites, the catalyst CeO2/CuO x-RGO exhibits a strikingly high catalytic oxidation activity at a low temperature coupled with a broader operation temperature window (i.e., CO conversion >99.0%, 140-220 °C) in the CO-selective oxidation reaction, which has been attributed to the high content of the active species Cu+ enriched on the surface, the highly dispersed copper oxide clusters subjected to a strong interaction with ceria, and the synergistic interactions between Cu-Ce mixed oxides and RGO.