Cs3Bi2Br9 nanoparticles decorated C3N4 nanotubes composite photocatalyst for highly selective oxidation of benzylic alcohol.

Solar-light driven oxidation of benzylic alcohols over photocatalysts endows significant prospects in value-added organics evolution owing to its facile, inexpensive and sustainable process. However, the unsatisfactory performance of actual photocatalysts due to the inefficient charge separation, low photoredox potential and sluggish surface reaction impedes the practical application of this process. Herein, we developed an innovative Z-Scheme Cs3BiBr9 nanoparticles@porous C3N4 tubes (CBB-NP@P-tube-CN) heterojunction photocatalyst for highly selective benzyl alcohol oxidation. Such composite combining increased photo-oxidation potential, Z-Scheme charge migration route as well as the structural advantages of porous tubular C3N4 ensures the accelerated mass and ions diffusion kinetics, the fast photoinduced carriers dissociation and sufficient photoredox potentials. The CBB-NP@P-tube-CN photocatalyst demonstrates an exceptional performance for selective photo-oxidation of benzylic alcohol into benzaldehyde with 19, 14 and 3 times higher benzylic alcohols conversion rate than those of C3N4 nanotubes, Cs3Bi2Br9 and Cs3Bi2Br9@bulk C3N4 photocatalysts, respectively. This work offers a sustainable photocatalytic system based on lead-free halide perovskite toward large scale solar-light driven value-added chemicals production.

Oxygen-Mediated (0D) Cs4PbX6 Formation during Open-Air Thermal Processing Improves Inorganic Perovskite Solar Cell Performance.

The desire to commercialize perovskite solar cells continues to mount, motivating the development of scalable production. Evaluations of the impact of open-air processing have revealed a variety of physical changes in the fabricated devices─with few changes having the capacity to be functionalized. Here, we highlight the beneficial role of ambient oxygen during the open-air thermal processing of metastable γ-CsPbI3-based perovskite thin films and devices. Physiochemical-sensitive probes elucidate oxygen intercalation and the formation of Pb-O bonds in the CsPbI3 crystal, entering via iodine vacancies at the surface, creating superoxide (O2-) through electron transfer reactions with molecular oxygen, which drives the formation of a zero-dimensional Cs4PbI6 capping layer during annealing (>330 °C). The chemical conversion permanently alters the film structure, helping to shield the subsurface perovskite from moisture and introduces lattice anchoring sites, stabilizing otherwise unstable γ-CsPbI3 films. This functional modification is demonstrated in γ-CsPbI2Br perovskite solar cells, boosting the operational stability and photoconversion efficiency of champion devices from 12.7 to 15.4% when annealed in dry air. Such findings prompt a reconsideration of glovebox-based perovskite solar cell research and establish a scenario where device fabrication can in fact greatly benefit from ambient oxygen.

Surface Oxygen Defect Engineering of A2B2O7 Pyrochlore Semiconductors Boosts the Electrocatalytic Reduction of CO2-to-HCOOH.

The electrocatalytic conversion of inert CO2 to value-added chemical fuels powered by renewable energy is one of the benchmark approaches to address excessive carbon emissions and achieve carbon-neutral energy restructuring. However, the adsorption/activation of supersymmetric CO2 is facing insurmountable challenges that constrain its industrial-scale applications. Here, this theory-guided study confronts these challenges by leveraging the synergies of bimetallic sites and defect engineering, where pyrochlore-type semiconductor A2B2O7 is employed as research platform and the conversion of CO2-to-HCOOH as the model reaction. Specifically, defect engineering intensified greatly the chemisorption-induced CO2 polarization via the bimetallic coordination, thermodynamically beneficial to the HCOOH production via the *HCO2 intermediate. The optimal V-BSO-430 electrocatalyst with abundant surface oxygen vacancies achieved a superior HCOOH yield of 116.7 mmol h-1 cm-2 at -1.2 VRHE, rivalling the incumbent similar reaction systems. Furthermore, the unique catalytic unit featured with a Bi1-Sn-Bi2 triangular structure, which is reconstructed by defect engineering, and altered the pathway of CO2 adsorption and activation to allow the preferential affinity of the suspended O atom in *HCO2 to H. As a result, V-BSO-430 gave an impressive FEHCOOH of 93% at -1.0 VRHE. This study held promises for inspiring the exploration of bimetallic materials from the massive semiconductor database.

Noble-Metal-Free High-Entropy Alloy Nanoparticles for Efficient Solar-Driven Photocatalytic CO2 Reduction.

Metal nanoparticle (NP) cocatalysts are widely investigated for their ability to enhance the performance of photocatalytic materials; however, their practical application is often limited by the inherent instability under light irradiation. This challenge has catalyzed interest in exploring high-entropy alloys (HEAs), which, with their increased entropy and lower Gibbs free energy, provide superior stability. In this study, 3.5 nm-sized noble-metal-free NPs composed of a FeCoNiCuMn HEA are successfully synthesized. With theoretic calculation and experiments, the electronic structure of HEA in augmenting the catalytic CO2 reduction has been uncovered, including the individual roles of each element and the collective synergistic effects. Then, their photocatalytic CO2 reduction capabilities are investigated when immobilized on TiO2. HEA NPs significantly enhance the CO2 photoreduction, achieving a 23-fold increase over pristine TiO2, with CO and CH4 production rates of 235.2 and 19.9 µmol g-1 h-1, respectively. Meanwhile, HEA NPs show excellent stability under simulated solar irradiation, as well high-energy X-ray irradiation. This research emphasizes the promising role of HEA NPs, composed of earth-abundant elements, in revolutionizing the field of photocatalysis.

FO-SPR Model for Full-Spectrum Signal Analysis of Back-reflecting FO-SPR Sensors to Monitor MOF Deposition.

In this study, we explore the full-spectrum capabilities of fiber-optic surface plasmon resonance (FO-SPR) for analyzing heterogeneous samples with increased comprehensiveness. Our approach involves refining a literature-derived FO-SPR model to more precisely reflect experimental data obtained using a back-reflecting sensor configuration. Key enhancements in our model include adjustments to the thickness and permittivity of the gold SPR-active layer on the FO-SPR sensor as well as improvements to the angular distribution of light within the system. We apply this optimized model to the investigation of the deposition process of a metal-organic framework (MOF), specifically ZIF-8, using FO-SPR. By closely examining the temporal variations in the FO-SPR signal during MOF layer formation, we simultaneously determine the evolving thickness and refractive index (RI) of the MOF layer, offering a dual-parameter analysis. Our results demonstrate that a full-spectrum analysis of the FO-SPR signal can extract critical information from samples exhibiting radial heterogeneity. This advancement significantly enhances the quantitative assessment of various phenomena that alter the refractive index in the sensor's domain, such as adsorption and binding processes. This work thus represents a significant step forward in the field of FO-SPR sensor technology, promising broad applications in areas requiring the precise detection and analysis of complex samples.

Twin boundary defect engineering in Au cocatalyst to promote alcohol splitting for coproduction of H2 and fine chemicals.

The microstructure of Au metal cocatalyst has been shown to significantly influence its optical and electronic properties. However, the impact of Au defect engineering on photocatalytic activity remains underexplored. In this study, we synthesize different Au-TiO2 composites by in-situ hybridizing face-centered cubic (F-Au) and twin boundary defect Au (T-Au) nanoparticles (NPs) onto the surface of TiO2. We find that T-Au NPs with twin defects serve as highly efficient cocatalysts for converting alcohols into their corresponding aldehydes while also generating H2. The optimized T-Au/TiO2 composite yields an H2 evolution rate of 6850 µmol h-1 g-1 and a BAD formation rate of 6830 µmol h-1 g-1, about 38 times higher than that of blank TiO2. Compared to F-Au/TiO2, the T-Au/TiO2 composite enhances charge separation, extends the lifetime of electrons, and provides more active sites for H2 reduction. The twin defect also improves alcohol reactant adsorption, boosting overall photocatalytic performance. This research paves the way for more studies on defect engineering in metal cocatalysts for enhanced catalytic activities in organic synthesis and H2 evolution.

Nanoscale Chemical Diversity of Coke Deposits on Nanoprinted Metal Catalysts Visualized by Tip-Enhanced Raman Spectroscopy.

Coke formation is the prime cause of catalyst deactivation, where undesired carbon wastes block the catalyst surface and hinder further reaction in a broad gamut of industrial chemical processes. Yet, the origins of coke formation and their distribution across the catalyst remain elusive, obstructing the design of coke-resistant catalysts. Here, the first-time application of tip-enhanced Raman spectroscopy (TERS) is demonstrated as a nanoscale chemical probe to localize and identify coke deposits on a post-mortem metal nanocatalyst. Monitoring coke at the nanoscale circumvents bulk averaging and reveals the local nature of coke with unmatched detail. The nature of coke is chemically diverse and ranges from nanocrystalline graphite to disordered and polymeric coke, even on a single nanoscale location of a top-down nanoprinted SiO2 -supported Pt catalyst. Surprisingly, not all Pt is an equal producer of coke, where clear isolated coke "hotspots" are present non-homogeneously on Pt which generate large amounts of disordered coke. After their formation, coke shifts to the support and undergoes long-range transport on the surrounding SiO2 surface, where it becomes more graphitic. The presented results provide novel guidelines to selectively free-up the coked metal surface at more mild rejuvenation conditions, thus securing the long-term catalyst stability.

Cation Substitution Strategy for Developing Perovskite Oxide with Rich Oxygen Vacancy-Mediated Charge Redistribution Enables Highly Efficient Nitrate Electroreduction to Ammonia.

The electrocatalytic nitrate (NO3-) reduction reaction (eNITRR) is a promising method for ammonia synthesis. However, its efficacy is currently limited due to poor selectivity, largely caused by the inherent complexity of the multiple-electron processes involved. To address these issues, oxygen-vacancy-rich LaFe0.9M0.1O3-δ (M = Co, Ni, and Cu) perovskite submicrofibers have been designed from the starting material LaFeO3-δ (LF) by a B-site substitution strategy and used as the eNITRR electrocatalyst. Consequently, the LaFe0.9Cu0.1O3-δ (LF0.9Cu0.1) submicrofibers with a stronger Fe-O hybridization, more oxygen vacancies, and more positive surface potential exhibit a higher ammonia yield rate of 349 ± 15 µg h-1 mg-1cat. and a Faradaic efficiency of 48 ± 2% than LF submicrofibers. The COMSOL Multiphysics simulations demonstrate that the more positive surface of LF0.9Cu0.1 submicrofibers can induce NO3- enrichment and suppress the competing hydrogen evolution reaction. By combining a variety of in situ characterizations and density functional theory calculations, the eNITRR mechanism is revealed, where the first proton-electron coupling step (*NO3 + H+ + e- → *HNO3) is the rate-determining step with a reduced energy barrier of 1.83 eV. This work highlights the positive effect of cation substitution in promoting eNITRR properties of perovskites and provides new insights into the studies of perovskite-type electrocatalytic ammonia synthesis catalysts.

Placental-fetal distribution of carbon particles in a pregnant rabbit model after repeated exposure to diluted diesel engine exhaust.

BACKGROUND: Airborne pollution particles have been shown to translocate from the mother's lung to the fetal circulation, but their distribution and internal placental-fetal tissue load remain poorly explored. Here, we investigated the placental-fetal load and distribution of diesel engine exhaust particles during gestation under controlled exposure conditions using a pregnant rabbit model. Pregnant dams were exposed by nose-only inhalation to either clean air (controls) or diluted and filtered diesel engine exhaust (1 mg/m3) for 2 h/day, 5 days/week, from gestational day (GD) 3 to GD27. At GD28, placental and fetal tissues (i.e., heart, kidney, liver, lung and gonads) were collected for biometry and to study the presence of carbon particles (CPs) using white light generation by carbonaceous particles under femtosecond pulsed laser illumination. RESULTS: CPs were detected in the placenta, fetal heart, kidney, liver, lung and gonads in significantly higher amounts in exposed rabbits compared with controls. Through multiple factor analysis, we were able to discriminate the diesel engine exposed pregnant rabbits from the control group taking all variables related to fetoplacental biometry and CP load into consideration. Our findings did not reveal a sex effect, yet a potential interaction effect might be present between exposure and fetal sex. CONCLUSIONS: The results confirmed the translocation of maternally inhaled CPs from diesel engine exhaust to the placenta which could be detected in fetal organs during late-stage pregnancy. The exposed can be clearly discriminated from the control group with respect to fetoplacental biometry and CP load. The differential particle load in the fetal organs may contribute to the effects on fetoplacental biometry and to the malprogramming of the fetal phenotype with long-term effects later in life.

Label-Free Identification of Carbonaceous Particles Using Nonlinear Optical Microscopy.

The adverse health effects of ambient carbonaceous particles (CPs) such as carbon black (CB), black carbon (BC), and brown carbon (BrC) are becoming more evident and depend on their composition and emission source. Therefore, identifying and quantifying these particles in biological samples are important to better understand their toxicity. Here, we report the development of a nonlinear optical approach for the identification of CPs such as CB and BrC using imaging conditions compatible with biomedical samples. The unique visible light fingerprint of CB and BrC nanoparticles (NPs) upon illumination with a femtosecond (fs) pulsed laser at 1300 nm excitation wavelength is an effective approach for their identification in their biological context. The emission from spectral features of these CPs was investigated with time-domain fluorescence lifetime imaging (FLIM) to further support their identification. This study is performed for different types of CPs embedded in agarose gel as well as in in vitro mammalian cells. The unique nonlinear emissive behavior of CP NPs used for their label-free identification is further complementary with fluorophores typically used for specific staining of biological samples thus providing the relevant bio-context.

Synthesis and Characterization of Gold Chiral Nanoparticles Functionalized by a Chiral Drug.

Inorganic chiral nanoparticles are attracting more and more attention due to their peculiar optical properties and potential biological applications, such as bioimaging, therapeutics, and diagnostics. Among inorganic chiral nanoparticles, gold chiral nanostructures were demonstrated to be very interesting in this context, with good physical chemical stability and also the possibility to decorate the surface, improving biomedical application as the interaction with the bio-systems. Gold (Au) nanostructures were synthesized according to a seed-mediated procedure which envisages the use of cetyltrimethylammonium bromide (CTAB) as the capping agent and L- and D-cysteine to promote chirality. Au nanostructures have been demonstrated to have opposite circular dichroism signals depending on the amino acid enantiomer used during the synthesis. Then, a procedure to decorate the Au surface with penicillamine, a drug used for the treatment of Wilson's disease, was developed. The composite material of gold nanoparticles/penicillamine was characterized using electron microscopy, and the penicillamine functionalization was monitored by means of UV-Visible, Raman, and infrared spectroscopy, highlighting the formation of the Au-S bond. Furthermore, electron circular dichroism was used to monitor the chirality of the synthesized nanostructures and it was demonstrated that both penicillamine enantiomers can be successfully bonded with both the enantiomers of the gold nanostructures without affecting gold nanoparticles' chirality. The effective modification of nanostructures' surfaces via penicillamine introduction allowed us to address the important issue of controlling chirality and surface properties in the chiral nano-system.

Single-particle optical study on the effect of chloride post-treatment of MAPbI3 nano/microcrystals.

Surface passivation by post-treatment with methylammonium chloride (MACl) is regarded as a promising strategy to suppress surface defects in organic-inorganic lead halide perovskites and elevate the efficiency of solar cells based on these materials. However, traditional MACl post-treatment methods often impede the performance of the final device, due to the creation of additional unwanted defects. Herein, we report a novel approach for chloride post-treatment by applying a mixed ethanol/toluene solvent and validate its beneficial effect on the structure, composition, and optical properties of methylammonium lead iodide nano/microcrystals and related photosensitive devices. An optimized (mild) Cl content improves the crystallinity, enhances photoluminescence (PL) intensity, provides longer PL lifetimes, and induces brighter and longer ON-states in single-particle emission trajectories. On top of a reduction in the population percentage of crystals showing gradual photodegradation, our Cl-treatment method even leads to photobrightening. Additionally, the extent of carrier communication throughout spatially distant nanodomains enhances after MACl-based post-modification. Our results demonstrate that surface-bound Cl significantly reduces the trap density induced by under-coordinated lead ions or iodide vacancies and reveal the importance of a careful consideration of the applied Cl content to avoid the generation of high-bandgap MAPbCl3 heterojunctions upon excessive Cl treatment. Importantly, significant trap passivation upon MACl treatment translates into a more stable and elevated photocurrent in the corresponding photodetector device. We anticipate these findings will be beneficial for designing durable, high-performance lead halide perovskite photonic devices.

Crystal structure engineering of metal halide perovskites for photocatalytic organic synthesis.

Engineering crystal structure of Cs3BiBr6 and Cs3Bi2Br9 is theoretically and experimentally demonstrated to modulate their photocatalytic performance. This work offers insights into the structure-photoactivity relationships of metal halide perovskites (MHPs) and provides a guideline for exploiting MHPs toward efficient photocatalytic organic synthesis.

Correction: Atomic-scale detection of individual lead clusters confined in Linde Type A zeolites.

Correction for 'Atomic-scale detection of individual lead clusters confined in linde type A zeolites' by Jarmo Fatermans et al., Nanoscale, 2022, 14, 9323-9330, https://doi.org/10.1039/D2NR01819E.

Deciphering the Role of Water in Promoting the Optoelectronic Performance of Surface-Engineered Lead Halide Perovskite Nanocrystals.

Lead halide perovskites are promising candidates for high-performance light-emitting diodes (LEDs); however, their applicability is limited by their structural instability toward moisture. Although a deliberate addition of water to the precursor solution has recently been shown to improve the crystallinity and optical properties of perovskites, the corresponding thin films still do not exhibit a near-unity quantum yield. Herein, we report that the direct addition of a minute amount of water to post-treated formamidinium lead bromide (FAPbBr3) nanocrystals (NCs) substantially enhances the stability while achieving a 95% photoluminescence quantum yield in a NC thin film. We unveil the mechanism of how moisture assists in the formation of an additional NH4Br component. Alongside, we demonstrate the crucial role of moisture in assisting localized etching of the perovskite crystal, facilitating the partial incorporation of NH4+, which is key for improved performance under ambient conditions. Finally, as a proof-of-concept, the application of post-treated and water-treated perovskites is tested in LEDs, with the latter exhibiting a superior performance, offering opportunities toward commercial application in moisture-stable optoelectronics.

Crystal phase engineering of Ru for simultaneous selective photocatalytic oxidations and H2 production.

Noble metal nanoparticles are often used as cocatalysts to enhance the photocatalytic efficiency. While the effect of cocatalyst nanoparticle size and shape has widely been explored, the effect of the crystal phase is largely overlooked. In this work, we investigate the effect of Ru nanoparticle crystal phase, specifically regular hexagonal close-packed (hcp) and allotropic face-centered cubic (fcc) crystal phases, as cocatalyst decorated onto the surface of TiO2 photocatalysts. As reference photocatalytic reaction the simultaneous photocatalytic production of benzaldehyde (BAD) and H2 from benzyl alcohol was chosen. Both the fcc Ru/TiO2 and hcp Ru/TiO2 composites exhibit enhanced BAD and H2 production rates compared to pristine TiO2 due to the formation of a Schottky barrier promoting the photogenerated charge separation. Moreover, a 1.9-fold photoactivity enhancement of the fcc Ru/TiO2 composite is achieved as compared to the hcp Ru/TiO2 composite, which is attributed to the fact that the fcc Ru NPs are more efficient in facilitating the charge transfer as compared to hcp Ru NPs, thus inhibiting the recombination of electron-hole pairs and enhancing the overall photoactivity.

Metal Nanocatalyst Sintering Interrogated at Complementary Length Scales.

Metal nanoparticle (NP) sintering is a prime cause of catalyst degradation, limiting its economic lifetime and viability. To date, sintering phenomena are interrogated either at the bulk scale to probe averaged NP properties or at the level of individual NPs to visualize atomic motion. Yet, "mesoscale" strategies which bridge these worlds can chart NP populations at intermediate length scales but remain elusive due to characterization challenges. Here, a multi-pronged approach is developed to provide complementary information on Pt NP sintering covering multiple length scales. High-resolution scanning electron microscopy (HRSEM) and Monte Carlo simulation show that the size evolution of individual NPs depends on the number of coalescence events they undergo during their lifetime. In its turn, the probability of coalescence is strongly dependent on the NP's mesoscale environment, where local population heterogeneities generate NP-rich "hotspots" and NP-free zones during sintering. Surprisingly, advanced in situ synchrotron X-ray diffraction shows that not all NPs within the small NP sub-population are equally prone to sintering, depending on their crystallographic orientation on the support surface. The demonstrated approach shows that mesoscale heterogeneities in the NP population drive sintering and mitigation strategies demand their maximal elimination via advanced catalyst synthesis strategies.

Tethered Small-Molecule Acceptors Simultaneously Enhance the Efficiency and Stability of Polymer Solar Cells.

For polymer solar cells (PSCs), the mixture of polymer donors and small-molecule acceptors (SMAs) is fine-tuned to realize a favorable kinetically trapped morphology and thus a commercially viable device efficiency. However, the thermodynamic relaxation of the mixed domains within the blend raises concerns related to the long-term operational stability of the devices, especially in the record-holding Y-series SMAs. Here, a new class of dimeric Y6-based SMAs tethered with differential flexible spacers is reported to regulate their aggregation and relaxation behavior. In their polymer blends with PM6, it is found that they favor an improved structural order relative to that of Y6 counterpart. Most importantly, the tethered SMAs show large glass transition temperatures to suppress the thermodynamic relaxation in mixed domains. For the high-performing dimeric blend, an unprecedented open circuit voltage of 0.87 V is realized with a conversion efficiency of 17.85%, while those of regular Y6-base devices only reach 0.84 V and 16.93%, respectively. Most importantly, the dimer-based device possesses substantially reduced burn-in efficiency loss, retaining more than 80% of the initial efficiency after operating at the maximum power point under continuous illumination for 700 h. The tethering approach provides a new direction to develop PSCs with high efficiency and excellent operating stability.

An embedded interfacial network stabilizes inorganic CsPbI3 perovskite thin films.

The black perovskite phase of CsPbI3 is promising for optoelectronic applications; however, it is unstable under ambient conditions, transforming within minutes into an optically inactive yellow phase, a fact that has so far prevented its widespread adoption. Here we use coarse photolithography to embed a PbI2-based interfacial microstructure into otherwise-unstable CsPbI3 perovskite thin films and devices. Films fitted with a tessellating microgrid are rendered resistant to moisture-triggered decay and exhibit enhanced long-term stability of the black phase (beyond 2.5 years in a dry environment), due to increasing the phase transition energy barrier and limiting the spread of potential yellow phase formation to structurally isolated domains of the grid. This stabilizing effect is readily achieved at the device level, where unencapsulated CsPbI3 perovskite photodetectors display ambient-stable operation. These findings provide insights into the nature of phase destabilization in emerging CsPbI3 perovskite devices and demonstrate an effective stabilization procedure which is entirely orthogonal to existing approaches.

Origin of the polychromatic photoluminescence of zeolite confined Ag clusters: temperature- and co-cation-dependent luminescence.

Zeolite confined silver clusters (AgCLs) have attracted extensive attention due to their remarkable luminescent properties, but the elucidation of the underlying photophysical processes and especially the excited-state dynamics remains a challenge. Herein, we investigate the bright photoluminescence of AgCLs confined in Linde Type A zeolites (LTA) by systematically varying the temperature (298-77 K) and co-cation composition (Li/Na) and examining their respective influence on the steady-state and time-resolved photoluminescence. The observed polychromatic emission of the tetrahedral Ag4(H2O) n 2+ clusters ranges from orange to violet and three distinct emitting species are identified, corresponding to three long-lived triplet states populated consecutively and separated by a small energy barrier. These long-lived species are at the origin of the polychromatic luminescence with high photoluminescence quantum yields. Furthermore, the Li-content dependence of decay times points to the importance of guest-host-guest interactions in tuning the luminescent properties with a 43% decrease of the dominating decay time by increasing Li content. Based on our findings, a simplified model for the photophysical kinetics is proposed that identifies the excited-state processes. The results outlined here pave the way for a rational design of confined metal clusters in various frames and inspire the specified applications of Ag-zeolites.