Tandem Catalysts Enabling Efficient C-N Coupling toward the Electrosynthesis of Urea.

The development of a methodology for synthesizing value-added urea (CO(NH2)2) via a renewable electricity-driven C-N coupling reaction under mild conditions is highly anticipated. However, the complex catalytic active sites that act on the carbon and nitrogen species make the reaction mechanism unclear, resulting in a low efficiency of C-N coupling from the co-reduction of carbon dioxide (CO2) and nitrate (NO3 -). Herein, we propose a novel tandem catalyst of Mo-PCN-222(Co), in which the Mo sites serve to facilitate nitrate reduction to the *NH2 intermediate, while the Co sites enhance CO2 reduction to carbonic oxide (CO), thus synergistically promoting C-N coupling. The synthesized Mo-PCN-222(Co) catalyst exhibited a noteworthy urea yield rate of 844.11 mg h-1 g-1, alongside a corresponding Faradaic efficiency of 33.90 % at -0.4 V vs. reversible hydrogen electrode (RHE). By combining in situ spectroscopic techniques with density functional theory calculations, we demonstrate that efficient C-N coupling is attributed to a tandem system in which the *NH2 and *CO intermediates produced by the Mo and Co active sites of Mo-PCN-222(Co) stabilize the formation of the *CONH2 intermediate. This study provides an effective avenue for the design and synthesis of tandem catalysts for electrocatalytic urea synthesis.

Electrokinetic Analyses Uncover the Rate-Determining Step of Biomass-Derived Monosaccharide Electroreduction on Copper.

Electrochemical biomass conversion holds promise to upcycle carbon sources and produce valuable products while reducing greenhouse gas emissions. To this end, deep insight into the interfacial mechanism is essential for the rational design of an efficient electrocatalytic route, which is still an area of active research and development. Herein, we report the reduction of dihydroxyacetone (DHA)-the simplest monosaccharide derived from glycerol feedstock-to acetol, the vital chemical intermediate in industries, with faradaic efficiency of 85±5 % on a polycrystalline Cu electrode. DHA reduction follows preceding dehydration by coordination with the carbonyl and hydroxyl groups and the subsequent hydrogenation. The electrokinetic profile indicates that the rate-determining step (RDS) includes a proton-coupled electron transfer (PCET) to the dehydrated intermediate, revealed by coverage-dependent Tafel slope and isotopic labeling experiments. An approximate zero-order dependence of H+ suggests that water acts as the proton donor for the interfacial PCET process. Leveraging these insights, we formulate microkinetic models to illustrate its origin that Eley-Rideal (E-R) dominates over Langmuir-Hinshelwood (L-H) in governing Cu-mediated DHA reduction, offering rational guidance that increasing the concentration of the adsorbed reactant alone would be sufficient to promote the activity in designing practical catalysts.

Defects in lead halide perovskite light-emitting diodes under electric field: from behavior to passivation strategies.

Lead halide perovskites (LHPs) are emerging semiconductor materials for light-emitting diodes (LEDs) owing to their unique structure and superior optoelectronic properties. However, defects that initiate degradation of LHPs through external stimuli and prompt internal ion migration at the interfaces remain a significant challenge. The electric field (EF), which is a fundamental driving force in LED operation, complicates the role of these defects in the physical and chemical properties of LHPs. A deeper understanding of EF-induced defect behavior is crucial for optimizing the LED performance. In this review, the origins and characterization of defects are explored, indicating the influence of EF-induced defect dynamics on LED performance and stability. A comprehensive overview of recent defect passivation approaches for LHP bulk films and nanocrystals (NCs) is also provided. Given the ubiquity of EF, a summary of the EF-induced defect behavior can enhance the performance of perovskite LEDs and related optoelectronic devices.

Stability and Degradation in Lead Halide Perovskite Nanocrystals via Regulation of Lattice Strain.

It is still quite challenging to achieve high-performance and stable blue perovskite materials due to their instability and degradation. The lattice strain provides an important pathway to investigate the degradation process. In this article, the lattice strain in perovskite nanocrystals was regulated by the ratio of Cs+, EA+, and Rb+ cations with different sizes. Their electrical structure, formation energy, and ion migration activation energy were calculated with the density functional theory (DFT) method. The luminescence properties and stability of blue lead bromide perovskite nanocrystals were analyzed with spectra regulation from 516 to 472 nm. It was demonstrated that the lattice strain plays an important role in the luminescence performance and degradation process of perovskite materials. The study provides the positive correlation between lattice strain and degradation as well as luminescence properties in lead halide perovskite materials, which is of great importance in uncovering their degradation mechanism and developing stable and high-performance blue perovskite materials.

Estimation of indoor soil/dust-skin adherence factors and health risks for adults and children in two typical cities in southern China.

Soil/dust (SD) skin adherence is key dermal exposure parameter used for calculating the health risk of dermal exposure to contaminants. However, few studies of this parameter have been conducted in Chinese populations. In this study, forearm SD samples were randomly collected using the wipe method from population in two typical cities in southern China as well as office staff in a fixed indoor environment. SD samples from the corresponding areas were also sampled. The wipes and SD were analyzed for tracer elements (aluminum, barium, manganese, titanium, and vanadium). The SD-skin adherence factors were 14.31 µg/cm2 for adults in Changzhou, 7.25 µg/cm2 for adults in Shantou, and 9.37 µg/cm2 for children in Shantou, respectively. Further, the recommended values for indoor SD-skin adherence factors for adults and children in Southern China were calculated to be 11.50 µg/cm2 and 9.37 µg/cm2, respectively, which were lower than the U.S. Environmental Protection Agency (USEPA) recommended values. And the SD-skin adherence factor value for the office staff was small (1.79 µg/cm2), but the data were more stable. In addition, PBDEs and PCBs in dust samples from industrial and residential area in Shantou were also determined, and health risks were assessed using the dermal exposure parameters measured in this study. None of the organic pollutants posed a health risk to adults and children via dermal contact. These studies emphasized the importance of localized dermal exposure parameters, and further studies should be conducted in the future.

Emission inventories, emission factors, and composition profiles of volatile organic compounds (VOCs) and heavy metals (HMs) from an e-waste dismantling park in southern China.

Electronic waste (e-waste) dismantling is a significant source of atmospheric pollutants, including volatile organic compounds (VOCs) and heavy metals (HMs), which may have adverse effects on the surrounding environment and residents. However, the organized emission inventories and emission characteristics of VOCs and HMs from e-waste dismantling are not well documented. In this study, the concentrations and components of VOCs and HMs were monitored at the exhaust gas treatment facility from two process areas of a typical e-waste dismantling park in southern China in 2021. Emission inventories of VOCs and HMs were established, with total emissions of 8.85 t/a and 18.3 kg/a for VOCs and HMs in this park, respectively. The cutting & crushing (CC) area was the largest emissions source, accounting for 82.6% of VOCs and 79.9% of HMs, respectively, while the baking plate (BP) area had higher emission factors. Additionally, the concentration and composition of VOCs and HMs in the park were also analyzed. For VOCs, the concentrations of halogenated hydrocarbons and aromatic hydrocarbons were comparable in the park, while m/p-xylene, o-xylene, and chlorobenzene were the key VOC species. The HM concentrations followed the order of Pb > Cu > Mn > Ni > As > Cd > Hg, with Pb and Cu being the main heavy metals released. This is the first VOC and HM emission inventory for the e-waste dismantling park, and our data will lay a solid ground for pollution control and management for the e-waste dismantling industry.

Isolated Electron-Rich Ruthenium Atoms in Intermetallic Compounds for Boosting Electrochemical Nitric Oxide Reduction to Ammonia.

The direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH3 with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body-centered cubic RuGa intermetallic compounds (i.e., bcc RuGa IMCs) via a substrate-anchored thermal annealing method. The electrocatalyst exhibits a remarkable NH4 + yield rate of 320.6 µmol h-1 mg-1 Ru with the corresponding Faradaic efficiency of 72.3 % at very low potential of -0.2 V vs. reversible hydrogen electrode (RHE) in neutral media. Theoretical calculations reveal that the electron-rich Ru atoms in bcc RuGa IMCs facilitate the adsorption and activation of *HNO intermediate. Hence, the energy barrier of the potential-determining step in NORR could be greatly reduced.

Dissociative Adsorption of Acetone on Platinum Single-Crystal Electrodes.

In this article, we investigate the poisoning reaction that occurs at platinum electrodes during the electrocatalytic hydrogenation of acetone. A better understanding of this poisoning reaction is important to develop electrocatalysts that are both active for the hydrogenation of carbonyl compounds and resilient against poisoning side reactions. We adsorb acetone to Pt(331), Pt(911), Pt(510), and Pt(533) (i.e., Pt[2(111) × (110)], Pt[5(100) × (111)], [5(100) × (110)], and Pt[4(111) × (100), respectively])) as well as Pt(100) single-crystal electrodes and perform reductive and oxidative stripping experiments after electrolyte exchange. We found that acetone adsorbs molecularly intact on all sites apart from Pt(100) terrace sites and can be stripped reductively from the electrode surface at a potential positive of hydrogen evolution. However, at Pt(100) terraces, acetone adsorbs dissociatively as carbon monoxide, which remains attached to the electrode surface and leads to its poisoning. Strikingly, dissociative adsorption does not occur on step sites with (100) geometry, which suggests that the dissociative adsorption of acetone is limited to Pt(100) terraces featuring a certain minimum "ensemble" number of freely available Pt atoms.

Design of oxa-spirocyclic PHOX ligands for the asymmetric synthesis of lorcaserin via iridium-catalyzed asymmetric hydrogenation.

Phosphine-oxazoline (PHOX) ligands are a very important class of privileged ligands in asymmetric catalysis. A series of highly rigid oxa-spiro phosphine-oxazoline (O-SIPHOX) ligands based on O-SPINOL was synthesized efficiently, and their iridium complexes were synthesized by coordination of the O-SIPHOX ligands to [Ir(cod)Cl]2 in the presence of sodium tetrakis-3,5-bis(trifluoromethyl)phenylborate (NaBArF). The cationic iridium complexes showed high reactivity and excellent enantioselectivity in the asymmetric hydrogenation of 1-methylene-tetrahydro-benzo[d]azepin-2-ones (up to 99% yield and up to 99% ee). A key intermediate of the anti-obesity drug lorcaserin could be efficiently synthesized using this protocol.

Molecular tuning of CO2-to-ethylene conversion.

The electrocatalytic reduction of carbon dioxide, powered by renewable electricity, to produce valuable fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of energy produced by intermittent renewable sources1. However, the highly selective generation of economically desirable products such as ethylene from the carbon dioxide reduction reaction (CO2RR) remains a challenge2. Tuning the stabilities of intermediates to favour a desired reaction pathway can improve selectivity3-5, and this has recently been explored for the reaction on copper by controlling morphology6, grain boundaries7, facets8, oxidation state9 and dopants10. Unfortunately, the Faradaic efficiency for ethylene is still low in neutral media (60 per cent at a partial current density of 7 milliamperes per square centimetre in the best catalyst reported so far9), resulting in a low energy efficiency. Here we present a molecular tuning strategy-the functionalization of the surface of electrocatalysts with organic molecules-that stabilizes intermediates for more selective CO2RR to ethylene. Using electrochemical, operando/in situ spectroscopic and computational studies, we investigate the influence of a library of molecules, derived by electro-dimerization of arylpyridiniums11, adsorbed on copper. We find that the adhered molecules improve the stabilization of an 'atop-bound' CO intermediate (that is, an intermediate bound to a single copper atom), thereby favouring further reduction to ethylene. As a result of this strategy, we report the CO2RR to ethylene with a Faradaic efficiency of 72 per cent at a partial current density of 230 milliamperes per square centimetre in a liquid-electrolyte flow cell in a neutral medium. We report stable ethylene electrosynthesis for 190 hours in a system based on a membrane-electrode assembly that provides a full-cell energy efficiency of 20 per cent. We anticipate that this may be generalized to enable molecular strategies to complement heterogeneous catalysts by stabilizing intermediates through local molecular tuning.

Author Correction: Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Dopant-tuned stabilization of intermediates promotes electrosynthesis of valuable C3 products.

The upgrading of CO2/CO feedstocks to higher-value chemicals via energy-efficient electrochemical processes enables carbon utilization and renewable energy storage. Substantial progress has been made to improve performance at the cathodic side; whereas less progress has been made on improving anodic electro-oxidation reactions to generate value. Here we report the efficient electroproduction of value-added multi-carbon dimethyl carbonate (DMC) from CO and methanol via oxidative carbonylation. We find that, compared to pure palladium controls, boron-doped palladium (Pd-B) tunes the binding strength of intermediates along this reaction pathway and favors DMC formation. We implement this doping strategy and report the selective electrosynthesis of DMC experimentally. We achieve a DMC Faradaic efficiency of 83 ± 5%, fully a 3x increase in performance compared to the corresponding pure Pd electrocatalyst.

Copper-on-nitride enhances the stable electrosynthesis of multi-carbon products from CO2.

Copper-based materials are promising electrocatalysts for CO2 reduction. Prior studies show that the mixture of copper (I) and copper (0) at the catalyst surface enhances multi-carbon products from CO2 reduction; however, the stable presence of copper (I) remains the subject of debate. Here we report a copper on copper (I) composite that stabilizes copper (I) during CO2 reduction through the use of copper nitride as an underlying copper (I) species. We synthesize a copper-on-nitride catalyst that exhibits a Faradaic efficiency of 64 ± 2% for C2+ products. We achieve a 40-fold enhancement in the ratio of C2+ to the competing CH4 compared to the case of pure copper. We further show that the copper-on-nitride catalyst performs stable CO2 reduction over 30 h. Mechanistic studies suggest that the use of copper nitride contributes to reducing the CO dimerization energy barrier-a rate-limiting step in CO2 reduction to multi-carbon products.

Metal-Organic Frameworks Mediate Cu Coordination for Selective CO2 Electroreduction.

The electrochemical carbon dioxide reduction reaction (CO2RR) produces diverse chemical species. Cu clusters with a judiciously controlled surface coordination number (CN) provide active sites that simultaneously optimize selectivity, activity, and efficiency for CO2RR. Here we report a strategy involving metal-organic framework (MOF)-regulated Cu cluster formation that shifts CO2 electroreduction toward multiple-carbon product generation. Specifically, we promoted undercoordinated sites during the formation of Cu clusters by controlling the structure of the Cu dimer, the precursor for Cu clusters. We distorted the symmetric paddle-wheel Cu dimer secondary building block of HKUST-1 to an asymmetric motif by separating adjacent benzene tricarboxylate moieties using thermal treatment. By varying materials processing conditions, we modulated the asymmetric local atomic structure, oxidation state and bonding strain of Cu dimers. Using electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) experiments, we observed the formation of Cu clusters with low CN from distorted Cu dimers in HKUST-1 during CO2 electroreduction. These exhibited 45% C2H4 faradaic efficiency (FE), a record for MOF-derived Cu cluster catalysts. A structure-activity relationship was established wherein the tuning of the Cu-Cu CN in Cu clusters determines the CO2RR selectivity.

Dipolar cations confer defect tolerance in wide-bandgap metal halide perovskites.

Efficient wide-bandgap perovskite solar cells (PSCs) enable high-efficiency tandem photovoltaics when combined with crystalline silicon and other low-bandgap absorbers. However, wide-bandgap PSCs today exhibit performance far inferior to that of sub-1.6-eV bandgap PSCs due to their tendency to form a high density of deep traps. Here, we show that healing the deep traps in wide-bandgap perovskites-in effect, increasing the defect tolerance via cation engineering-enables further performance improvements in PSCs. We achieve a stabilized power conversion efficiency of 20.7% for 1.65-eV bandgap PSCs by incorporating dipolar cations, with a high open-circuit voltage of 1.22 V and a fill factor exceeding 80%. We also obtain a stabilized efficiency of 19.1% for 1.74-eV bandgap PSCs with a high open-circuit voltage of 1.25 V. From density functional theory calculations, we find that the presence and reorientation of the dipolar cation in mixed cation-halide perovskites heals the defects that introduce deep trap states.

Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons.

The electrochemical reduction of CO2 to multi-carbon products has attracted much attention because it provides an avenue to the synthesis of value-added carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the efficiency of CO2 conversion to C2 products remains below that necessary for its implementation at scale. Modifying the local electronic structure of copper with positive valence sites has been predicted to boost conversion to C2 products. Here, we use boron to tune the ratio of Cuδ+ to Cu0 active sites and improve both stability and C2-product generation. Simulations show that the ability to tune the average oxidation state of copper enables control over CO adsorption and dimerization, and makes it possible to implement a preference for the electrosynthesis of C2 products. We report experimentally a C2 Faradaic efficiency of 79 ± 2% on boron-doped copper catalysts and further show that boron doping leads to catalysts that are stable for in excess of ~40 hours while electrochemically reducing CO2 to multi-carbon hydrocarbons.

Water-resistant, monodispersed and stably luminescent CsPbBr3/CsPb2Br5 core-shell-like structure lead halide perovskite nanocrystals.

Lead halide perovskite materials are thriving in optoelectronic applications due to their excellent properties, while their instability due to the fact that they are easily hydrolyzed is still a bottleneck for their potential application. In this work, water-resistant, monodispersed and stably luminescent cesium lead bromine perovskite nanocrystals coated with CsPb2Br5 were obtained using a modified non-stoichiometric solution-phase method. CsPb2Br5 2D layers were coated on the surface of CsPbBr3 nanocrystals and formed a core-shell-like structure in the synthetic processes. The stability of the luminescence of the CsPbBr3 nanocrystals in water and ethanol atmosphere was greatly enhanced by the photoluminescence-inactive CsPb2Br5 coating with a wide bandgap. The water-stable enhanced nanocrystals are suitable for long-term stable optoelectronic applications in the atmosphere.

Upconversion Nanocrystals Mediated Lateral-Flow Nanoplatform for in Vitro Detection.

Upconversion phosphors (UCPs) that are free from interference from biological sample autofluorescence have attracted attention for in vivo and in vitro bioapplications. However, UCPs need to be water-dispersible, nanosized, and highly luminous to realize broad applications. Therefore, the aim of this research is to develop UCPs that meet these comprehensive criteria for in vitro diagnosis. To combine nano size with high luminous intensity, ß-NaYF4:Yb3+,Er3+ upconversion nanocrystals (UCNPs) codoped with Li+ and K+ are prepared that display high upconversion intensities as well as small size. The strongest green and red emissions of the Na0.9Li0.07K0.03YF4:Yb3+,Er3+ nanocrystals are increased by 7 and 10 times, respectively, compared with those of the undoped NaYF4:Yb3+,Er3+ nanocrystals. A mild sol-gel surface modification method is used to produce water-phase dispersions and allow covalent biomolecule conjugation. The bioactivated UCNPs are used as a bioreporter and integrated with a classical lateral flow assay to establish an assay to accomplish simultaneous dual-target detection of Yersinia pestis and Burkholderia pseudomallei. The assay achieves a sensitivity of 103 CFU/test without cross-interference between two targets. The research provides a way to produce UCNPs with comprehensive properties for use as excellent optical reporters in in vivo and in vitro bioapplications.

Shape-Controlled Synthesis of All-Inorganic CsPbBr3 Perovskite Nanocrystals with Bright Blue Emission.

We developed a colloidal synthesis of CsPbBr3 perovskite nanocrystals (NCs) at a relative low temperature (90 °C) for the bright blue emission which differs from the original green emission (∼510 nm) of CsPbBr3 nanocubes as reported previously. Shapes of the obtained CsPbBr3 NCs can be systematically engineered into single and lamellar-structured 0D quantum dots, as well as face-to-face stacking 2D nanoplatelets and flat-lying 2D nanosheets via tuning the amounts of oleic acid (OA) and oleylamine (OM). They exhibit sharp excitonic PL emissions at 453, 472, 449, and 452 nm, respectively. The large blue shift relative to the emission of CsPbBr3 bulk crystal can be ascribed to the strong quantum confinement effects of these various nanoshapes. PL decay lifetimes are measured, ranging from several to tens of nanoseconds, which infers the higher ratio of exciton radiative recombination to the nonradiative trappers in the obtained CsPbBr3 NCs. These shape-controlled CsPbBr3 perovskite NCs with the bright blue emission will be widely used in optoelectronic applications, especially in blue LEDs which still lag behind compared to the better developed red and green LEDs.

Enantioselective N-heterocyclic carbene-catalyzed synthesis of saccharine-derived dihydropyridinones with cis-selectivity.

The enantioselective N-heterocyclic carbene-catalyzed [2 + 4] cyclocondensation of α-chloroaldehydes and saccharine-derived 1-azadienes was developed, giving the corresponding saccharine-derived dihydropyridinones in good yields with exclusive cis-selectivities and excellent enantioselectivities.