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Lead (Pb) halide perovskite solar cells (PSCs) exhibit impressive power conversion efficiencies close to those of their silicon counterparts. However, they suffer from moisture instability and Pb safety concerns. Previous studies have endeavoured to address these issues independently, yielding minimal advancements. Here, a general nanoencapsulation platform using natural polyphenols is reported for Pb-halide PSCs that simultaneously addresses both challenges. The polyphenol-based encapsulant is solution-processable, inexpensive (≈1.6 USD m-2), and requires only 5 min for the entire process, highlighting its potential scalability. The encapsulated devices with a power conversion efficiency of 20.7% retained up to 80% of their peak performance for 2000 h and up to 70% for 7000 h. Under simulated rainfall conditions, the encapsulant rich in catechol groups captures the Pb ions released from the degraded perovskites via coordination, keeping the Pb levels within the safe drinking water threshold of 15 ppb.
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Nano zero-valent metals (nZVMs) have been extensively utilized for decades in the reductive remediation of groundwater contaminated with chlorinated organic compounds, owing to their robust reducing capabilities, simple application, and cost-effectiveness. Nevertheless, there remains a dearth of information regarding the efficient reductive defluorination of linear or branched per- and polyfluoroalkyl substances (PFASs) using nZVMs as reductants, largely due to the absence of appropriate catalysts. In this work, various soluble porphyrin ligands [[mesotetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·7H2O (CoTCPP), [[mesotetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H2O (CoTPPS), and [[mesotetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I)4·4H2O (CoTMpyP) have been explored for defluorination of PFASs in the presence of the nZn0 as reductant. Among these, the cationic CoTMpyP showed best defluorination efficiencies for br-perfluorooctane sulfonate (PFOS) (94%), br-perfluorooctanoic acid (PFOA) (89%), and 3,7-Perfluorodecanoic acid (PFDA) (60%) after 1 day at 70 °C. The defluorination rate constant of this system (CoTMpyP-nZn0) is 88-164 times higher than the VB12-nZn0 system for the investigated br-PFASs. The CoTMpyP-nZn0 also performed effectively at room temperature (55% for br-PFOS, 55% for br-PFOA and 25% for 3,7-PFDA after 1day), demonstrating the great potential of in-situ application. The effect of various solubilizing substituents, electron transfer flow and corresponding PFASs defluorination pathways in the CoTMpyP-nZn0 system were investigated by both experiments and density functional theory (DFT) calculations. SYNOPSIS: Due to the unavailability of active catalysts, available information on reductive remediation of PFAS by zero-valent metals (ZVMs) is still inadequate. This study explores the effective defluorination of various branched PFASs using soluble porphyrin-ZVM systems and offers a systematic approach for designing the next generation of catalysts for PFAS remediation.
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Zinco , Zinco/química , Porfirinas/química , Fluorocarbonos/química , Metaloporfirinas/química , Poluentes Químicos da Água/química , OxirreduçãoRESUMO
Alloyed metal nanoparticles are a promising platform for plasmonically enabled hot-carrier generation, which can be used to drive photochemical reactions. Although the non-plasmonic component in these systems has been investigated for its potential to enhance catalytic activity, its capacity to affect the photochemical process favorably has been underexplored by comparison. Here, we study the impact of surface alloy species and concentration on hot-carrier generation in Ag nanoparticles. By first-principles simulations, we photoexcite the localized surface plasmon, allow it to dephase, and calculate spatially and energetically resolved hot-carrier distributions. We show that the presence of non-noble species in the topmost surface layer drastically enhances hot-hole generation at the surface at the expense of hot-hole generation in the bulk, due to the additional d-type states that are introduced to the surface. The energy of the generated holes can be tuned by choice of the alloyant, with systematic trends across the d-band block. Already low surface alloy concentrations have a large impact, with a saturation of the enhancement effect typically close to 75% of a monolayer. Hot-electron generation at the surface is hindered slightly by alloying, but here a judicious choice of the alloy composition allows one to strike a balance between hot electrons and holes. Our work underscores the promise of utilizing multicomponent nanoparticles to achieve enhanced control over plasmonic catalysis and provides guidelines for how hot-carrier distributions can be tailored by designing the electronic structure of the surface through alloying.
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The use of liquid gallium as a solvent for catalytic reactions has enabled access to well-dispersed metal atoms configurations, leading to unique catalytic phenomena, including activation of neighbouring liquid atoms and mobility-induced activity enhancement. To gain mechanistic insights into liquid metal catalysts, here we introduce a GaSn0.029Ni0.023 liquid alloy for selective propylene synthesis from decane. Owing to their mobility, dispersed atoms in a Ga matrix generate configurations where interfacial Sn and Ni atoms allow for critical alignments of reactants and intermediates. Computational modelling, corroborated by experimental analyses, suggests a particular reaction mechanism by which Sn protrudes from the interface and an adjacent Ni, below the interfacial layer, aligns precisely with a decane molecule, facilitating propylene production. We then apply this reaction pathway to canola oil, attaining a propylene selectivity of ~94.5%. Our results offer a mechanistic interpretation of liquid metal catalysts with an eye to potential practical applications of this technology.
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The production of aluminum (Al) metal-organic frameworks (MOFs) by electrosynthesis using solid-state Al electrodes always faces significant challenges due to the formation of a passivating aluminum oxide layer in the process. Here, we developed a liquid-metal-based method to electrosynthesize an aluminum Al-MOF (MIL-53). This method uses a liquid-state gallium (Ga) anode as a reservoir and activator for a light metal, Al, in the form of Al-Ga alloys that releases Al3+ for the electrosynthesis of Al-MOFs. Introducing Ga into the system inhibits the formation of aluminum oxide passivation layer and promotes the electrochemical reaction for Al-MOF synthesis. The electrosynthesis using liquid Al-Ga alloy is conducted at ambient temperatures for long durations without requiring pretreatment for aluminum oxide removal. We show that the Al-MOF products synthesized from 0.40 wt % Al in liquid Ga lead to the highest crystallinity and possess a specific surface area greater than 800 m2 g-1 and a low capacity for CO2 adsorption that can be used as a potential matrix for CO2/N2 separation. This work provides evidence that employing liquid-metal electrodes offers a viable pathway to circumvent surface passivation effects that inevitably occur when using conventional solid metals. It also introduces an efficient electrosynthesis method based on liquid metals for producing atomically porous materials.
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Ni-based hydroxides are promising electrocatalysts for biomass oxidation reactions, supplanting the oxygen evolution reaction (OER) due to lower overpotentials while producing value-added chemicals. The identification and subsequent engineering of their catalytically active sites are essential to facilitate these anodic reactions. Herein, the proportional relationship between catalysts' deprotonation propensity and Faradic efficiency of 5-hydroxymethylfurfural (5-HMF)-to-2,5 furandicarboxylic acid (FDCA, FEFDCA ) is revealed by thorough density functional theory (DFT) simulations and atomic-scale characterizations, including in situ synchrotron diffraction and spectroscopy methods. The deprotonation capability of ultrathin layer-double hydroxides (UT-LDHs) is regulated by tuning the covalency of metal (M)-oxygen (O) motifs through defect site engineering and selection of M3+ co-chemistry. NiMn UT-LDHs show an ultrahigh FEFDCA of 99% at 1.37 V versus reversible hydrogen electrode (RHE) and retain a high FEFDCA of 92.7% in the OER-operating window at 1.52 V, about 2× that of NiFe UT-LDHs (49.5%) at 1.52 V. Ni-O and Mn-O motifs function as dual active sites for HMF electrooxidation, where the continuous deprotonation of Mn-OH sites plays a dominant role in achieving high selectivity while suppressing OER at high potentials. The results showcase a universal concept of modulating competing anodic reactions in aqueous biomass electrolysis by electronically engineering the deprotonation behavior of metal hydroxides, anticipated to be translatable across various biomass substrates.
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Metallic nanoarchitectures hold immense value as functional materials across diverse applications. However, major challenges lie in effectively engineering their hierarchical porosity while achieving scalable fabrication at low processing temperatures. Here we present a liquid-metal solvent-based method for the nanoarchitecting and transformation of solid metals. This was achieved by reacting liquid gallium with solid metals to form crystalline entities. Nanoporous features were then created by selectively removing the less noble and comparatively softer gallium from the intermetallic crystals. By controlling the crystal growth and dealloying conditions, we realized the effective tuning of the micro-/nanoscale porosities. Proof-of-concept examples were shown by applying liquid gallium to solid copper, silver, gold, palladium, and platinum, while the strategy can be extended to a wider range of metals. This metallic-solvent-based route enables low-temperature fabrication of metallic nanoarchitectures with tailored porosity. By demonstrating large-surface-area and scalable hierarchical nanoporous metals, our work addresses the pressing demand for these materials in various sectors.
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Bayesian optimisation (BO) has been increasingly utilised to guide material discovery. While BO is advantageous due to its sample efficiency, flexibility and versatility, it is constrained by a range of core issues including high-dimensional optimisation, mixed search space, multi-objective optimisation and multi-fidelity data. Although various studies have attempted to tackle one or some challenges, a comprehensive BO framework for material discovery is yet to be uncovered. This work provides a short review aiming at connecting algorithmic advancement to material applications. Open algorithmic challenges are discussed and supported by recent material applications. Various open-source packages are compared to assist the selection. Furthermore, three exemplary material design problems are analysed to demonstrate how BO could be useful. The review concludes with an outlook on BO-aided autonomous laboratory.
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The coupling of oxygen evolution reaction (OER) catalysts with photoanodes is a promising strategy for enhancing the photoelectrochemical (PEC) performance by passivating photoanode's surface defect states and facilitating charge transfer at the photoanode/electrolyte interface. However, a serious interface recombination issue caused by poor interface and OER catalysts coating quality often limits further performance improvement of photoanodes. Herein, a rapid Fenton-like reaction method is demonstrated to produce ultrathin amorphous Ni:FeOOH catalysts with in situ-induced oxygen vacancies (Vo) to improve the water oxidation activity and stability of BiVO4 photoanodes. The combined physical characterizations, PEC studies, and density functional theory calculations revealed that the reductive environment in a Fenton-like reaction in situ produces abundant Vo in Ni:FeOOH catalysts, which significantly improves charge separation and charge transfer efficiency of BiVO4 while also offering abundant active sites and a reduced energy barrier for OER. As a result, Ni:FeOOH-Vo catalysts yielded a more than 2-fold increased photocurrent density in the BiVO4 photoanode (from 1.54 to 4.15 mA cm-2 at 1.23 VRHE), accompanied by high stability for 5 h. This work not only highlights the significance of abundant Vo in catalysts but also provides new insights into the rational design and fabrication of efficient and stable solar water-splitting systems.
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Single-atom catalysts (SACs) have shown potential for achieving an efficient electrochemical CO2 reduction reaction (CO2RR) despite challenges in their synthesis. Here, Ag2S/Ag nanowires provide initial anchoring sites for Cu SACs (Cu/Ag2S/Ag), then Cu/Ag(S) was synthesized by an electrochemical treatment resulting in complete sulfur removal, i.e., Cu SACs on a defective Ag surface. The CO2RR Faradaic efficiency (FECO2RR) of Cu/Ag(S) reaches 93.0% at a CO2RR partial current density (jCO2RR) of 2.9 mA/cm2 under -1.0 V vs RHE, which outperforms sulfur-removed Ag2S/Ag without Cu SACs (Ag(S), 78.5% FECO2RR with 1.8 mA/cm2jCO2RR). At -1.4 V vs RHE, both FECO2RR and jCO2RR over Cu/Ag(S) reached 78.6% and 6.1 mA/cm2, which tripled those over Ag(S), respectively. As revealed by in situ and ex situ characterizations together with theoretical calculations, the interacted Cu SACs and their neighboring defective Ag surface increase microstrain and downshift the d-band center of Cu/Ag(S), thus lowering the energy barrier by â¼0.5 eV for *CO formation, which accounts for the improved CO2RR activity and selectivity toward related products such as CO and C2+ products.
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Establishing generic catalyst design principles by identifying structural features of materials that influence their performance will advance the rational engineering of new catalytic materials. In this study, by investigating metal-substituted manganese oxide (spinel) nanoparticles, Mn3 O4 :M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn3 O4 :M for the electrocatalytic oxygen reduction reaction (ORR) on the enthalpy of formation of the binary MO oxide, Δf H°(MO), and the Lewis acidity of the M2+ substituent. Incorporation of elements M with low Δf H°(MO) enhances the oxygen binding strength in Mn3 O4 :M, which affects its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis relying on the rational substitution/doping by redox-inactive elements.
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MXenes, due to their tailorable chemistry and favourable physical properties, have great promise in electrocatalytic energy conversion reactions. To exploit fully their enormous potential, further advances specific to electrocatalysis revolving around their performance, stability, compositional discovery and synthesis are required. The most recent advances in these aspects are discussed in detail: surface functional and stoichiometric modifications which can improve performance, Pourbaix stability related to their electrocatalytic operating conditions, density functional theory and advances in machine learning for their discovery, and prospects in large scale synthesis and solution processing techniques to produce membrane electrode assemblies and integrated electrodes. This Review provides a perspective that is complemented by new density functional theory calculations which show how these recent advances in MXene material design are paving the way for effective electrocatalysts required for the transition to integrated renewable energy systems.
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Insights into metal-matrix interactions in atomically dispersed catalytic systems are necessary to exploit the true catalytic activity of isolated metal atoms. Distinct from catalytic atoms spatially separated but immobile in a solid matrix, here we demonstrate that a trace amount of platinum naturally dissolved in liquid gallium can drive a range of catalytic reactions with enhanced kinetics at low temperature (318 to 343 K). Molecular simulations provide evidence that the platinum atoms remain in a liquid state in the gallium matrix without atomic segregation and activate the surrounding gallium atoms for catalysis. When used for electrochemical methanol oxidation, the surface platinum atoms in the gallium-platinum system exhibit an activity of [Formula: see text] three orders of magnitude higher than existing solid platinum catalysts. Such a liquid catalyst system, with a dynamic interface, sets a foundation for future exploration of high-throughput catalysis.
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Creating high surface area nanocatalysts that contain stacking faults is a promising strategy to improve catalytic activity. Stacking faults can tune the reactivity of the active sites, leading to improved catalytic performance. The formation of branched metal nanoparticles with control of the stacking fault density is synthetically challenging. In this work, we demonstrate that varying the branch width by altering the size of the seed that the branch grows off is an effective method to precisely tune the stacking fault density in branched Ni nanoparticles. A high density of stacking faults across the Ni branches was found to lower the energy barrier for Ni2+/Ni3+ oxidation and result in enhanced activity for electrocatalytic oxidation of 5-hydroxylmethylfurfural. These results show the ability to synthetically control the stacking fault density in branched nanoparticles as a basis for enhanced catalytic activity.
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Nanopartículas Metálicas , Níquel , Catálise , Nanopartículas Metálicas/química , Níquel/químicaRESUMO
Angstrom-confined solvents in 2D laminates can travel through interlayer spacings, through gaps between adjacent sheets, and via in-plane pores. Among these, experimental access to investigate the mass transport through in-plane pores is lacking. Our experiments allow an understanding of this mass transport via the controlled variation of oxygen functionalities, size and density of in-plane pores in graphene oxide membranes. Contrary to expectations, our transport experiments show that higher in-plane pore densities may not necessarily lead to higher water permeability. We observed that membranes with a high in-plane pore density but a low amount of oxygen functionalities exhibit a complete blockage of water. However, when water-ethanol mixtures with a weaker hydrogen network are used, these membranes show an enhanced permeation. Our combined experimental and computational results suggest that the transport mechanism is governed by the attraction of the solvents toward the pores with functional groups and hindered by the strong hydrogen network of water formed under angstrom confinement.
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Platinum is the most efficient catalyst for hydrogen evolution reaction in acidic conditions, but its widespread use has been impeded by scarcity and high cost. Herein, Pt atomic clusters (Pt ACs) containing Pt-O-Pt units were prepared using Co/N co-doped carbon (CoNC) as support. Pt ACs are anchored to single Co atoms on CoNC by forming strong interactions. Pt-ACs/CoNC exhibits only 24 mV overpotential at 10 mA cm-2 and a high mass activity of 28.6 A mg-1 at 50 mV, which is more than 6 times higher than commercial Pt/C with any Pt loadings. Spectroscopic measurements and computational modeling reveal the enhanced hydrogen generation activity attributes to the charge redistribution between Pt and O atoms in Pt-O-Pt units, making Pt atoms the main active sites and O linkers the assistants, thus optimizing the proton adsorption and hydrogen desorption. This work opens an avenue to fabricate noble-metal-based ACs stabilized by single-atom catalysts with desired properties for electrocatalysis.
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Transforming natural resources to energy sources, such as converting CH4 to H2 and carbon, at high efficiency and low cost is crucial for many industries and environmental sustainability. The high temperature requirement of CH4 conversion regarding many of the current methods remains a critical bottleneck for their practical uptake. Here we report an approach based on gallium (Ga) liquid metal droplets, Ni(OH)2 cocatalysts, and mechanical energy input that offers low-temperature and scalable CH4 conversion into H2 and carbon. Mainly driven by the triboelectric voltage, originating from the joint contributions of the cocatalysts during agitation, CH4 is converted at the Ga and Ni(OH)2 interface through nanotribo-electrochemical reaction pathways. The efficiency of the system is enhanced when the reaction is performed at an increased pressure. The dehydrogenation of other nongaseous hydrocarbons using this approach is also demonstrated. This technology presents a possible low energy route for CH4 conversion without involving high temperature and harsh operating conditions.
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MgO-based CO2 sorbents promoted with molten alkali metal nitrates (e.g., NaNO3) have emerged as promising materials for CO2 capture and storage technologies due to their low cost and high theoretical CO2 uptake capacities. Yet, the mechanism by which molten alkali metal nitrates promote the carbonation of MgO (CO2 capture reaction) remains debated and poorly understood. Here, we utilize 18O isotope labeling experiments to provide new insights into the carbonation mechanism of NaNO3-promoted MgO sorbents, a system in which the promoter is molten under operation conditions and hence inherently challenging to characterize. To conduct the 18O isotope labeling experiments, we report a facile and large-scale synthesis procedure to obtain labeled MgO with a high 18O isotope content. We use Raman spectroscopy and in situ thermogravimetric analysis in combination with mass spectrometry to track the 18O label in the solid (MgCO3), molten (NaNO3), and gas (CO2) phases during the CO2 capture (carbonation) and regeneration (decarbonation) reactions. We discovered a rapid oxygen exchange between CO2 and MgO through the reversible formation of surface carbonates, independent of the presence of the promoter NaNO3. On the other hand, no oxygen exchange was observed between NaNO3 and CO2 or NaNO3 and MgO. Combining the results of the 18O labeling experiments, with insights gained from atomistic calculations, we propose a carbonation mechanism that, in the first stage, proceeds through a fast, surface-limited carbonation of MgO. These surface carbonates are subsequently dissolved as [Mg2+···CO3 2-] ionic pairs in the molten NaNO3 promoter. Upon reaching the solubility limit, MgCO3 crystallizes at the MgO/NaNO3 interface.
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Magic-sized clusters (MSCs) of semiconductor are typically defined as specific molecular-scale arrangements of atoms that exhibit enhanced stability. They often grow in discrete jumps, creating a series of crystallites, without the appearance of intermediate sizes. However, despite their long history, the mechanism behind their special stability and growth remains poorly understood. It is particularly difficult to explain experiments that have shown discrete evolution of MSCs to larger sizes well beyond the "cluster" regime and into the size range of colloidal quantum dots. Here, we study the growth of MSCs, including these larger magic-sized CdSe nanocrystals, to unravel the underlying growth mechanism. We first introduce a synthetic protocol that yields a series of nine magic-sized nanocrystals of increasing size. By investigating these crystallites, we obtain important clues about the mechanism. We then develop a microscopic model that uses classical nucleation theory to determine kinetic barriers and simulate the growth. We show that magic-sized nanocrystals are consistent with a series of zinc-blende crystallites that grow layer by layer under surface-reaction-limited conditions. They have a tetrahedral shape, which is preserved when a monolayer is added to any of its four identical facets, leading to a series of discrete nanocrystals with special stability. Our analysis also identifies strong similarities with the growth of semiconductor nanoplatelets, which we then exploit to further increase the size range of our magic-sized nanocrystals. Although we focus here on CdSe, these results reveal a fundamental growth mechanism that can provide a different approach to nearly monodisperse nanocrystals.
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Graphene oxide has shown exceptional properties in terms of water permeability and filtration characteristics. Here the suitability of graphene oxide membranes for the spatial separation of hydronium and hydroxide ions after photocatalytic water splitting is demonstrated. Instead of relying on classical size exclusion by adjusting the membrane laminates' interlayer spacings, nonmodified graphene oxide is used to exploit the presence of its natural functional groups and surface charges for filtration. Despite a significantly larger interlayer spacing inside the membrane compared with the size of the hydrated radii of the ions, highly asymmetric transport behavior and a 6 times higher mobility for hydronium than for hydroxide are observed. DFT simulations reveal that hydroxide ions are more prone to interact and stick to the functional groups of graphene oxide, while diffusion of hydronium ions through the membrane is less impeded and aligns well with the concept of the Grotthuss mechanism.