Colloidal Atomic Layer Deposition on Nanocrystals Using Ligand-Modified Precursors.

Atomic layer deposition (ALD) is a method to grow thin metal oxide layers on a variety of materials for applications spanning from electronics to catalysis. Extending ALD to colloidally stable nanocrystals promises to combine the benefits of thin metal oxide coatings with the solution processability of the nanocrystals. However, challenges persist in applying this method, which relate to finding precursors that promote the growth of the metal oxide while preserving colloidal stability throughout the process. Herein, we introduce a colloidal ALD method to coat nanocrystals with amorphous metal oxide shells using metal and oxygen precursors that act as colloidal stabilizing ligands. Our scheme involves metal-amide precursors modified with solubilizing groups and oleic acid as the oxygen source. The growth of the oxide is self-limiting and proceeds in a layer-by-layer fashion. Our protocol is generalizable and intrinsically scalable. Potential applications in display, light detection, and catalysis are envisioned.

Long live(d) CsPbBr3 superlattices: colloidal atomic layer deposition for structural stability.

Superlattice formation afforded by metal halide perovskite nanocrystals has been a phenomenon of interest due to the high structural order induced in these self-assemblies, an order that is influenced by the surface chemistry and particle morphology of the starting building block material. In this work, we report on the formation of superlattices from aluminum oxide shelled CsPbBr3 perovskite nanocrystals where the oxide shell is grown by colloidal atomic layer deposition. We demonstrate that the structural stability of these superlattices is preserved over 25 days in an inert atmosphere and that colloidal atomic layer deposition on colloidal perovskite nanocrystals yields structural protection and an enhancement in photoluminescence quantum yields and radiative lifetimes as opposed to gas phase atomic layer deposition on pre-assembled superlattices or excess capping group addition. Structural analyses found that shelling resulted in smaller nanocrystals that form uniform supercrystals. These effects are in addition to the increasingly static capping group chemistry initiated where oleic acid is installed as a capping ligand directly on aluminum oxide. Together, these factors lead to fundamental observations that may influence future superlattice assembly design.

Hybrid oxide coatings generate stable Cu catalysts for CO2 electroreduction.

Hybrid organic/inorganic materials have contributed to solve important challenges in different areas of science. One of the biggest challenges for a more sustainable society is to have active and stable catalysts that enable the transition from fossil fuel to renewable feedstocks, reduce energy consumption and minimize the environmental footprint. Here we synthesize novel hybrid materials where an amorphous oxide coating with embedded organic ligands surrounds metallic nanocrystals. We demonstrate that the hybrid coating is a powerful means to create electrocatalysts stable against structural reconstruction during the CO2 electroreduction. These electrocatalysts consist of copper nanocrystals encapsulated in a hybrid organic/inorganic alumina shell. This shell locks a fraction of the copper surface into a reduction-resistant Cu2+ state, which inhibits those redox processes responsible for the structural reconstruction of copper. The electrocatalyst activity is preserved, which would not be possible with a conventional dense alumina coating. Varying the shell thickness and the coating morphology yields fundamental insights into the stabilization mechanism and emphasizes the importance of the Lewis acidity of the shell in relation to the retention of catalyst structure. The synthetic tunability of the chemistry developed herein opens new avenues for the design of stable electrocatalysts and beyond.

Surface Chemistry Dictates the Enhancement of Luminescence and Stability of InP QDs upon c-ALD ZnO Hybrid Shell Growth.

Indium phosphide quantum dots (InP QDs) are a promising example of Restriction of Hazardous Substances directive (RoHS)-compliant light-emitting materials. However, they suffer from low quantum yield and instability upon processing under ambient conditions. Colloidal atomic layer deposition (c-ALD) has been recently proposed as a methodology to grow hybrid materials including QDs and organic/inorganic oxide shells, which possess new functions compared to those of the as-synthesized QDs. Here, we demonstrate that ZnO shells can be grown on InP QDs obtained via two synthetic routes, which are the classical sylilphosphine-based route and the more recently developed aminophosphine-based one. We find that the ZnO shell increases the photoluminescence emission only in the case of aminophosphine-based InP QDs. We rationalize this result with the different chemistry involved in the nucleation step of the shell and the resulting surface defect passivation. Furthermore, we demonstrate that the ZnO shell prevents degradation of the InP QD suspension under ambient conditions by avoiding moisture-induced displacement of the ligands from their surface. Overall, this study proposes c-ALD as a methodology for the synthesis of alternative InP-based core@shell QDs and provides insight into the surface chemistry that results in both enhanced photoluminescence and stability required for application in optoelectronic devices and bioimaging.

Voltage-Driven Chemical Reactions Enable the Synthesis of Tunable Liquid Ga-Metal Nanoparticles.

Nanosized particles of liquid metals are emerging materials that hold promise for applications spanning from microelectronics to catalysis. Yet, knowledge of their chemical reactivity is largely unknown. Here, we study the reactivity of liquid Ga and Cu nanoparticles under the application of a cathodic voltage. We discover that the applied voltage and the spatial proximity of these two particle precursors dictate the reaction outcome. In particular, we find that a gradual voltage ramp is crucial to reduce the native oxide skin of gallium and enable reactive wetting between the Ga and Cu nanoparticles; instead, a voltage step causes dewetting between the two. We determine that the use of liquid Ga/Cu nanodimer precursors, which consist of an oxide-covered Ga domain interfaced with a metallic Cu domain, provides a more uniform mixing and results in more homogeneous reaction products compared to a physical mixture of Ga and Cu NPs. Having learned this, we obtain CuGa2 alloys or solid@liquid CuGa2@Ga core@shell nanoparticles by tuning the stoichiometry of Ga and Cu in the nanodimer precursors. These products reveal an interesting complementarity of thermal and voltage-driven syntheses to expand the compositional range of bimetallic NPs. Finally, we extend the voltage-driven synthesis to the combination of Ga with other elements (Ag, Sn, Co, and W). By rationalizing the impact of the native skin reduction rate, the wetting properties, and the chemical reactivity between Ga and other metals on the results of such voltage-driven chemical manipulation, we define the criteria to predict the outcome of this reaction and set the ground for future studies targeting various applications for multielement nanomaterials based on liquid Ga.

Colloidal-ALD-Grown Metal Oxide Shells Enable the Synthesis of Photoactive Ligand/Nanocrystal Composite Materials.

Colloidal nanocrystals (NCs) are ideal materials for a variety of applications and devices, which span from catalysis and optoelectronics to biological imaging. Organic chromophores are often combined with NCs as photoactive ligands to expand the functionality of NCs or to achieve optimal device performance. The most common methodology to introduce these chromophores involves ligand exchange procedures. Despite their ubiquitous nature, ligand exchanges suffer from a few limitations, which include reversible binding, restricted access to binding sites, and the need for purification of the samples, which can result in loss of colloidal stability. Herein, we propose a methodology to bypass these inherent issues of ligand exchange through the growth of an amorphous alumina shell by colloidal atomic layer deposition (c-ALD). We demonstrate that c-ALD creates colloidally stable composite materials, which comprise NCs and organic chromophores as photoactive ligands, by trapping the chromophores around the NC core. As representative examples, we functionalize semiconductor NCs, which include PbS, CsPbBr3, CuInS2, Cu2-xX, and lanthanide-based upconverting NCs, with polyaromatic hydrocarbons (PAH) ligands. Finally, we prove that triplet energy transfer occurs through the shell and we realize the assembly of a triplet exciton funnel structure, which cannot be obtained via conventional ligand exchange procedures. The formation of these organic/inorganic hybrid shells promises to synergistically boost catalytic and multiexcitonic processes while endowing enhanced stability to the NC core.

Alloying as a Strategy to Boost the Stability of Copper Nanocatalysts during the Electrochemical CO2 Reduction Reaction.

Copper nanocatalysts are among the most promising candidates to drive the electrochemical CO2 reduction reaction (CO2RR). However, the stability of such catalysts during operation is sub-optimal, and improving this aspect of catalyst behavior remains a challenge. Here, we synthesize well-defined and tunable CuGa nanoparticles (NPs) and demonstrate that alloying Cu with Ga considerably improves the stability of the nanocatalysts. In particular, we discover that CuGa NPs containing 17 at. % Ga preserve most of their CO2RR activity for at least 20 h while Cu NPs of the same size reconstruct and lose their CO2RR activity within 2 h. Various characterization techniques, including X-ray photoelectron spectroscopy and operando X-ray absorption spectroscopy, suggest that the addition of Ga suppresses Cu oxidation at open-circuit potential (ocp) and induces significant electronic interactions between Ga and Cu. Thus, we explain the observed stabilization of the Cu by Ga as a result of the higher oxophilicity and lower electronegativity of Ga, which reduce the propensity of Cu to oxidize at ocp and enhance the bond strength in the alloyed nanocatalysts. In addition to addressing one of the major challenges in CO2RR, this study proposes a strategy to generate NPs that are stable under a reducing reaction environment.

The spatial distribution of cobalt phthalocyanine and copper nanocubes controls the selectivity towards C2 products in tandem electrocatalytic CO2 reduction.

The coupling of CO-generating molecular catalysts with copper electrodes in tandem schemes is a promising strategy to boost the formation of multi-carbon products in the electrocatalytic reduction of CO2. While the spatial distribution of the two components is important, this aspect remains underexplored for molecular-based tandem systems. Herein, we address this knowledge gap by studying tandem catalysts comprising Co-phthalocyanine (CoPc) and Cu nanocubes (Cucub). In particular, we identify the importance of the relative spatial distribution of the two components on the performance of the tandem catalyst by preparing CoPc-Cucub/C, wherein the CoPc and Cucub share an interface, and CoPc-C/Cucub, wherein the CoPc is loaded first on carbon black (C) before mixing with the Cucub. The electrocatalytic measurements of these two catalysts show that the faradaic efficiency towards C2 products almost doubles for the CoPc-Cucub/C, whereas it decreases by half for the CoPc-C/Cucub, compared to the Cucub/C. Our results highlight the importance of a direct contact between the CO-generating molecular catalyst and the Cu to promote C-C coupling, which hints at a surface transport mechanism of the CO intermediate between the two components of the tandem catalyst instead of a transfer via CO diffusion in the electrolyte followed by re-adsorption.

Tandem electrocatalytic CO2 reduction with Fe-porphyrins and Cu nanocubes enhances ethylene production.

Copper-based tandem schemes have emerged as promising strategies to promote the formation of multi-carbon products in the electrocatalytic CO2 reduction reaction. In such approaches, the CO-generating component of the tandem catalyst increases the local concentration of CO and thereby enhances the intrinsic carbon-carbon (C-C) coupling on copper. However, the optimal characteristics of the CO-generating catalyst for maximizing the C2 production are currently unknown. In this work, we developed tunable tandem catalysts comprising iron porphyrin (Fe-Por), as the CO-generating component, and Cu nanocubes (Cucub) to understand how the turnover frequency for CO (TOFCO) of the molecular catalysts impacts the C-C coupling on the Cu surface. First, we tuned the TOFCO of the Fe-Por by varying the number of orbitals involved in the π-system. Then, we coupled these molecular catalysts with the Cucub and assessed the current densities and faradaic efficiencies. We discovered that all of the designed Fe-Por boost ethylene production. The most efficient Cucub/Fe-Por tandem catalyst was the one including the Fe-Por with the highest TOFCO and exhibited a nearly 22-fold increase in the ethylene selectivity and 100 mV positive shift of the onset potential with respect to the pristine Cucub. These results reveal that coupling the TOFCO tunability of molecular catalysts with copper nanocatalysts opens up new possibilities towards the development of Cu-based catalysts with enhanced selectivity for multi-carbon product generation at low overpotential.

Tailoring Morphology and Elemental Distribution of Cu-In Nanocrystals via Galvanic Replacement.

The compositional and structural diversity of bimetallic nanocrystals (NCs) provides a superior tunability of their physico-chemical properties, making them attractive for a variety of applications, including sensing and catalysis. Nevertheless, the manipulation of the properties-determining features of bimetallic NCs still remains a challenge, especially when moving away from noble metals. In this work, we explore the galvanic replacement reaction (GRR) of In NCs and a copper molecular precursor to obtain Cu-In bimetallic NCs with an unprecedented variety of morphologies and distribution of the two metals. We obtain spherical Cu11In9 intermetallic and patchy phase-segregated Cu-In NCs, as well as dimer-like Cu-Cu11In9 and Cu-In NCs. In particular, we find that segregation of the two metals occurs as the GRR progresses with time or with a higher copper precursor concentration. We discover size-dependent reaction kinetics, with the smaller In NCs undergoing a slower transition across the different Cu-In configurations. We compare the obtained results with the bulk Cu-In phase diagram and, interestingly, find that the bigger In NCs stabilize the bulk-like Cu-Cu11In9 configuration before their complete segregation into Cu-In NCs. Finally, we also prove the utility of the new family of Cu-In NCs as model catalysts to elucidate the impact of the metal elemental distribution on the selectivity of these bimetallics toward the electrochemical CO2 reduction reaction. Generally, we demonstrate that the GRR is a powerful synthetic approach beyond noble metal-containing bimetallic structures, yet that the current knowledge on this reaction is challenged when oxophilic and poorly miscible metal pairs are used.

Copper Phosphonate Lamella Intermediates Control the Shape of Colloidal Copper Nanocrystals.

Understanding the structure and behavior of intermediates in chemical reactions is the key to developing greater control over the reaction outcome. This principle is particularly important in the synthesis of metal nanocrystals (NCs), where the reduction, nucleation, and growth of the reaction intermediates will determine the final size and shape of the product. The shape of metal NCs plays a major role in determining their catalytic, photochemical, and electronic properties and, thus, the potential applications of the material. In this work, we demonstrate that layered coordination polymers, called lamellae, are reaction intermediates in Cu NC synthesis. Importantly, we discover that the lamella structure can be fine-tuned using organic ligands of different lengths and that these structural changes control the shape of the final NC. Specifically, we show that short-chain phosphonate ligands generate lamellae that are stable enough at the reaction temperature to facilitate the growth of Cu nuclei into anisotropic Cu NCs, being primarily triangular plates. In contrast, lamellae formed from long-chain ligands lose their structure and form spherical Cu NCs. The synthetic approach presented here provides a versatile tool for the future development of metal NCs, including other anisotropic structures.

The Native Oxide Skin of Liquid Metal Ga Nanoparticles Prevents Their Rapid Coalescence during Electrocatalysis.

Liquid metals (LMs) have been used in electrochemistry since the 19th century, but it is only recently that they have emerged as electrocatalysts with unique properties, such as inherent resistance to coke poisoning, which derives from the dynamic nature of their surface. The use of LM nanoparticles (NPs) as electrocatalysts is highly desirable to enhance any surface-related phenomena. However, LM NPs are expected to rapidly coalesce, similarly to liquid drops, which makes their implementation in electrocatalysis hard to envision. Herein, we demonstrate that liquid Ga NPs (18 nm, 26 nm, 39 nm) drive the electrochemical CO2 reduction reaction (CO2RR) while remaining well-separated from each other. CO is generated with a maximum faradaic efficiency of around 30% at -0.7 VRHE, which is similar to that of bulk Ga. The combination of electrochemical, microscopic, and spectroscopic techniques, including operando X-ray absorption, indicates that the native oxide skin of the Ga NPs is still present during CO2RR and provides a barrier to coalescence during operation. This discovery provides an avenue for future development of Ga-based LM NPs as a new class of electrocatalysts.

Colloidal-ALD-Grown Hybrid Shells Nucleate via a Ligand-Precursor Complex.

Colloidal atomic layer deposition (c-ALD) enables the growth of hybrid organic-inorganic oxide shells with tunable thickness at the nanometer scale around ligand-functionalized inorganic nanoparticles (NPs). This recently developed method has demonstrated improved stability of NPs and of their dispersions, a key requirement for their application. Nevertheless, the mechanism by which the inorganic shells form is still unknown, as is the nature of multiple complex interfaces between the NPs, the organic ligands functionalizing the surface, and the shell. Here, we demonstrate that carboxylate ligands are the key element that enables the synthesis of these core-shell structures. Dynamic nuclear polarization surface-enhanced nuclear magnetic resonance spectroscopy (DNP SENS) in combination with density functional theory (DFT) structure calculations shows that the addition of the aluminum organometallic precursor forms a ligand-precursor complex that interacts with the NP surface. This ligand-precursor complex is the first step for the nucleation of the shell and enables its further growth.

Shaping Copper Nanocatalysts to Steer Selectivity in the Electrochemical CO2 Reduction Reaction.

The carbon-neutral production of fuels and chemical feedstocks is one of the grand challenges for our society to solve. The electrochemical conversion of CO2 is emerging as a promising technology contributing to this goal. Despite the huge amount of progress made over the past decade, selectivity still remains a challenge. This Account presents an overview of recent progress in the design of selective catalysts by exploiting the structural sensitivity of the electrochemical CO2 reduction reaction (CO2RR). In particular, it shows that the accurate and precise control of the shape and size of Cu nanocatalysts is instrumental in understanding and in discovering the structure-selectivity relationships governing the reduction of CO2 to valuable hydrocarbons, such as methane and ethylene. It further illustrates the use of faceted Cu nanocatalysts to interrogate catalytic pathways and to increase selectivity toward oxygenates, such as ethanol, in the framework of tandem schemes. The last part of the Account highlights the role of well-defined nanocatalysts in identifying reconstruction mechanisms which might occur during operation. An outlook for the emerging paradigms which will empower the design of novel catalysts for CO2RR concludes the Account.

Investigation of Ethylene and Propylene Production from CO2 Reduction over Copper Nanocubes in an MEA-Type Electrolyzer.

Previous work carried out in fully liquid environments and at low current densities has demonstrated that highly uniform faceted copper nanocrystals display different selectivity profiles in CO2 reduction compared to polycrystalline copper. As part of ongoing upscaling efforts, it is a matter of interest to investigate whether the high selectivity toward ethylene of copper nanocubes, which show a preferential (100) orientation, is maintained in gas-fed electrolyzers, thus enabling the energy-efficient production of this valuable commodity chemical at industrially relevant current densities. In this work, we assessed the electrochemical CO2 reduction reaction performance of highly uniform copper nanocubes loaded onto gas diffusion electrodes (GDEs) in a zero-gap device. The copper nanocube-loaded GDEs maintained high Faradaic efficiencies toward ethylene at elevated total current densities, resulting in higher overall partial current densities toward this product compared to benchmark electrodes. Interestingly, CO2 reduction to propylene, albeit with low partial current densities, was also observed. However, double-layer capacitance measurements revealed that the performance observed at high current densities is significantly influenced by electrode flooding. The findings of this study can inform future efforts geared toward optimizing the electrodes with this promising class of catalysts.

Modulating the Reactivity of Liquid Ga Nanoparticle Inks by Modifying Their Surface Chemistry.

Micro- and nanosized particles of liquid metals, particularly Ga-based alloys, are attracting increasing attention for applications in several fields. The surface functionalization of Ga-based nanoparticles (NPs) with organic ligands renders easily processable inks. However, little is known about the interaction of these molecules with the native oxide skin, which regulates many properties of liquid metal NPs. Here, we investigate the impact of selected capping ligands on the native oxide thickness of Ga NPs and on their chemical reactivity, choosing the galvanic replacement reaction (GRR) as one example. We demonstrate that amines and carboxylic acids promote thicker oxide shells while thiols and phosphines hinder the oxide growth. Upon pondering thermodynamics and kinetics factors, we conclude the affinity of the anchoring group toward the metal core being the major driver in determining the oxide thickness. We go on to prove that thicker shells foster the formation of Cu-Ga nanodimers following the reaction of the Ga NPs with a copper-amine complex. In contrast, thinner oxides lead to formation of isolated Cu NPs. This study reveals the importance of the choice of ligand when studying Ga-based metal NPs for different applications since both their surface chemistry and reactivity are largely affected by this decision.

Crystal-Phase Control of Ternary Metal Oxides by Solid-State Synthesis with Nanocrystals.

Ternary metal oxides are materials of interest for many applications, from batteries to catalysis. Their crystalline structure and composition determine their properties, and thus it is important to achieve control over these features. Here, we demonstrate that solid-state chemistry among nanocrystalline precursors is a promising approach for their synthesis. We show that the crystalline phase of nanocrystal precursors direct that of the ternary reaction product. The combination of X-ray and electron microscopy techniques reveals that the spinel and rhombohedral phases of copper iron oxide are obtained by reacting copper nanocrystals with spinel γ-Fe2O3 and corundum α-Fe2O3 nanocrystals, respectively. Considering the available library of nanocrystals with tunable crystal phases, this discovery opens up an alternative pathway toward the synthesis of a wide variety of ternary and quaternary materials, including those with metastable phases.

Elucidating the structure-dependent selectivity of CuZn towards methane and ethanol in CO2 electroreduction using tailored Cu/ZnO precatalysts.

Understanding the catalyst compositional and structural features that control selectivity is of uttermost importance to target desired products in chemical reactions. In this joint experimental-computational work, we leverage tailored Cu/ZnO precatalysts as a material platform to identify the intrinsic features of methane-producing and ethanol-producing CuZn catalysts in the electrochemical CO2 reduction reaction (CO2RR). Specifically, we find that Cu@ZnO nanocrystals, where a central Cu domain is decorated with ZnO domains, and ZnO@Cu nanocrystals, where a central ZnO domain is decorated with Cu domains, evolve into Cu@CuZn core@shell catalysts that are selective for methane (∼52%) and ethanol (∼39%), respectively. Operando X-ray absorption spectroscopy and various microscopy methods evidence that a higher degree of surface alloying along with a higher concentration of metallic Zn improve the ethanol selectivity. Density functional theory explains that the combination of electronic and tandem effects accounts for such selectivity. These findings mark a step ahead towards understanding structure-property relationships in bimetallic catalysts for the CO2RR and their rational tuning to increase selectivity towards target products, especially alcohols.

Developing the Chemistry of Colloidal Cu Nanocrystals to Advance the CO2 Electrochemical Reduction.

The ability to tailor make materials with atomic scale precision is crucial for understanding the sensitivities of their performance parameters and for achieving the design specification corresponding to optimal device operation. Herein, this topic is discussed in the context of catalysis. The electrochemical CO2 reduction reaction (CO2 RR) holds the promise to close the carbon cycle by storing renewable energies in chemical feedstocks, yet it suffers from the lack of efficient and selective catalysts. This article highlights how colloidal chemistry can contribute to tackle this compelling issue by designing shape-controlled nanocatalysts. In particular, two case studies relative to copper nanocrystals are discussed.

Ligand Locking on Quantum Dot Surfaces via a Mild Reactive Surface Treatment.

At the outermost surface of colloidal QDs are organic surface ligands which dynamically bind and release in solution to control the growth kinetics, control the size/shape of the crystals, passivate surface states, and provide colloidal stability through favorable interactions with the solvent. However, the dynamicity comes at the expense of the stability of the QD suspension. Here, we show that ligands can be permanently locked on the QD surface by a thin layer of an inert metal oxide which forms within the ligand shell, over the headgroup. By interrogating the surface chemistry with different spectroscopic methods, we prove the ligand locking on the QD surface. As a result, an exceptional stability of the coated QD inks is achieved in a wide concentration range, even in the presence of chemically competing surface ligands in solution. We anticipate that this critical breakthrough will benefit different areas related to colloidal QDs, spanning from single-particle studies to displays and solar cells and biological applications. Furthermore, the same chemistry could be easily translated to surface treatments of bulk materials and thin films.