Accelerated size-focusing light activated synthesis of atomically precise fluorescent Au(Lys-Cys-Lys) clusters.

Atomically precise metal nanoclusters are promising candidates for various biomedical applications, including their use as photosensitizers in photodynamic therapy (PDT). However, typical synthetic routes of clusters often result in complex mixtures, where isolating and characterizing pure samples becomes challenging. In this work, a new Au(Lys-Cys-Lys) cluster is synthesized using photochemistry, followed by a new type of light activated, accelerated size-focusing.

Solar Hydrocarbons: Single-Step, Atmospheric-Pressure Synthesis of C -C Alkanes and Alkenes from CO.

Cobalt ferrite (CoFe O ) spinel has been found to produce C -C hydrocarbons in a single-step, ambient-pressure, photocatalytic hydrogenation of CO with a rate of 1.1 mmol g  h , selectivity of 29.8 % and conversion yield of 12.

Engineered disorder in CO photocatalysis.

Light harvesting, separation of charge carriers, and surface reactions are three fundamental steps that are essential for an efficient photocatalyst. Here we show that these steps in the TiO can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO forms a core-shell c-TiO@a-TiO(OH) heterostructure, comprised of HO-Ti-[O]-Ti surface frustrated Lewis pairs (SFLPs) embedded in an amorphous shell surrounding a crystalline core, which enables a new genre of chemical reactivity.

New black indium oxide-tandem photothermal CO-H methanol selective catalyst.

It has long been known that the thermal catalyst Cu/ZnO/AlO(CZA) can enable remarkable catalytic performance towards CO hydrogenation for the reverse water-gas shift (RWGS) and methanol synthesis reactions. However, owing to the direct competition between these reactions, high pressure and high hydrogen concentration (≥75%) are required to shift the thermodynamic equilibrium towards methanol synthesis. Herein, a new black indium oxide with photothermal catalytic activity is successfully prepared, and it facilitates a tandem synthesis of methanol at a low hydrogen concentration (50%) and ambient pressure by directly using by-product CO as feedstock.

Bismuth atom tailoring of indium oxide surface frustrated Lewis pairs boosts heterogeneous CO photocatalytic hydrogenation.

The surface frustrated Lewis pairs (SFLPs) on defect-laden metal oxides provide catalytic sites to activate H and CO molecules and enable efficient gas-phase CO photocatalysis. Lattice engineering of metal oxides provides a useful strategy to tailor the reactivity of SFLPs. Herein, a one-step solvothermal synthesis is developed that enables isomorphic replacement of Lewis acidic site In ions in InO by single-site Bi ions, thereby enhancing the propensity to activate CO molecules.

Plasmonic Titanium Nitride Facilitates Indium Oxide CO Photocatalysis.

Nanoscale titanium nitride TiN is a metallic material that can effectively harvest sunlight over a broad spectral range and produce high local temperatures via the photothermal effect. Nanoscale indium oxide-hydroxide, In O (OH) , is a semiconducting material capable of photocatalyzing the hydrogenation of gaseous CO ; however, its wide electronic bandgap limits its absorption of photons to the ultraviolet region of the solar spectrum. Herein, the benefits of both nanomaterials in a ternary heterostructure: TiN@TiO @In O (OH) are combined.

High-performance light-driven heterogeneous CO catalysis with near-unity selectivity on metal phosphides.

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO hydrogenation. Selected as an archetype, NiP affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range.

Flash Solid-Solid Synthesis of Silicon Oxide Nanorods.

1D silicon-based nanomaterials, renowned for their unique chemical and physical properties, have enabled the development of numerous advanced materials and biomedical technologies. Their production often necessitates complex and expensive equipment, requires hazardous precursors and demanding experimental conditions, and involves lengthy processes. Herein, a flash solid-solid (FSS) process is presented for the synthesis of silicon oxide nanorods completed within seconds.

Black indium oxide a photothermal CO hydrogenation catalyst.

Nanostructured forms of stoichiometric InO are proving to be efficacious catalysts for the gas-phase hydrogenation of CO. These conversions can be facilitated using either heat or light; however, until now, the limited optical absorption intensity evidenced by the pale-yellow color of InO has prevented the use of both together. To take advantage of the heat and light content of solar energy, it would be advantageous to make indium oxide black.

The next big thing for silicon nanostructures - CO photocatalysis.

Silicene is a relatively new member of the growing family of two-dimensional single-element materials. Both top-down and bottom-up approaches provide access to silicene, the former via vapor deposition on a substrate and the latter via exfoliation of the layered CaSi2 precursor. Most top-down research has been concerned with understanding the various electronic, optical, magnetic, mechanical, electrical, thermal transport and gas-adsorption properties of silicene.

Building a Bridge from Papermaking to Solar Fuels.

Black liquor, an industrial waste product of papermaking, is primarily used as a low-grade combustible energy source. Despite its high lignin content, the potential utility of black liquor as a feedstock in products manufacturing, remains to be exploited. Demonstrated here in is the use of black liquor as a primary feed-stock for synthesizing graphene quantum dots that exhibit both up-conversion and photoluminescence when excited using visible/near-infrared radiation, thereby enabling the photosensitization of ultraviolet-absorbing TiO nanosheets.

Fundamentals and applications of photocatalytic CO methanation.

The extraction and combustion of fossil natural gas, consisting primarily of methane, generates vast amounts of greenhouse gases that contribute to climate change. However, as a result of recent research efforts, "solar methane" can now be produced through the photocatalytic conversion of carbon dioxide and water to methane and oxygen. This approach could play an integral role in realizing a sustainable energy economy by closing the carbon cycle and enabling the efficient storage and transportation of intermittent solar energy within the chemical bonds of methane molecules.

Nickel@Siloxene catalytic nanosheets for high-performance CO methanation.

Two-dimensional (2D) materials are of considerable interest for catalyzing the heterogeneous conversion of CO to synthetic fuels. In this regard, 2D siloxene nanosheets, have escaped thorough exploration, despite being composed of earth-abundant elements. Herein we demonstrate the remarkable catalytic activity, selectivity, and stability of a nickel@siloxene nanocomposite; it is found that this promising catalytic performance is highly sensitive to the location of the nickel component, being on either the interior or the exterior of adjacent siloxene nanosheets.

Towards Solar Methanol: Past, Present, and Future.

This work aims to provide an overview of producing value-added products affordably and sustainably from greenhouse gases (GHGs). Methanol (MeOH) is one such product, and is one of the most widely used chemicals, employed as a feedstock for ≈30% of industrial chemicals. The starting materials are analogous to those feeding natural processes: water, CO, and light.

Golden single-atomic-site platinum electrocatalysts.

Bimetallic nanoparticles with tailored structures constitute a desirable model system for catalysts, as crucial factors such as geometric and electronic effects can be readily controlled by tailoring the structure and alloy bonding of the catalytic site. Here we report a facile colloidal method to prepare a series of platinum-gold (PtAu) nanoparticles with tailored surface structures and particle diameters on the order of 7 nm. Samples with low Pt content, particularly PtAu, exhibited unprecedented electrocatalytic activity for the oxidation of formic acid.

Tailoring Surface Frustrated Lewis Pairs of InO (OH) for Gas-Phase Heterogeneous Photocatalytic Reduction of CO by Isomorphous Substitution of In with Bi.

Frustrated Lewis pairs (FLPs) created by sterically hindered Lewis acids and Lewis bases have shown their capacity for capturing and reacting with a variety of small molecules, including H and CO, and thereby creating a new strategy for CO reduction. Here, the photocatalytic CO reduction behavior of defect-laden indium oxide (InO (OH) ) is greatly enhanced through isomorphous substitution of In with Bi, providing fundamental insights into the catalytically active surface FLPs (i.e.

Fe Stabilization by Intermetallic L1-FePt and Pt Catalysis Enhancement in L1-FePt/Pt Nanoparticles for Efficient Oxygen Reduction Reaction in Fuel Cells.

We report in this article a detailed study on how to stabilize a first-row transition metal (M) in an intermetallic L1-MPt alloy nanoparticle (NP) structure and how to surround the L1-MPt with an atomic layer of Pt to enhance the electrocatalysis of Pt for oxygen reduction reaction (ORR) in fuel cell operation conditions. Using 8 nm FePt NPs as an example, we demonstrate that Fe can be stabilized more efficiently in a core/shell structured L1-FePt/Pt with a 5 Å Pt shell. The presence of Fe in the alloy core induces the desired compression of the thin Pt shell, especially the two atomic layers of Pt shell, further improving the ORR catalysis.

Promoting Effect of Ni(OH) on Palladium Nanocrystals Leads to Greatly Improved Operation Durability for Electrocatalytic Ethanol Oxidation in Alkaline Solution.

Most electrocatalysts for the ethanol oxidation reaction suffer from extremely limited operational durability and poor selectivity toward the CC bond cleavage. In spite of tremendous efforts over the past several decades, little progress has been made in this regard. This study reports the remarkable promoting effect of Ni(OH) on Pd nanocrystals for electrocatalytic ethanol oxidation reaction in alkaline solution.

Pd Nanoparticles Coupled to WO Nanorods for Enhanced Electrochemical Oxidation of Formic Acid.

We synthesize a new type of hybrid Pd/WO structure with 5 nm Pd nanoparticles (NPs) anchored on 50 × 5 nm WO nanorods. The strong Pd/WO coupling results in the lattice expansion of Pd from 0.23 to 0.

Ultrasmall and phase-pure WC nanoparticles for efficient electrocatalytic and photoelectrochemical hydrogen evolution.

Earlier research has been primarily focused on WC as one of the most promising earth-abundant electrocatalysts for hydrogen evolution reaction (HER), whereas the other compound in this carbide family-WC-has received far less attention. Our theoretical calculations suggest that such a focus is misplaced and WC is potentially more HER-active than WC. Nevertheless, the preparation of phase pure and sintering-free WC nanostructures represents a formidable challenge.

Luminescent Gold Nanoparticles with Size-Independent Emission.

Size-independent emission has been widely observed for ultrasmall thiolated gold nanoparticles (AuNPs) but our understanding of the photoluminescence mechanisms of noble metals on the nanoscale has remained limited. Herein, we report how the emission wavelength of a AuNP and the local binding geometry of a thiolate ligand (glutathione) on the AuNP are correlated, as these AuNPs emit at different wavelengths in spite of their identical size (ca. 2.

A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature.

Coordinatively unsaturated (CUS) iron sites are highly active in catalytic oxidation reactions; however, maintaining the CUS structure of iron during heterogeneous catalytic reactions is a great challenge. Here, we report a strategy to stabilize single-atom CUS iron sites by embedding highly dispersed FeN4 centers in the graphene matrix. The atomic structure of FeN4 centers in graphene was revealed for the first time by combining high-resolution transmission electron microscopy/high-angle annular dark-field scanning transmission electron microscopy with low-temperature scanning tunneling microscopy.

Highly active and durable methanol oxidation electrocatalyst based on the synergy of platinum-nickel hydroxide-graphene.

Active and durable electrocatalysts for methanol oxidation reaction are of critical importance to the commercial viability of direct methanol fuel cell technology. Unfortunately, current methanol oxidation electrocatalysts fall far short of expectations and suffer from rapid activity degradation. Here we report platinum-nickel hydroxide-graphene ternary hybrids as a possible solution to this long-standing issue.