Paul N. Duchesne

Interfacial Effects in Iron-Nickel Hydroxide–Platinum Nanoparticles Enhance Catalytic Oxidation

Improving Reactions at Interfaces Alloying precious metals such as platinum with more abundant transition metals, such as iron and nickel, can both improve their catalytic reactivity and lower catalyst cost. Chen et al. (p. 495) explored using coatings of iron oxide–hydroxide layers on supported platinum nanoparticles for CO oxidation. The presence of this layer allowed the reaction to run rapidly at room temperature by bringing together different reaction sites on the two metals. The addition of nickel improved catalyst lifetime, and an oxidative transformation created a more complex nanoparticle morphology that increased platinum utilization. An alloy catalyst for room-temperature CO creates sites for O2 activation when the CO2 product is released. Hybrid metal nanoparticles can allow separate reaction steps to occur in close proximity at different metal sites and accelerate catalysis. We synthesized iron-nickel hydroxide–platinum (transition metal-OH-Pt) nanoparticles with diameters below 5 nanometers and showed that they are highly efficient for carbon monoxide (CO) oxidation catalysis at room temperature. We characterized the composition and structure of the transition metal–OH-Pt interface and showed that Ni2+ plays a key role in stabilizing the interface against dehydration. Density functional theory and isotope-labeling experiments revealed that the OH groups at the Fe3+-OH-Pt interfaces readily react with CO adsorbed nearby to directly yield carbon dioxide (CO2) and simultaneously produce coordinatively unsaturated Fe sites for O2 activation. The oxide-supported PtFeNi nanocatalyst rapidly and fully removed CO from humid air without decay in activity for 1 month.

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

A coordinatively unsaturated single iron site confined in a graphene matrix shows an ultrahigh activity for catalytic oxidation. 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. These confined single-atom iron sites exhibit high performance in the direct catalytic oxidation of benzene to phenol at room temperature, with a conversion of 23.4% and a yield of 18.7%, and can even proceed efficiently at 0°C with a phenol yield of 8.3% after 24 hours. Both experimental measurements and density functional theory calculations indicate that the formation of the Fe═O intermediate structure is a key step to promoting the conversion of benzene to phenol. These findings could pave the way toward highly efficient nonprecious catalysts for low-temperature oxidation reactions in heterogeneous catalysis and electrocatalysis.

Highly efficient, NiAu-catalyzed hydrogenolysis of lignin into phenolic chemicals

A highly efficient, stable NiAu catalyst that exhibits unprecedented low temperature activity in lignin hydrogenolysis was for the first time developed, leading to the formation of 14 wt% aromatic monomers from organosolv lignin at 170 °C in pure water.

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. The incorporation of highly defective nickel hydroxide nanostructures is believed to play the decisive role in promoting the dissociative adsorption of water molecules and subsequent oxidative removal of carbonaceous poison on neighbouring platinum sites. As a result, the ternary hybrids exhibit exceptional activity and durability towards efficient methanol oxidation reaction. Under periodic reactivations, the hybrids can endure at least 500,000 s with negligible activity loss, which is, to the best of our knowledge, two to three orders of magnitude longer than all available electrocatalysts.

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. 2.5 nm). By using circular dichroism, X-ray absorption, and fluorescence spectroscopy, we found that a high Au-S coordination number (CN) and a high surface coverage resulted in strong Au(I) -ligand charge transfer, a chiral conformation, and 600 nm emission, whereas a low Au-S CN and a low surface coverage led to weak charge transfer, an achiral conformation, and 810 nm emission. These two size-independent emissions can be integrated into one single 2.5 nm AuNP by fine-tuning of the surface coverage; a ratiometric pH response was then observed owing to strong energy transfer between two emission centers, opening up new possibilities for the design of ultrasmall ratiometric pH nanoindicators.

The surface structure of silver-coated gold nanocrystals and its influence on shape control

Understanding the surface structure of metal nanocrystals with specific facet indices is important due to its impact on controlling nanocrystal shape and functionality. However, this is particularly challenging for halide-adsorbed nanocrystals due to the difficulty in analysing interactions between metals and light halides (for example, chloride). Here we uncover the surface structures of chloride-adsorbed, silver-coated gold nanocrystals with {111}, {110}, {310} and {720} indexed facets by X-ray absorption spectroscopy and density functional theory modelling. The silver–chloride, silver–silver and silver–gold bonding structures are markedly different between the nanocrystal surfaces, and are sensitive to their formation mechanism and facet type. A unique approach of combining the density functional theory and experimental/simulated X-ray spectroscopy further verifies the surface structure models and identifies the previously indistinguishable valence state of silver atoms on the nanocrystal surfaces. Overall, this work elucidates the thus-far unknown chloride–metal nanocrystal surface structures and sheds light onto the halide-induced growth mechanism of anisotropic nanocrystals.

Local structure of fluorescent platinum nanoclusters

Fluorescent nanoclusters synthesized from a variety of noble metals have recently been reported in the scientific literature. Various characterization methods have been employed in their study, but uncertainty still remains regarding the local structure of such materials. Herein we present the results of employing X-ray absorption spectroscopy to probe the local structure and electronic properties of platinum nanoclusters reduced and stabilized using N,N-dimethylformamide. Most notable amongst these results is an apparent lack of metallic bonding in the samples studied; in light of these findings, it is proposed that a non-metallic platinum nanocluster is instead responsible for the observed fluorescence behaviour.

Pd Nanoparticles Coupled to WO2.72 Nanorods for Enhanced Electrochemical Oxidation of Formic Acid

We synthesize a new type of hybrid Pd/WO2.72 structure with 5 nm Pd nanoparticles (NPs) anchored on 50 × 5 nm WO2.72 nanorods. The strong Pd/WO2.72 coupling results in the lattice expansion of Pd from 0.23 to 0.27 nm and the decrease of Pd surface electron density. As a result, the Pd/WO2.72 shows much enhanced catalysis toward electrochemical oxidation of formic acid in 0.1 M HClO4; it has a mass activity of ∼1600 mA/mgPd in a broad potential range of 0.4-0.85 V (vs RHE) and shows no obvious activity loss after a 12 h chronoamperometry test at 0.4 V. Our work demonstrates an important strategy to enhance Pd NP catalyst efficiency for energy conversion reactions.

X-ray spectroscopy studies on the surface structural characteristics and electronic properties of platinum nanoparticles

The surface structural characteristics and electronic behavior of three platinum nanoparticle (NP) samples prepared with tertiary amine (Pt-TA), primary amine (Pt-PA), and thiol (Pt-SR) molecules were studied using Pt 4f, 5d, and S 2p x-ray photoelectron spectroscopy (XPS), Pt L(3)-edge x-ray absorption spectroscopy (XAS), and theoretical projected local density of states (l-DOS) calculations. Transmission electron microscopy and XPS composition analysis indicated that the three NPs were all very small (1-2 nm), the NP size decreasing in the order of Pt-TA>Pt-PA approximately Pt-SR. All the three samples showed a positive Pt 4f binding energy (BE) shift relative to that of the bulk, in the order of bulk<Pt-TA<Pt-PA<Pt-SR. The origin of the BE shift was elucidated by XAS and deconvolution of the Pt 4f XPS peak, indicating that the observed BE shifts were largely associated with the initial state effect (i.e., nanosize and surface structure). The surface and size effects on the electronic behavior of Pt were further studied by valence band XPS and the results were interpreted with calculated d-DOS of three Pt(55) model clusters with varied surface structures. Finally, the implication of these results on tuning the electronic properties of Pt NPs with size, surface, and alloying effects was discussed.

Gold nanoparticles on titanium and interaction with prototype protein.

Modifying titanium (Ti) implant surfaces with functional proteins can strengthen the interface between prosthesis and bone. A prototype system was developed using gold nanoparticles (AuNPs) to immobilize proteins onto Ti. An electroless (galvanic displacement) deposition method was first used to form AuNPs of controlled size and coverage on commercial Ti foil (giving Ti-AuNPs). Parameters were then modified to create two groups of discs (n = 26) with different average AuNP diameters. Scanning electron microscopy and X-ray photoelectron spectroscopy were used to characterize the morphology and surface structure of Ti-AuNPs. To study the interaction of Ti-AuNPs with proteins, Ti discs (n = 8) modified with plain AuNPs and discs (n = 8) modified with thiol (HS--R--COOH)-functionalized AuNPs were treated with lysozyme solution. The amount and activity of the lysozyme on the discs were examined with Micro-BCA and enzymatic assays. Lysozyme was immobilized onto the discs, and the assays showed that the discs with thiol-functionalized AuNPs, discs with bare AuNPs, and Ti controls had average lysozyme adsorptions of 23 x 10(4), 2.3 x 10(4), and 5.7 x 10(4) microg/m2, respectively. The activity assays showed that 21.5, 18.4, and 12.5% of the adsorbed lysozyme was active on the discs with thiol-functionalized AuNPs, discs with bare AuNPs, and Ti controls, respectively. This technique holds promise for binding functional biomolecules to surgical implants, hence possibly creating implant surfaces that react to their local environment.