Showing papers by "Christopher J. Kiely published in 2018"

Unravelling structure sensitivity in CO 2 hydrogenation over nickel

Abstract: Continuous efforts in the field of materials science have allowed us to generate smaller and smaller metal nanoparticles, creating new opportunities to understand catalytic properties that depend on the metal particle size. Structure sensitivity is the phenomenon where not all surface atoms in a supported metal catalyst have the same activity. Understanding structure sensitivity can assist in the rational design of catalysts, allowing control over mechanisms, activity and selectivity, and thus even the viability of a catalytic reaction. Here, using a unique set of well-defined silica-supported Ni nanoclusters (1–7 nm) and advanced characterization methods, we prove how structure sensitivity influences the mechanism of catalytic CO2 reduction, the nature of which has been long debated. These findings bring fundamental new understanding of CO2 hydrogenation over Ni and allow us to control both activity and selectivity, which can be a means for CO2 emission abatement through its valorization as a low- or even negative-cost feedstock on a low-cost transition-metal catalyst.

Elucidating the role of CO2 in the soft oxidative dehydrogenation of propane over ceria-based catalysts

Abstract: A mixed oxide support containing Ce, Zr, and Al was synthesized using a physical grinding method and applied in the oxidative dehydrogenation of propane using CO2 as the oxidant. The activity of the support was compared with that of fully formulated catalysts containing palladium. The Pd/CeZrAlOx material exhibited long-term stability and selectivity to propene (during continuous operation for 140 h), which is not normally associated with dehydrogenation catalysts. From temperature-programmed desorption of NH3 and CO2 it was found that the catalyst possessed both acidic and basic sites. In addition, temperature-programmed reduction showed that palladium promoted both the reduction and reoxidation of the support. When the role of CO2 was investigated in the absence of gas-phase oxidant, using a temporal analysis of products (TAP) reactor, it was found that CO2 dissociates over the reduced catalyst, leading to formation of CO and selective oxygen species. It is proposed that CO2 has the dual role of regener...

Deactivation of a Single-Site Gold-on-Carbon Acetylene Hydrochlorination Catalyst: An X-ray Absorption and Inelastic Neutron Scattering Study

Abstract: Single-site Au species supported on carbon have been shown to be the active sites for acetylene hydrochlorination. The evolution of these single-site species has been monitored by Au L3 X-ray Absorption Spectroscopy (XAS). Alternating between a standard reaction mixture of HCl/C2H2 and the single reactants, has provided insights into the reaction mechanism and catalyst deactivation processes. We demonstrate that oxidative addition of HCl across an Au(I) chloride species requires concerted addition with C2H2, in accordance with both the XAS measurements of Au oxidation state and the reaction kinetics being 1st order with respect to each reactant. The addition of excess C2H2 changes the Au speciation and results in the formation of oligomeric acetylene species which were detected by inelastic neutron scattering. Catalyst deactivation at extended reaction times can be correlated with the formation of metallic Au particles. The presence of this Au(0) species generated during the sequential gas experiments or after prolonged reaction times, results in the analysis of the normalised near edge white line intensity of the Au L3 X-ray absorption spectrum alone becoming an unsuitable guide for identifying the active Au species, affecting the strong correlation between normalized white line height and VCM productivity usually observed in the active catalyst. Thus, a combination of scanning transmission electron microscopy and detailed modelling of whole XAS spectrum was required to distinguish active Au(I) and Au(III) species from the spectator Au(0) component.

Ambient temperature aqueous synthesis of ultrasmall copper doped ceria nanocrystals for the water gas shift and carbon monoxide oxidation reactions

Abstract: Ceria substitutionally doped with copper is a promising heterogeneous catalyst for a range of oxidation reactions. Herein we describe the aqueous phase, scalable, and direct precipitation of CuxCe1−xO2−δ (x = 0–0.35) solid solution oxide nanocrystals at room temperature without the need for calcination at elevated temperatures. This direct precipitation of the crystalline oxide is enabled through ligand exchange prior to pH adjustment to prevent the precipitation of the hydroxide phase. By producing particles at room temperature, dopant exsolution and particle growth by sintering can be minimized and/or controlled. Using our methodology, copper dopant concentrations of up to 35 mol% could be produced in 1.7 nm diameter ceria nanocrystals. The resulting materials showed high catalytic activity towards both the water gas shift reaction (WGS) and CO oxidation, with improved performance following the trend of increasing copper content. In comparison to pure ceria nanocrystals, the WGS activation energy decreased from 89.0 to 49.2 kJ mol−1 and the CO oxidation light-off temperature decreased from 262 to 159 °C at a space velocity of 25 000 h−1 upon doping with 35 mol% copper.

The Role of Copper Speciation in the Low Temperature Oxidative Upgrading of Short Chain Alkanes over Cu/ZSM-5 Catalysts.

Abstract: Partial oxidative upgrading of C1–C3 alkanes over Cu/ZSM‐5 catalysts prepared by chemical vapour impregnation (CVI) has been studied. The undoped ZSM‐5 support is itself able to catalyse selective oxidations, for example, methane to methanol, using mild reaction conditions and the green oxidant H2O2. Addition of Cu suppresses secondary oxidation reactions, affording methanol selectivities of up to 97 %. Characterisation studies attribute this ability to population of specific Cu sites below the level of total exchange (Cu/Al<0.5). These species also show activity for radical‐based methane oxidation, with productivities exceeding those of the parent zeolite supports. When tested for ethane and propane oxidation reactions, comparable trends are observed

Improving the selectivity of photocatalytic NOx abatement through improved O2 reduction pathways using Ti0.909W0.091O2Nx semiconductor nanoparticles: from characterisation to photocatalytic performance

Abstract: In this paper, we provide detailed insight into the electronic–crystallographic–structural relationship for Ti0.909W0.091O2Nx semiconductor nanoparticles, explaining the mutual electronic and magnetic influence of the photoinduced stable N- and W-based paramagnetic centers, their involvement in the photoinduced charge-carrier trapping, and their role in improving the nitrate selectivity of the photocatalytic oxidation of NOx to nitrates. In particular, reduced tungsten species in various crystallographic environments within the anatase host lattice were observed as playing a fundamental role in the storage and stabilization of photogenerated electrons. Here, we show how these reduced centers can catalyze multielectron transfer events without the need for rare and expensive platinum-group metals (PGMs). This allows for the versatile and elegant configuration of redox potentials. As a result, electron-transfer processes that are kinetically inaccessible with metal oxides such as TiO2 can now be accessed, en...

Homocoupling of phenylboronic acid using atomically dispersed gold on carbon catalysts: catalyst evolution before reaction

Abstract: Coupling reactions to form new C-C bonds are extensively used in industrial synthetic processes. Gold has been shown to be an active catalyst for such reactions however, conflicting reports exist as to whether cationic Au or metallic Au is acting as the active species. We prepared a heterogeneous catalyst consisting of atomically dispersed Au-Clx supported on carbon and showed this to be active in the homocoupling of phenylboronic acid to biphenyl. However; characterisation of the catalyst materials, even after just a short exposure time to the reactants, revealed rapid reduction and sintering of the Au species into larger metallic nanoparticles which we propose to be the true active species in this instance. This study suggests that if cationic Au is an active catalyst, it must be stabilised against reduction and agglomeration by either forming complexes which are more stable than common chlorides or by strongly anchoring them firmly onto alternative support materials; as in this case the carbon supported Au-Cl species were easily reduced.

Low temperature aqueous synthesis of size-controlled nanocrystals through size focusing: a quantum dot biomineralization case study.

Abstract: Traditional quantum dot synthesis techniques rely on the separation of nucleation and growth to control nanocrystal size. However, the same goal can be achieved through slow and continuous introduction of reactive precursors to keep the growth mechanism in the size focusing regime throughout synthesis. In this work, we demonstrate the efficacy of this approach within the framework of functional material biomineralization where, despite simultaneous nucleation and growth of particles, this growth mechanism enables size-controlled nanocrystal synthesis. Herein, the single enzyme cystathionine γ-lyase (CSE) is utilized to biomineralize CdS nanocrystals via the slow, but continuous turnover of the amino acid l-cysteine to produce H2S. Nanocrystal nucleation and growth theories confirm that consistent addition of monomers will result in a high supersaturation term, driving the nanocrystal growth mechanism into the size focusing regime. We further confirm this theory by mimicking biomineralization via chemical routes and demonstrate the influence of varying supersaturation, to further control the average nanocrystal size. Finally, altering the chelation strength of the capping agent l-cysteine is found to play a key role in balancing nanocrystal growth in solution and long-term stability.

Publisher Correction: Unravelling structure sensitivity in CO 2 hydrogenation over nickel

Abstract: In the version of this Article originally published online, in Fig. 2b, the y axis unit incorrectly included superscript –1 on Ni; it should have been just Ni. In the PDF only, in Fig. 2d–f, the label ‘Particle size (nm)’ was missing from the x axes. All of these corrections have now been made.