Browsing by Author "Tilley, Richard D."

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    Cascade Reactions in Nanozymes: Spatially Separated Active Sites inside Ag-Core−Porous-Cu-Shell Nanoparticles for Multistep Carbon Dioxide Reduction to Higher Organic Molecules
    (Journal of the American Chemical Society, 2019) O’Mara, Peter B.; Wilde, Patrick; Benedetti, Tania M.; Andrones, Corina; Cheong, Soshan; Gooding, Justin; Tilley, Richard D.; Schuhmann, Wolfgang
    Enzymes can perform complex multistep cascade reactions by linking multiple distinct catalytic sites via substrate channeling. We mimic this feature in a generalized approach with an electrocatalytic nanoparticle for the carbon dioxide reduction reaction comprising a Ag core surrounded by a porous Cu shell, providing different active sites in nanoconfined volumes. The architecture of the nanozyme provides the basis for a cascade reaction, which promotes C−C coupling reactions. The first step occurs on the Ag core, and the subsequent steps on the porous copper shell, where a sufficiently high CO concentration due to the nanoconfinement facilitates C−C bond formation. The architecture yields the formation of n-propanol and propionaldehyde at potentials as low as −0.6 V vs RHE.
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    Colloidal silicon quantum dots: from preparation to the modification of self-assembled monolayers for bioimaging and sensing applications
    (Biomedical Applications, 2017) Cheng, Xiaoyu; McVey, Benjamin F.P.; Robinson, Andrew B.; Longatte, Guillaume; O’Mara, Peter B.; Tan, Vincent T. G.; Thordarson, Pall; Tilley, Richard D.; Gaus, Katharina; Gooding, Justin
    In this paper we present recent advances in Förster resonance energy transfer (FRET) sensing and bioimaging using nontoxic silicon quantum dots. (SiQDs) In our work, we prepare SiQDs-dye conjugates, with SiQDs serving as the donor which are covalently attached to organic dye acceptors via self-assembled monolayer linkers. Enzymatic cleavage of the peptide leads to changes in FRET response which was monitored using fluorescence lifetime imaging microscopy (FLIM-FRET). The combination of interfacial design and optical imaging presented in this work opens new opportunities for bio-applications using nontoxic silicon quantum dots.
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    Combining Nanoconfinement in Ag Core/Porous Cu Shell Nanoparticles with Gas Diffusion Electrodes for Improved Electrocatalytic Carbon Dioxide Reduction
    (ChemElectroChem, 2021) Junqueira, João R. C.; O’Mara, Peter B.; Wilde, Patrick; Dieckhöfer, Stefan; Benedetti, Tania M.; Andronescu, Corina; Tilley, Richard D.; Gooding, J. Justin; Schuhmann, Wolfgang
    Bimetallic silver-copper electrocatalysts are promising materials for electrochemical CO2 reduction reaction (CO2RR) to fuels and multi-carbon molecules. Here, we combine Ag core/porous Cu shell particles, which entrap reaction intermediates and thus facilitate the formation of C2+ products at low overpotentials, with gas diffusion electrodes (GDE). Mass transport plays a crucial role in the product selectivity in CO2RR. Conventional Hcell configurations suffer from limited CO2 diffusion to the reaction zone, thus decreasing the rate of the CO2RR. In contrast, in the case of GDE-based cells, the CO2RR takes place under enhanced mass transport conditions. Hence, investigation of the Ag core/porous Cu shell particles at the same potentials under different mass transport regimes reveals: (i) a variation of product distribution including C3 products, and (ii) a significant change in the local OH- activity under operation.
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    Is Cu instability during the CO2 reduction reaction governed by the applied potential or the local CO concentration?
    (Chemical science, 2021) Wilde, Patrick; O'Mara, Peter B.; Junqueira, Joao R. C.; Tarnev, Tsvetan; Benedetti, Tania M.; Andronescu, Corina; Chen, Yen-Ting; Tilley, Richard D.; Schuhmann, Wolfgang; Gooding, J. Justin
    have shown structural instability during the electrochemical CO2 reduction reaction (CO2RR). However, studies on monometallic Cu catalysts do not allow a nuanced differentiation between the contribution of the applied potential and the local concentration of CO as the reaction intermediate since both are inevitably linked. We first use bimetallic Ag-core/porous Cu-shell nanoparticles, which utilise nanoconfinement to generate high local CO concentrations at the Ag core at potentials at w
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    Role of the Secondary Metal in Ordered and Disordered Pt−M Intermetallic Nanoparticles: An Example of Pt3Sn Nanocubes for the Electrocatalytic Methanol Oxidation
    (ACS Catalysis, 2021) Chen, Hsiang-Sheng; Benedetti, Tania M.; Lian, Jiaxin; Cheong, Soshan; O’Mara, Peter B.; Sulaiman, Kazeem O.; Kelly, Cameron H. W.; Cameron, H. W. Kelly,; Robert, W. J.; Justin Gooding, Scott, J.; Tilley, Richard D.
    When comparing alloy catalysts with different degrees of ordering, it is important to maintain surface facets to understand the effect of different arrangements of surface atoms. This is even more important when both metals are involved in the reaction steps, which is the case of Pt3Sn for the methanol oxidation reaction (MOR). We have prepared 95 and 60% ordered Pt3Sn nanocubes with {100} facets for the MOR. We show that the Sn atoms in the 60% ordered Pt3Sn nanocubes can be electrochemically oxidized to Sn4+, whereas the Sn atoms in the 95% ordered Pt3Sn nanocubes are more resistant to oxidation. The Sn4+ in the disordered catalysts makes them more active than the ordered catalysts. At low overpotentials, the electrochemically formed Sn4+ in the 60% ordered Pt3Sn nanocubes bind OH, oxidizing the CO intermediate adsorbed on Pt more efficiently. At high overpotentials, Sn4+ prevents the passivation of the Pt sites due to adsorption of OH. These effects lead to a 5.6 times higher activity of the 60% ordered nanocubes compared to the 95% ordered nanocubes. These results illustrate the importance in catalyst design of controlling the environment and especially the atoms neighboring Pt for intermetallic Pt−M electrocatalysts.