Localized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel‐cell‐relevant reaction. The electrocatalyst consists of PdxAg alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible‐light plasmonic response of Ag. The alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the PdxAg NTs.

The preparation of metal electrocatalysts with excellent comprehensive properties for application in alcohol fuel cells is an urgent issue. This study reports a novel 3D Au‐doped PtBi intermetallic phase woven by sub‐7 nm building blocks. The high‐efficiency “active auxiliary” Au advances the activity and in situ anti‐CO poisoning upon ethylene glycol electrooxidation on 3D PtBiAu, along with high CC bond cleavage and attainment of a ten‐electron complete electrooxidation via a CO‐free pathway. The interface‐rich 3D structure with “nanocontainer” function, electronic effect, and dual functional sites of “Pt–Au” or “Pt–Bi” enable the 3D PtBiAu to outperform industrial Pt black and 3D PtBi intermetallics significantly. The mass activity on the 3D Pt53.1Bi43.4Au3.5 intermetallics boosts to 28.72 A mgPt−1, higher than that reported in a previous study. The 3D Pt53.1Bi43.4Au3.5 exhibits superior performance to industrial Pt/C in direct ethylene glycol fuel cells (DEGFCs). The peak power density of 3D Pt53.1Bi43.4Au3.5 is 145/92 mW cm−2 in O2/air (80 °C). Importantly, the cell voltage shows a negligible decay in both O2 and air during the 20 h durability testing. This study results in the development of novel 3D PtBiAu intermetallics as high‐performance anode electrocatalysts for application in DEGFCs.

An homologous series of divinylchalcogenophene‐bridged binuclear ruthenium complexes [{(PMe3)3Cl(CO)Ru}2(µ‐CH=CH‐C4H2E‐CH=CH)] (4a–4d, E = O, S, Se, Te) have been synthesised and fully characterised by X‐ray crystallography and various spectroscopic techniques. The single‐crystal X‐ray diffraction results reveal a distinct short/long bond‐length alternation along the polyene‐like hydrocarbon backbone, with geometric constraints imposed by the chalcogenophene leading to an increasing distance between the two metal centres (dRu–Ru) in complexes 4a–4d as the heteroatom in the five‐membered ring is changed from oxygen (9.980 Å in 4a) to tellurium (11.063 Å in 4d). The complexes undergo two sequential one‐electron oxidation processes, the half‐wave potential and separation of which appear to be sensitive to a range of factors, including aromatic stabilisation and re‐organisation energies. Analysis of [4a–4d]n+ (n = 0, 1, 2) by UV/Vis/NIR and IR spectroelectrochemical methods, supported by DFT calculations (n = 0, 1), revealed that the redox character of the complexes is dominated by the polyene‐like backbone with the chalcogenide playing a subtle but influential, structural rather than electronic, role. In the radical cations [4a–4d]+, the charge is rather effectively delocalised over the 10‐atom Ru–[4‐s‐cis‐all‐trans‐(CH=CH)4]–Ru chain, giving rise to a species with spectroscopic properties not dissimilar to oxidised polyaceylene.