Recently, a large number of nanostructured metal-containing materials have been developed for the electrochemical CO 2 reduction reaction (eCO 2 RR). However, it remains a challenge to achieve high activity and selectivity with respect to the metal load due to the limited concentration of surface metal atoms. Here, it is reported that the bismuth-based metal-organic framework Bi(1,3,5-tris(4-carboxyphenyl)benzene), herein denoted Bi(btb), works as a precatalyst and undergoes a structural rearrangement at reducing potentials to form highly active and selective catalytic Bi-based nanoparticles dispersed in a porous organic matrix. The structural change is investigated by electron microscopy, X-ray diffraction, total scattering, and spectroscopic techniques. Due to the periodic arrangement of Bi cations in highly porous Bi(btb), the in situ formed Bi nanoparticles are well-dispersed and hence highly exposed for surface catalytic reactions. As a result, high selectivity over a broad potential range in the eCO 2 RR toward formate production with a Faradaic efficiency up to 95(3)% is achieved. Moreover, a large current density with respect to the Bi load, i.e., a mass activity, up to 261(13) A g −1 is achieved, thereby outperforming most other nanostructured Bi materials.
Metal borides, a class of materials intensively used in industry as superconductors, magnetic materials, or hot cathodes, remain largely unexplored at the nanoscale mainly due to the difficulty in synthesizing single-phase nanocrystals. Recent works have shown that synthetic methods at lower temperatures (<400 °C) yield amorphous polydisperse nanoparticles, while phase purity is an issue at higher temperatures. Among all the metal-rich borides, nickel borides (Ni x B) could be a potential catalyst for a broad range of applications (hydrogenations, electrochemical hydrogen, and oxygen evolution reactions) under challenging conditions (such as high pH or high temperatures). Here, we report a novel solid-state method to synthesize Ni x B nanopowders (with a diameter of approximately 45 nm) and their conversion into colloidal suspensions (inks) through treatment of the nanocrystal surface. For the solid-state synthesis, we used commercially available salts and explored the reaction between the Ni and B sources while varying the synthetic parameters under mild and solvent-free reaction conditions. We show that pure phase Ni3B and Ni2B NCs can be obtained with high yield in the pure phase using as precursors NiCl2 and Ni, respectively. Through extensive mechanistic studies, we show that Ni nanoclusters (1–2 nm) are an intermediate in the boriding process, while the metal co-reactant lowers the decomposition temperature of NaBH4 (used as a reducing agent and B source). Size control can instead be exerted through reaction mediators, as seen from the differential nucleation and growth of Ni (clusters) or Ni x B NCs when employing L- (amine, phosphine) and X-type (carboxylate) mediators. Applying surface engineering methods to our Ni x B NCs, we stabilized them with inorganic (NOBF4) or organic (borane tert-butyl amine, oleylamine) ligands in the appropriate solvent (DMSO, hexane). With this method, we produce stable inks for further solution processing applications. Our results provide tools for further development of catalysts based on Ni x B NCs and pave the way for synthesizing other metal boride colloidal nanostructures.
An optical sensor based on the localized surface plasmon resonance (LSPR) of chiral Au nanohooks with increased refractive index (RI) sensitivity via circular dichroism (CD) measurements is presented. Programmed control of sample rotation combined with angled physical vapor deposition is applied to hole-mask colloidal lithography to provide in process modification of the hole-masks and generate arrays of chiral nanostructures with an adjustable optical response. Extinction spectra with unpolarized light as well as circular dichroism measurements are compared for left- and right-handed hook structures. Analysis of the LSPR peak shift of the substrate-attached nanostructures revealed the CD measurements to be twice as sensitive as the measurements with unpolarized light (304 and 146 nm RIU–1, respectively) and close to the maximum predicted for LSPR sensing at this spectral region (∼700 nm). Finite-difference time-domain simulations with different substrate materials show that the difference in RI sensitivity can be attributed to the limiting effect of the substrate for the unpolarized extinction measurements, while CD-based sensing retains a high sensitivity, unaffected by the limiting effect of the substrate. CD-based readout could provide a complementary and improved sensitivity for substrate-bound LSPR sensor formats.
Oxidative chemical vapor deposition (oCVD) is an extremely effective method for solvent-free deposition of highly conductive polypyrrole films, where polymer synthesis, doping, and film formation are combined in a single...
We report a cost-effective, straightforward synthesis of a novel electrocatalyst for the reduction of CO2 to formate, which achieves nearly complete Faradaic Efficiency (FE) at an overpotential () of 0.88...
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