Person:

Lattimer, Judith

A highly modular synthesis of designed catalysts with controlled bimetallic nanoparticle size and composition and a well-defined structural hierarchy is demonstrated. Exemplary catalysts—bimetallic dilute Ag-in-Au nanoparticles partially embedded in a porous SiO2 matrix (SiO2-AgxAuy)—were synthesized by the decoration of polymeric colloids with the bimetallic nanoparticles followed by assembly into a colloidal crystal backfilled with the matrix precursor and subsequent removal of the polymeric template. We show that these new catalysts architectures are significantly better than nanoporous dilute AgAu alloy catalysts (nanoporous Ag0.03Au0.97) while retaining a clear predictive relationship between their surface reactivity with that of single crystal Au surfaces. This paves the way for broadening the range of new catalyst architectures required for translating the designed principles developed under controlled conditions to designed catalysts under operating conditions for highly selective coupling of alcohols to form esters. Excellent catalytic performance of the porous SiO2-AgxAuy structure for selective oxidation of both methanol and ethanol to produce esters with high conversion efficiency, selectivity, and stability was demonstrated, illustrating the ability to translate design principles developed for support-free materials to the colloid-templated structures. The synthetic methodology reported is customizable for the design of a wide range of robust catalytic systems inspired by design principles derived from model studies. Fine control over the composition, morphology, size, distribution and availability of the supported nanoparticles was demonstrated.

Utilizing solar energy to fix carbon dioxide (CO2) with water into chemical fuels and oxygen, a mimic process of photosynthesis in nature, is becoming increasingly important but still challenged by the low selectivity and activity, especially in CO2 electrocatalytic reduction. Here we report transition metal atoms coordinated in graphene shell as active centers for aqueous CO2 reduction to carbon monoxide (CO), with high Faradaic efficiencies over 90 % under significant currents up to ~ 60 mA/mg (12 mA/cm2). Three-dimensional atom probe tomography was employed to directly identify the single Ni atomic sites in graphene vacancies. Theoretical simulations suggest that compared to metallic Ni, the Ni atomic sites present significantly different electronic structures which facilitate CO2 to CO conversion and suppress the competing hydrogen evolution reaction dramatically.