Particle size effects in the catalytic electroreduction of CO2 on Cu nanoparticles.

A study of particle size effects during the catalytic CO2 electroreduction on size-controlled Cu nanoparticles (NPs) is presented. Cu NP catalysts in the 2-15 nm mean size range were prepared, and their catalytic activity and selectivity during CO2 electroreduction were analyzed and compared to a bulk Cu electrode. A dramatic increase in the catalytic activity and selectivity for H2 and CO was observed with decreasing Cu particle size, in particular, for NPs below 5 nm. Hydrocarbon (methane and ethylene) selectivity was increasingly suppressed for nanoscale Cu surfaces. The size dependence of the surface atomic coordination of model spherical Cu particles was used to rationalize the experimental results. Changes in the population of low-coordinated surface sites and their stronger chemisorption were linked to surging H2 and CO selectivities, higher catalytic activity, and smaller hydrocarbon selectivity. The presented activity-selectivity-size relations provide novel insights in the CO2 electroreduction reaction on nanoscale surfaces. Our smallest nanoparticles (~2 nm) enter the ab initio computationally accessible size regime, and therefore, the results obtained lend themselves well to density functional theory (DFT) evaluation and reaction mechanism verification.

Exceptional size-dependent activity enhancement in the electroreduction of CO2 over Au nanoparticles.

The electrocatalytic reduction of CO2 to industrial chemicals and fuels is a promising pathway to sustainable electrical energy storage and to an artificial carbon cycle, but it is currently hindered by the low energy efficiency and low activity displayed by traditional electrode materials. We report here the size-dependent catalytic activity of micelle-synthesized Au nanoparticles (NPs) in the size range of ∼1-8 nm for the electroreduction of CO2 to CO in 0.1 M KHCO3. A drastic increase in current density was observed with decreasing NP size, along with a decrease in Faradaic selectivity toward CO. Density functional theory calculations showed that these trends are related to the increase in the number of low-coordinated sites on small NPs, which favor the evolution of H2 over CO2 reduction to CO. We show here that the H2/CO product ratio can be specifically tailored for different industrial processes by tuning the size of the catalyst particles.

Quantification of photocatalytic hydrogen evolution.

A new photoreactor with defined irradiation geometry was developed and tested for the water reduction reaction using carbon nitride ("C(3)N(4)") as a photocatalyst. The hydrogen evolution rate was investigated with a sun simulator (I = 1000 W m(-2)) in two different operation modes: circulation and stirring of the catalyst dispersion. Only in the stirred mode, where shear stress is lower, a stable hydrogen evolution rate of about 0.41 L m(-2) h(-1) is obtained. It is confirmed by experiments with D(2)O that hydrogen is obtained from the water splitting process and not by dehydrogenation of the sacrificial agent. The obtained rate results in an efficiency of <0.1% based on a reference experiment with a photovoltaic-powered electrolysis setup. The change from distilled water to tap or simulated sea water results in a lower hydrogen evolution rate of about 50%.