Selective reduction of CO to acetaldehyde with CuAg electrocatalysts.

Electrochemical CO reduction can serve as a sequential step in the transformation of CO2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of -0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.

Engineering Cu surfaces for the electrocatalytic conversion of CO2: Controlling selectivity toward oxygenates and hydrocarbons.

In this study we control the surface structure of Cu thin-film catalysts to probe the relationship between active sites and catalytic activity for the electroreduction of CO2 to fuels and chemicals. Here, we report physical vapor deposition of Cu thin films on large-format (∼6 cm2) single-crystal substrates, and confirm epitaxial growth in the <100>, <111>, and <751> orientations using X-ray pole figures. To understand the relationship between the bulk and surface structures, in situ electrochemical scanning tunneling microscopy was conducted on Cu(100), (111), and (751) thin films. The studies revealed that Cu(100) and (111) have surface adlattices that are identical to the bulk structure, and that Cu(751) has a heterogeneous kinked surface with (110) terraces that is closely related to the bulk structure. Electrochemical CO2 reduction testing showed that whereas both Cu(100) and (751) thin films are more active and selective for C-C coupling than Cu(111), Cu(751) is the most selective for >2e- oxygenate formation at low overpotentials. Our results demonstrate that epitaxy can be used to grow single-crystal analogous materials as large-format electrodes that provide insights on controlling electrocatalytic activity and selectivity for this reaction.

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts.

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2 R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2 R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO2 R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.

Biologically inspired highly durable iron phthalocyanine catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells.

In the present work, we have designed and synthesized a new highly durable iron phtalocyanine based nonprecious oxygen reduction reaction (ORR) catalyst (Fe-SPc) for polymer electrolyte membrane fuel cells (PEMFCs). The Fe-SPc, with a novel structure inspired by that of naturally occurring oxygen activation catalysts, is prepared by a nonpyrolyzing method, allowing adequate control of the atomic structure and surface properties of the material. Significantly improved ORR stability of the Fe-SPc is observed compared with the commercial Fe-Pc catalysts. The Fe-SPc has similar activity to that of the commercial Fe-Pc initially, while the Fe-SPc displays 4.6 times higher current density than that of the commercial Fe-Pc after 10 sweep potential cycles, and a current density that is 7.4 times higher after 100 cycles. This has been attributed to the incorporation of electron-donating functional groups, along with a high degree of steric hindrance maintaining active site isolation. Nonprecious Fe-SPc is promising as a potential alternative ORR electrocatalyst for PEMFCs.

A Spin Coating Method To Deposit Iridium-Based Catalysts onto Silicon for Water Oxidation Photoanodes.

Silicon has shown promise for use as a small band gap (1.1 eV) absorber material in photoelectrochemical (PEC) water splitting. However, the limited stability of silicon in acidic electrolyte requires the use of protection strategies coupled with catalysts. Herein, spin coating is used as a versatile method to directly coat silicon photoanodes with an IrOx oxygen evolution reaction (OER) catalyst, reducing the processing complexity compared to conventional fabrication schemes. Biphasic strontium chloride/iridium oxide (SrCl2:IrOx) catalysts are also developed, and both catalysts form photoactive junctions with silicon and demonstrate high photoanode activity. The iridium oxide photoanode displays a photocurrent onset at 1.06 V vs reversible hydrogen electrode (RHE), while the SrCl2:IrOx photoanode onsets earlier at 0.96 V vs RHE. The differing potentials are consistent with the observed photovoltages of 0.43 and 0.53 V for the IrOx and SrCl2:IrOx, respectively. By measuring the oxidation of a reversible redox couple, Fe(CN)63-/4-, we compare the charge carrier extraction of the devices and show that the addition of SrCl2 to the IrOx catalyst improves the silicon-electrolyte interface compared to pure IrOx. However, the durability of the strontium-containing photoanode remains a challenge, with its photocurrent density decreasing by 90% over 4 h. The IrOx photoanode, on the other hand, maintained a stable photocurrent density over this timescale. Characterization of the as-prepared and post-tested material structure via Auger electron spectroscopy identifies catalyst film cracking and delamination as the primary failure modes. We propose that improvements to catalyst adhesion should further the viability of spin coating as a technique for photoanode preparation.

In Situ Polymer Graphenization Ingrained with Nanoporosity in a Nitrogenous Electrocatalyst Boosting the Performance of Polymer-Electrolyte-Membrane Fuel Cells.

Rich, porous graphene frameworks decorated with uniformly dispersed active sites are prepared by using polyaniline as a graphene precursor and introducing phenanthroline as a pore-forming agent. The unprecedented fuel-cell performance of this electrocatalyst is linked to the graphene frameworks with vast distribution of pore sizes, which maximizes the active-sites accessibility, facilitates mass-transport properties, and improves the carbon corrosion resistance.

Controlled growth of platinum nanowire arrays on sulfur doped graphene as high performance electrocatalyst.

Graphene supported Pt nanostructures have great potential to be used as catalysts in electrochemical energy conversion and storage technologies; however the simultaneous control of Pt morphology and dispersion, along with ideally tailoring the physical properties of the catalyst support properties has proven very challenging. Using sulfur doped graphene (SG) as a support material, the heterogeneous dopant atoms could serve as nucleation sites allowing for the preparation of SG supported Pt nanowire arrays with ultra-thin diameters (2-5 nm) and dense surface coverage. Detailed investigation of the preparation technique reveals that the structure of the resulting composite could be readily controlled by fine tuning the Pt nanowire nucleation and growth reaction kinetics and the Pt-support interactions, whereby a mechanistic platinum nanowire array growth model is proposed. Electrochemical characterization demonstrates that the composite materials have 2-3 times higher catalytic activities toward the oxygen reduction and methanol oxidation reaction compared with commercial Pt/C catalyst.