Richard T. Haasch

Robust carbon dioxide reduction on molybdenum disulphide edges

Electrochemical reduction of carbon dioxide has been recognized as an efficient way to convert carbon dioxide to energy-rich products. Noble metals (for example, gold and silver) have been demonstrated to reduce carbon dioxide at moderate rates and low overpotentials. Nevertheless, the development of inexpensive systems with an efficient carbon dioxide reduction capability remains a challenge. Here we identify molybdenum disulphide as a promising cost-effective substitute for noble metal catalysts. We uncover that molybdenum disulphide shows superior carbon dioxide reduction performance compared with the noble metals with a high current density and low overpotential (54 mV) in an ionic liquid. Scanning transmission electron microscopy analysis and first principle modelling reveal that the molybdenum-terminated edges of molybdenum disulphide are mainly responsible for its catalytic performance due to their metallic character and a high d-electron density. This is further experimentally supported by the carbon dioxide reduction performance of vertically aligned molybdenum disulphide.

Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid

Small and salty CO2 reduction scheme Most artificial photosynthesis approaches focus on making hydrogen. Modifying CO2, as plants and microbes do, is more chemically complex. Asadi et al. report that fashioning WSe2 and related electrochemical catalysts into nanometer-scale flakes greatly improves their activity for the reduction of CO2 to CO. An ionic liquid reaction medium further enhances efficiency. An artificial leaf with WSe2 reduced CO2 on one side while a cobalt catalyst oxidized water on the other side. Science, this issue p. 467 Nanostructuring tungsten diselenide enhances catalytic activity for carbon dioxide conversion to carbon monoxide in an ionic liquid medium. Conversion of carbon dioxide (CO2) into fuels is an attractive solution to many energy and environmental challenges. However, the chemical inertness of CO2 renders many electrochemical and photochemical conversion processes inefficient. We report a transition metal dichalcogenide nanoarchitecture for catalytic electrochemical CO2 conversion to carbon monoxide (CO) in an ionic liquid. We found that tungsten diselenide nanoflakes show a current density of 18.95 milliamperes per square centimeter, CO faradaic efficiency of 24%, and CO formation turnover frequency of 0.28 per second at a low overpotential of 54 millivolts. We also applied this catalyst in a light-harvesting artificial leaf platform that concurrently oxidized water in the absence of any external potential.

Electroreduction of Carbon Dioxide to Hydrocarbons Using Bimetallic Cu–Pd Catalysts with Different Mixing Patterns

Electrochemical conversion of CO2 holds promise for utilization of CO2 as a carbon feedstock and for storage of intermittent renewable energy. Presently Cu is the only metallic electrocatalyst known to reduce CO2 to appreciable amounts of hydrocarbons, but often a wide range of products such as CO, HCOO-, and H2 are formed as well. Better catalysts that exhibit high activity and especially high selectivity for specific products are needed. Here a range of bimetallic Cu-Pd catalysts with ordered, disordered, and phase-separated atomic arrangements (Cuat:Pdat = 1:1), as well as two additional disordered arrangements (Cu3Pd and CuPd3 with Cuat:Pdat = 3:1 and 1:3), are studied to determine key factors needed to achieve high selectivity for C1 or C2 chemicals in CO2 reduction. When compared with the disordered and phase-separated CuPd catalysts, the ordered CuPd catalyst exhibits the highest selectivity for C1 products (>80%). The phase-separated CuPd and Cu3Pd achieve higher selectivity (>60%) for C2 chemicals than CuPd3 and ordered CuPd, which suggests that the probability of dimerization of C1 intermediates is higher on surfaces with neighboring Cu atoms. Based on surface valence band spectra, geometric effects rather than electronic effects seem to be key in determining the selectivity of bimetallic Cu-Pd catalysts. These results imply that selectivities to different products can be tuned by geometric arrangements. This insight may benefit the design of catalytic surfaces that further improve activity and selectivity for CO2 reduction.

Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts

The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

Annealing free, clean graphene transfer using alternative polymer scaffolds

We examine the transfer of graphene grown by chemical vapor deposition (CVD) with polymer scaffolds of poly(methyl methacrylate) (PMMA), poly(lactic acid) (PLA), poly(phthalaldehyde) (PPA), and poly(bisphenol A carbonate) (PC). We find that optimally reactive PC scaffolds provide the cleanest graphene transfers without any annealing, after extensive comparison with optical microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Comparatively, films transferred with PLA, PPA, PMMA/PC, and PMMA have a two-fold higher roughness and a five-fold higher chemical doping. Using PC scaffolds, we demonstrate the clean transfer of CVD multilayer graphene, fluorinated graphene, and hexagonal boron nitride. Our annealing free, PC transfers enable the use of atomically-clean nanomaterials in biomolecule encapsulation and flexible electronic applications.

Chemical sensors based on randomly stacked graphene flakes

We demonstrate a simple fabrication method to produce randomly stacked graphene chemiresistors using surfactant-assisted exfoliation of graphite. We analyze the sensitivity of such chemiresistors as a function of vacuum filtration volume and temperature. At low vacuum filtration volumes (<∼5 mL) the sensors exhibit superior sensitivity towards target molecules compared to previously developed polycrystalline graphene, polycrystalline graphene microribbon, and carbon nanotube chemical sensors. Temperature dependent measurements, transmission electron microscopy and scanning electron microscopy suggest the improved sensitivity in the randomly stacked graphene chemiresistors is due to 2-dimensional charge carrier hopping through edge defects.

Doping-Induced Tunable Wettability and Adhesion of Graphene.

We report that substrate doping-induced charge carrier density modulation leads to the tunable wettability and adhesion of graphene. Graphenes water contact angle changes by as much as 13° as a result of a 300 meV change in doping level. Upon either n- or p-type doping with subsurface polyelectrolytes, graphene exhibits increased hydrophilicity. Adhesion force measurements using a hydrophobic self-assembled monolayer-coated atomic force microscopy probe reveal enhanced attraction toward undoped graphene, consistent with wettability modulation. This doping-induced wettability modulation is also achieved via a lateral metal-graphene heterojunction or subsurface metal doping. Combined first-principles and atomistic calculations show that doping modulates the binding energy between water and graphene and thus increases its hydrophilicity. Our study suggests that the doping-induced modulation of the charge carrier density in graphene influences its wettability and adhesion [corrected]. This opens up unique and new opportunities for the tunable wettability and adhesion of graphene for advanced coating materials and transducers.

Alkanetelluroxide-protected gold nanoparticles.

The synthesis and characterization of the first air-stable tellurium-containing ligand-protected gold nanoparticles (NPs) are reported. Although the synthesis largely followed the well-known Brust two-phase approach, the starting ligand was dioctyl ditelluride rather than alkanetellurol, which is an analogue of the widely used alkanethiol. Dioctyl ditelluride was used because alkanetellurol is unstable. The 1H and 13C NMR spectra, as well as infrared spectra (IR) of the formed Au NPs, indicated that the Te-Te bond in the starting ligand was broken but the octyl group was intact. This was further corroborated by the solid-state 125Te NMR spectrum that displayed a very broad and significantly downfield-shifted peak, indicating that tellurium was directly bound to the Au core. Furthermore, the O 1s and Te 3d XPS spectra of the Au NPs indicated that the capping ligands were octanetelluroxide. An average particle size of 2.7 nm diameter as measured by transmission electron microscopy (TEM) corresponded to an Au607 core. A two-step weight loss of approximately 22.2% in total was observed in the thermogravimetric analysis, which indicated about 53% ligand monolayer coverage (i.e., Au607(Te(=O)C8H17)133). Additionally, dioctyl ditelluride demonstrated an intriguing reductive power that led to a more sophisticated chemistry of forming the air-stable octanetelluroxide-protected gold NPs. It has been found that (1) when the ratio of Au to Te was about 1.5 a colorless intermediate state similar to Au(I)-SR (the intermediate state widely accepted in the synthesis of thiolate-protected Au NPs) could be obtained and (2) this kind of intermediate state played a key role in the formation of stable Au NPs.

Characterization of the metal–insulator interface of field-effect chemical sensors

The metal-insulator interface of hydrogen-sensitive metal-insulator-semiconductor capacitors, with SiO2 as the insulator and Pt as the metal contact, was discussed. It was found that the difference ...

Sn-mediated Ge/Ge(001) growth by low-temperature molecular-beam epitaxy: Surface smoothening and enhanced epitaxial thickness

Fully strained single-crystal metastable Ge1−xSnx layers were grown on Ge(001) in order to probe the role of Sn dopant and alloy concentrations (CSn=1×1018cm−3to6.1at.%) on surface roughening pathways leading to epitaxial breakdown during low-temperature (155°C) molecular-beam epitaxy of compressively strained films. The addition of Sn was found to mediate Ge(001) surface morphological evolution through two competing pathways. At very low Sn concentrations (x≲0.02), the dominant effect is a Sn-induced enhancement in both the Ge surface diffusivity and the probability of interlayer mass transport. This, in turn, results in more efficient filling of interisland trenches, and thus delays epitaxial breakdown. In fact, breakdown is not observed at all for Sn concentrations in the doping regime, 1×1018⩽CSn<4.4×1020cm−3 (2.3×10−5⩽x<0.010)! At higher concentrations, there is a change in Ge1−xSnx(001) growth kinetics due to a rapid increase in the amount of compressive strain. This leads to a gradual reduction in ...