Synthesis gas (CO + H2) conversion is a promising route to converting coal, natural gas, or biomass into synthetic liquid fuels. Rhodium has long been studied as it is the only elemental catalyst that has demonstrated selectivity to ethanol and other C2+ oxygenates. However, the fundamentals of syngas conversion over rhodium are still debated. In this work a microkinetic model is developed for conversion of CO and H2 into methane, ethanol, and acetaldehyde on the Rh (211) and (111) surfaces, chosen to describe steps and close-packed facets on catalyst particles. The model is based on DFT calculations using the BEEF-vdW functional. The mean-field kinetic model includes lateral adsorbate-adsorbate interactions, and the BEEF-vdW error estimation ensemble is used to propagate error from the DFT calculations to the predicted rates. The model shows the Rh(211) surface to be ∼6 orders of magnitude more active than the Rh(111) surface, but highly selective toward methane, while the Rh(111) surface is intrinsically selective toward acetaldehyde. A variety of Rh/SiO2 catalysts are synthesized, tested for catalytic oxygenate production, and characterized using TEM. The experimental results indicate that the Rh(111) surface is intrinsically selective toward acetaldehyde, and a strong inverse correlation between catalytic activity and oxygenate selectivity is observed. Furthermore, iron impurities are shown to play a key role in modulating the selectivity of Rh/SiO2 catalysts toward ethanol. The experimental observations are consistent with the structure-sensitivity predicted from theory. This work provides an improved atomic-scale understanding and new insight into the mechanism, active site, and intrinsic selectivity of syngas conversion over rhodium catalysts and may also guide rational design of alloy catalysts made from more abundant elements.
Atomic layer deposition (ALD) provides a promising route for depositing uniform thin coatings of electrocatalysts useful in many technologies, including the splitting of water. For materials such as NiO x that readily form hydrous oxides, however, the smooth, compact films deposited by ALD may result in higher overpotentials due to low catalyst surface area compared to other deposition methods. Here, the use of ALD–NiO thin films as oxygen evolution reaction (OER) electrocatalysts is explored. Thin films of crystalline ALD–NiO are deposited and OER activity is tested using cyclic voltammetry (CV). Fe incorporated from the electrolyte can increase the activity of NiO, and it is shown that the turnover frequency (TOF) increases tenfold by going from an Fe‐poor to Fe‐rich KOH electrolyte. Applying a potential exfoliates the NiO, increasing the number of electrochemically accessible Ni sites. Interestingly, by X‐ray photoelectron spectroscopy (XPS) and CV, it is found that an Fe‐rich electrolyte reduces the amount of restructuring and oxidation is found. It is shown that a high surface area, high TOF catalyst may be created by using a two‐step process in which the sample is sequentially conditioned in Fe‐poor then Fe‐rich KOH. This work highlights the importance of pretreatment on catalytic activity for compact NiO films deposited by ALD.
A new generation of catalysts is needed to meet society's energy and resource requirements. Current catalyst synthesis does not fully achieve optimum control of composition, size, and structure. Atomic layer deposition (ALD) is an emerging technique that allows for synthesis of highly controlled catalysts in the form of films, nanoparticles, and single sites. The addition of ALD coatings can also be used to introduce promoters and improve the stability of traditional catalysts. Evolving research shows promise for applying ALD to understand catalytically active sites and create next-generation catalysts using advanced 3D nanostructures.
Rhodium (Rh) catalysts are among the major candidates for syngas conversion to higher oxygenates (C2+oxy), with manganese (Mn) as a commonly used promoter for enhancing the activity and selectivity toward C2+oxy. In this study, we use atomic layer deposition (ALD) to controllably modify Rh catalysts with MnO, by depositing manganese oxide as a support layer or an overlayer, in order to identify the function of the Mn promoter. We also compare the ALD-modified catalysts with those prepared by coimpregnation. An ultrathin MnO support layer shows the most effective enhancement for C2+oxy production. Transmission electron microscopy, temperature-programmed reduction, and diffuse reflectance infrared Fourier transform spectroscopy characterization indicates that formation of Rh–MnO interface sites is responsible for the observed activity and selectivity improvements, while ruling out Rh nanoparticle size and alloy or mixed oxide formation as significant contributors. MnO overlayers on Rh appear to suffer from poor stability upon CO adsorption and are less effective than a MnO support layer. Density functional theory (DFT) calculations show that MnO species on the Rh(111) surface lower the transition state energy for CO bond dissociation and stabilize the key transition state for C2+oxy synthesis more significantly than that for methane synthesis, leading to enhanced activity and C2+oxy selectivity.
Colloidal quantum dots (CQDs) have received recent attention for low cost, solution processable, high efficiency solid-state photovoltaic devices due to the possibility of tailoring their optoelectronic properties by tuning size, composition, and surface chemistry. However, the device performance is limited by the diffusion length of charge carriers due to recombination. In this work, we show that band engineering of PbS QDs is achievable by changing the dipole moment of the passivating ligand molecules surrounding the QD. The valence band maximum and conduction band minimum of PbS QDs passivated with three different thiophenol ligands (4-nitrothiophenol, 4-fluorothiophenol, and 4-methylthiophenol) are determined by UV–visible absorption spectroscopy and photoelectron spectroscopy in air (PESA), and the experimental results are compared with DFT calculations. These band-engineered QDs have been used to fabricate heterojunction solar cells in both unidirectional and bidirectional configurations. The results show that proper band alignment can improve the directionality of charge carrier collection to benefit the photovoltaic performance.
Rh-based catalysts have shown promise for the direct conversion of syngas to higher oxygenates. Although improvements in higher oxygenate yield have been achieved by combining Rh with metal oxide promoters, details of the structure of the promoted catalyst and the role of the promoter in enhancing catalytic performance are not well understood. In this work, we show that MoO 3 -promoted Rh nanoparticles form a novel catalyst structure in which Mo substitutes into the Rh surface, leading to both a 66-fold increase in turnover frequency and an enhancement in oxygenate yield. By applying a combination of atomically controlled synthesis, in situ characterization, and theoretical calculations, we gain an understanding of the promoter-Rh interactions that govern catalytic performance for MoO 3 -promoted Rh. We use atomic layer deposition to modify Rh nanoparticles with monolayer-precise amounts of MoO 3 , with a high degree of control over the structure of the catalyst. Through in situ X-ray absorption spectroscopy, we find that the atomic structure of the catalytic surface under reaction conditions consists of Mo−OH species substituted into the surface of the Rh nanoparticles. Using density functional theory calculations, we identify two roles of MoO 3 : first, the presence of Mo−OH in the catalyst surface enhances CO dissociation and also stabilizes a methanol synthesis pathway not present in the unpromoted catalyst; and second, hydrogen spillover from Mo−OH sites to adsorbed species on the Rh surface enhances hydrogenation rates of reaction intermediates.
The production of liquid fuels and industrial feedstocks from renewable carbon sources is an ongoing scientific challenge. Using atomic layer deposition together with conventional techniques, we synthesize Pt−Co bimetallic catalysts that show improvement for syngas conversion to alcohols. By combining reaction testing, X-ray diffraction, electron microscopy, and in situ infrared spectroscopy experiments, supported by density functional theory calculations, we uncover insights into how Pt modulates the selectivity of Co catalysts. The prepared Pt− Co catalysts demonstrate increased selectivity toward methanol and low molecular weight hydrocarbons as well as a modest increase in selectivity toward higher alcohols. The in situ infrared spectroscopic measurements suggest that these changes in selectivity result from an interplay between linear and bridging carbon monoxide configurations on the catalyst surface.
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