Reactions on Inverse Model Catalyst Surfaces: Atomic Views by STM

Planar “inverse catalyst” model systems, i.e. noble metal single crystal surfaces decorated by oxide nanostructures, have been used to visualise surface processes in the STM with atomic level precision. The processes chosen for their prototypical relevance in heterogeneous catalysis systems comprise the oxidation-reduction of surface oxide phases, the effects of the metal-oxide phase boundary in promoting the CO oxidation reaction and the O₂+H₂ water reaction, and the mass transport processes of oxide materials over metal surfaces via the diffusion of oxide clusters.     

Fast and exergy efficient start-up of micro-solid oxide fuel cell systems by using the reformer or the post-combustor for start-up heating

The start-up process of a micro-solid oxide fuel cell system strongly influences its overall efficiency, especially for portable applications where a frequent switch-on and switch-off is required. We present herein a novel start-up process for such systems that exploits existing units, such as the post-combustor or the reformer, as a heat source to reach the operation temperature of the cell at 600 °C. Our experimental results show that the employment of platinum catalysts in the post-combustor or rhodium catalysts in the reformer for total oxidation of butane by air combined with an electrically heated wire led to a faster and more efficient start-up than conventional start-up methods using only electrical energy. By using the post-combustor as heat source, the start-up time could be reduced by 79% and the exergy cost by 86%. The latter includes the cost of the stand-alone fuel cell system to produce electrical energy for the joule heating of the wire (i.e. the system efficiency is accounted for). There are several advantages to use the reformer as heat source during start-up, such as prevention of coking of the fuel cell or improved heat transfer by internal heating of the other components. The start-up performance, however, was lower than that of the post-combustor: the start-up time could be reduced by 65% and the exergy cost by 68% compared to a conventional start-up.     

Indication of water in the coordination sphere of rhodium by conversions of 2,5-dimethoxy-2,5-dihydrofuran with syngas

2,5-Dimethoxy-2,5-dihydrofuran did not form the expected aldehydes when water-soluble rhodium-catalysts were used for the conversion with syngas. Instead of hydroformylation, hydrogenation was the main reaction path in water, where 2,5-dimethoxytetrahydrofuran and its hydrolysis product, succinic dialdehyde, were obtained. The formation of hydrogenation products indicates water in the coordination sphere of rhodium. This may provide us with information on the environment of an active metal in aggregated structures like micelles and vesicles which are gaining in importance in biphasic catalysis.     

Alkali-metal promoted rhodium-on-alumina catalysts for nitrous oxide decomposition

Catalytic activity of γ-alumina supported rhodium catalysts in nitrous oxide decomposition into dinitrogen and dioxygen has been determined, the total conversion being reached at 450 °C. Rhodium is present at alumina surface in three forms: metal particles, Rh₂O₃ and rhodium zero valent atoms interacting with oxygen ions at the metal/support interface. Linear dependence of the catalytic activity on rhodium dispersion has been found. Deposition of alkali metal cations: Li, Na, K and Cs as promoters at the surface of alumina results in a considerable increase of rhodium dispersion and hence catalytic activity. The effect of promoters depends strongly on the speciation of alkali metals and rhodium used in the preparation of the catalyst. Both alkali metal cations and rhodium compete for the same OH groups at the alumina surface. The electronegativity of alkali metal oxides is much greater than that of alumina and their deposition increases the negative charge of surface oxide ions hindering the diffusion of rhodium and preventing the growth of its larger particles.     

Activity and characterization of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for the SCR of NO with CO in the presence of SO2 and HCl

SO₂ and HCl are major pollutants emitted from waste incineration processes. Both pollutants are difficult to remove completely and can enter the catalytic reactor. In this work, the effects of SO₂ and HCl on the performance of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for NO removal were investigated in simulated waste incineration conditions. The characterizations of the catalysts were analyzed by BET, SEM/EDS, XRD, and ESCA. Experimental results indicated the 1%Rh/Al₂O₃ catalyst was significantly deactivated for NO and CO conversions when SO₂ and HCl coexisted in the flue gas. The addition of between 2 and 10 wt.% Na promoted the activity of the 1%Rh/Al₂O₃ catalyst for NO removal, but decreased the CO oxidation and BET surface area. The catalytic activity for NO removal was inhibited by HCl as a result of the formation of RhCl₃. Adding Na to the Rh/Al₂O₃ catalyst decreased the inhibition of SO₂ because of the formation of Na₂SO₄, which was observed in the XRD and ESCA analyses. SEM mapping/EDS showed that more S was residual on the surface of the Rh-Na/Al₂O₃ catalyst than Cl.     

In situ FTIR spectroscopic studies of electrooxidation of ethanol on Pd electrode in alkaline media

Electrooxidation of ethanol on a polycrystalline Pd disk electrode in alkaline media was studied by in situ Fourier transform infrared (FTIR) reflection spectroscopy. The emphasis was put on the quantitative determination of intermediates and products involved in the oxidation. It has revealed that most of ethanol was incompletely oxidized to acetate. The selectivity for ethanol oxidation to CO₂ (existing as CO₃²⁻ in alkaline media) was determined as low as 2.5% in the potential region where Pd electrode exhibited considerable electrocatalytic activity (−0.60 to 0.0 V vs. SCE). Nevertheless, the ability of Pd for breaking C-C bond in ethanol is still slightly better than that of Pt under the same conditions. Besides, a very weak band of adsorbed intermediate, bridge-bonded CO (CO_B) was identified on the Pd electrode for the first time, suggesting that CO₂ and CO₃²⁻ species may also be generated through CO pathway (i.e., indirect pathway).     

Perovskite-based electrocatalyst discovery and design using word embeddings from retrained SciBERT language model

With the ever-increasing volume of scientific literature, there is a strong need to develop methods that allow rigorous information identification. In this contribution, a state-of-the-art natural language processing (NLP) model was used to select perovskite materials for electrocatalytic applications from literature. This was accomplished by obtaining word embeddings for perovskite materials from the NLP model and subsequently designing downstream tasks to discover perovskite-based electrocatalyst materials. However, embeddings could be obtained only for materials available in the literature. Consequently, a novel methodology was devised to generate embeddings for newly designed materials. Results from the analysis showed that the computed embeddings could be used to rank materials for their suitability for electrocatalytic applications. Further, the word embeddings were also employed as features in predicting the electrocatalytic activity of perovskite-based electrocatalysts. The analysis demonstrated that the fidelity of regression models increased when the embeddings were used as features.     

Chromium doping and in-grown heterointerface construction for modifying Ni3FeN toward bifunctional electrocatalyst toward alkaline water splitting

Exploring high-performance non-noble metal electrocatalysts is pivotal for eco-friendly hydrogen energy applications. Herein, featuring simultaneous Chromium doping and in-grown heterointerface engineering, the Cr doping Ni₃FeN/Ni heterostructure supported on N-doped graphene tubes (denoted as Cr–Ni₃FeN/Ni@N-GTs) was successfully constructed, which exhibits the superior bifunctional electrocatalytic performances (88 mV and 262 mV at 10 mA cm⁻² for HER and OER, respectively). Furthermore, an alkaline electrolyzer, employing Ni₃FeN/Ni@N-GTs as both the cathode and the anode, requires a low cell voltage of 1.57 V at 10 mA⋅cm⁻². Cr doping not only modulates the electronic structure of host Ni and Fe but also synchronously induces nitrogen vacancies, leading to a higher number of active sites; the in-grown heterointerface Cr–Ni₃FeN/Ni induces the charge redistribution by spontaneous electron transfer across the heterointerface, enhancing the intrinsic catalytic activity; the N-GTs skeleton with excellent electrical conductivity improves the electron transport and mass transfer. The synergy of the above merits endows the designed Cr–Ni₃FeN/Ni@ N-GTs with outstanding electrocatalytic properties for alkaline overall water splitting.     

Manganese oxide embedded graphene nanohybrid for pH-universal electrochemical overall water splitting

Efficient non-noble metal bifunctional electrocatalysts for overall water splitting in pH universal is highly desired in application. Herein, MnO₂/graphene composition are applied as efficient electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in pH-universal electrolytes with the help of plasma dc arc method. The couple of MnO₂ and graphene highly benefits to the H₂O, H⁺ and OH⁻ absorption respectively. The defects and stable Mn³⁺ contribute to the transfer of electron and charge. The low overpotentials and small Tafel slopes reveal attractive activities of HER and OER. The good electrocatalytic performances are attributed to the synergistic effect and abundant heterogeneous interfaces in MnO₂/graphene. These can offer rich electroactive sites and accelerate electron transfer. Thus, it may provide facile route for developing nonprecious electrocatalysts of water splitting.     

Dynamic and kinetic modeling of isotopic transient responses for CO insertion on Rh and Mn–Rh catalysts

Isotopic transient tracer techniques have been employed to study heterogeneous hydroformylation on Rh/SiO₂ and Mn–Rh/SiO₂. Pulse injection of D₂ and allowed tracing of the deuterium and CO incorporation pathway into the aldehyde product. The d₁- and d₂-propionaldehyde responses showed a double-peak, or two-hump, response to the D₂ pulse, while showed a single-hump response to the pulse. Analysis of the product responses to the D₂ pulse in CO/H₂/C₂H₄ and CO/H₂/C₂H₄/C₂H₅CHO suggests that the first hump of the d₁- and d₂-propionaldehyde responses was due to rapid H/D exchange with adsorbed propionaldehyde via enol intermediates. The decay of the second hump was due to reaction of adsorbed acyl with spillover hydrogen/deuterium. The response was due to CO insertion followed by acyl hydrogenation. Compartment modeling of the product responses from the and D₂ pulse inputs allowed determination of residence times of adsorbed intermediates, surface coverages of adsorbed intermediates, and the elementary rate constants for acyl hydrogenation and CO insertion. Elementary rate constants for acyl hydrogenation determined from this study were consistent with the value calculated by transition state theory (TST). The addition of Mn promoter to Rh/SiO₂ increased coverages of , , and and shifted the rate-limiting step for propionaldehyde formation. Acyl hydrogenation is the rate-limiting step on Rh/SiO₂ while CO insertion and acyl hydrogenation are both kinetically significant on Mn–Rh/SiO₂.