Reactivity of nitrogen atoms from Zif-8 structure deposited over Ti3C2 MXene in the electrochemical nitrogen reduction reaction.

The electrochemical nitrogen reduction reaction (NRR) to produce NH3 is the most efficient, eco-friendly and cost-effective alternative to the Haber-Bosch process. It is crucial to investigate and develop electrocatalysts selective for NH3 synthesis. In recent studies, the Ti3C2 MXene has emerged as a highly promising electrocatalyst for the NRR process. In this work, we explore the effect of Zif-8 addition over MXene sheets in order to control the rate of hydrogen evolution reaction (HER). Despite the better result obtained for Zif-8@Ti3C2 (3.0 µg NH3 gcat-1 h-1 at -0.55 V/RHE), the ammonia produced when using Zif-8@Ti3C2 as cathode material is shown to be originated from nitrogen atoms contained in the Zif-8 structure instead of those of N2. The results shed light to the need to fully understand the N2 electroreduction process over N-containing electrocatalysts.

High-Surface-Area Synthesis of Iron-Doped CaTiO3 at Low Temperatures: New Insights into Oxygen Activation, Iron States, and the Impact on Methane Oxidation.

In the present work, a series of CaTi1-xFexO3-δ (0 < x < 0.5) materials are prepared using a modified Pechini method based on citric acid and a polyol as chelating agents. The synthesis conditions are optimized with respect to the specific surface area and phase purity by varying polyols (ethylene glycol, glycerol, and 1.6-hexanediol) and the ratio between citric acid, polyols, and cations. The impact of the polyols and the iron content (up to 40 mol % on the B site) is studied with respect to the oxygen exchange rate, reducibility using H2-TPR, and catalytic performance for methane total oxidation. A correlation between the oxygen exchange rate studied using 18O exchange in powdered samples of CaTi1-xFexO3-δ (0 < x < 0.5) and ferric sites determined using Mössbauer spectroscopy and H2-TPR is established. The oxygen activation and diffusion in CaTi1-xFexO3-δ (0 < x < 0.5) continuously increase in the studied range of Ti substitution. The methane oxidation performance does not increase above x = 0.3, showing that methane oxidation is not limited by surface oxygen activation and CH4 is activated by specific iron sites in Fe-doped perovskites.

Combination of theoretical and in situ experimental investigations of the role of lithium dopant in manganese nitride: a two-stage reagent for ammonia synthesis.

Manganese nitride related materials are of interest as two-stage reagents for ammonia synthesis via nitrogen chemical looping. However, unless they are doped with a co-cation, manganese nitrides are thermochemically stable and a high temperature is required to produce ammonia under reducing conditions, thereby hindering their use as nitrogen transfer materials. Nevertheless, when lithium is used as dopant, ammonia generation can be observed at a reaction temperature as low as 300 °C. In order to develop strategies for the improvement of the reactivity of nitride materials in the context of two-stage reagents, it is necessary to understand the intrinsic role of the dopant in the mechanism of ammonia synthesis. To this end, we have investigated the role of lithium in increasing the manganese nitride reactivity by in situ neutron diffraction studies and N2 and H2 isotopic exchange reactions supplemented by DFT calculations.

Operando Isotopic Exchange in Solid Oxide Fuel Cells: Oxygen-Transport Dependency on Applied Potential.

The oxygen isotopic exchange technique is a powerful tool to investigate the oxygen transport kinetics in an oxide solid. In a solid oxide fuel cell, isotopic surface exchange and diffusion coefficients are classically determined by using the Isotopic Exchange Depth Profiling method followed by ex situ SIMS characterizations. Despite its relevance, the utilization of in situ or operando techniques to measure the isotopic exchange under an electrical bias remains marginal. We developed here a set-up which enables operando monitoring of oxygen exchange in SOFC type cells under polarization. The system has been used for studying the oxygen mobility dependency upon polarization on a symmetrical Pt/YSZ/Pt cell (YSZ: yttria-stabilized zirconia). Homomolecular and heterolytic exchange reactions were undertaken to investigate the oxygen activation step and discriminate the limiting step among the sequence of elementary steps which constitute the oxygen transport process in the SOFC system. Oxygen ions incorporation into the dense ionic conductor was identified to be the rate determining step, and its first order rate constant dependency on applied potential was established.

Remarkable active-site dependent H2O promoting effect in CO oxidation.

The interfacial sites of supported metal catalysts are often critical in determining their performance. Single-atom catalysts (SACs), with every atom contacted to the support, can maximize the number of interfacial sites. However, it is still an open question whether the single-atom sites possess similar catalytic properties to those of the interfacial sites of nanocatalysts. Herein, we report an active-site dependent catalytic performance on supported gold single atoms and nanoparticles (NPs), where CO oxidation on the single-atom sites is dramatically promoted by the presence of H2O whereas on NPs' interfacial sites the promoting effect is much weaker. The remarkable H2O promoting effect makes the Au SAC two orders of magnitude more active than the commercial three-way catalyst. Theoretical studies reveal that the dramatic promoting effect of water on SACs originates from their unique local atomic structure and electronic properties that facilitate an efficient reaction channel of CO + OH.

Unexpected redox behaviour of large surface alumina containing highly dispersed ceria nanoclusters.

Cerium-containing oxide materials have several very interesting applications due to their capacity to store and release oxygen under oxidizing and reducing conditions respectively. In the case of pure ceria this property is highly size dependent inasmuch as the phenomenon is limited to the surface and subsurface oxygen atoms. As a consequence, the design of nanocrystals of ceria has been attracting much attention. In this paper, the evaporation-induced self-assembly method was used to prepare a series of mixed oxide materials composed of nanoclusters of ceria very well dispersed over large surface mesoporous alumina. We observed a total and reversible reduction of Ce4+ into Ce3+ at 400 °C for the materials with a Ce loading between 20 and 35 wt%. A combination of analyses including in situ X-ray diffraction, temperature-programmed reduction, oxygen storage capacity, isotopic exchange, 27-Al and 17-O solid state NMR, and X-ray absorption spectroscopy at the Ce L3-edge was employed to investigate this unexpected redox behavior. The results reveal that the strong structural disorder observed in both CeO2 and Al2O3 nanoclusters favors the formation of non-crystallized CeAlO3 pseudo phase at the interface between the two oxides.

Investigation of Methane Oxidation Reactions Over a Dual-Bed Catalyst System using 18 O Labelled DRIFTS coupling.

Low loading Pd-supported (0.2 wt % Pd) Y-stabilized zirconia (YSZ) and LaMnO3 (LM) perovskite were associated to study the partial oxidation of methane using labelled 18 O2 in the gas phase. Synthesis gas production was demonstrated to occur through an indirect reaction in which oxygen is first consumed in the total methane combustion. A Mars-van Krevelen mechanism was observed over Pd/YSZ at 425 °C to yield C16 O2 and C16 O. A significant enhancement of the Pd/YSZ catalyst activity was achieved by the association of LM-Pd/YSZ in a dual catalyst bed, resulting in a significant increase of the oxidation rate. Vibration bands of adsorbed formate species, assumed to be intermediates to the gas production, were observed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) coupling experiments. It was proposed that LM enables the generation of highly active singlet O2 , which is activated on the YSZ oxygen vacancies to assist a rapid recovery of surface PdO and increase formate decomposition into CO and H2 in Pd-supported catalyst.

Remarkable enhancement of O2 activation on yttrium-stabilized zirconia surface in a dual catalyst bed.

Yttrium-stabilized zirconia (YSZ) has been extensively studied as an electrolyte material for solid oxide fuel cells (SOFC) but its performance in heterogeneous catalysis is also the object of a growing number of publications. In both applications, oxygen activation on the YSZ surface remains the step that hinders utilization at moderate temperature. It was demonstrated by oxygen isotope exchange that a dual catalyst bed system consisting of two successive LaMnO3 and YSZ beds without intimate contact drastically enhances oxygen activation on the YSZ surface at 698 K. It can be concluded that LaMnO3 activates the triplet ground-state of molecular oxygen into a low-lying singlet state, thereby facilitating the activation of the O2 molecule on the YSZ oxygen vacancy sites. This phenomenon is shown to improve the catalytic activity of the LaMnO3-Pd/YSZ system for the partial oxidation of methane.

Clear microstructure-performance relationships in Mn-containing perovskite and hexaaluminate compounds prepared by activated reactive synthesis.

Microstructural properties of mixed oxides play essential roles in their oxygen mobility and consequently in their catalytic performances. Two families of mixed oxides (perovskite and hexaaluminate) with different microstructural features, such as crystal size and specific surface area, were prepared using the activated reactive synthesis (ARS) method. It was shown that ARS is a flexible route to synthesize both mixed oxides with nano-scale crystal size and high specific surface area. Redox properties and oxygen mobility were found to be strongly affected by the material microstructure. Catalytic activities of hexaaluminate and perovskite materials for methane oxidation were discussed in the light of structural, redox and oxygen mobility properties.

A Study of 15N/14N Isotopic Exchange over Cobalt Molybdenum Nitrides.

The 14N/15N isotopic exchange pathways over Co3Mo3N, a material of interest as an ammonia synthesis catalyst and for the development of nitrogen transfer reactions, have been investigated. Both the homomolecular and heterolytic exchange processes have been studied, and it has been shown that lattice nitrogen species are exchangeable. The exchange behavior was found to be a strong function of pretreatment with ca. 25% of lattice N atoms being exchanged after 40 min at 600 °C after N2 pretreatment at 700 °C compared to only 6% following similar Ar pretreatment. This observation, for which the potential contribution of adsorbed N species can be discounted, is significant in terms of the application of this material. In the case of the Co6Mo6N phase, regeneration to Co3Mo3N under 15N2 at 600 °C occurs concurrently with 14N15N formation. These observations demonstrate the reactivity of nitrogen in the Co-Mo-N system to be a strong function of pretreatment and worthy of further consideration.

Preparation of crystal-like periodic mesoporous phenylene-silica derivatized with ferrocene and its use as a catalyst for the oxidation of styrene.

The surface silanol groups in crystal-like mesoporous phenylene-silica have been derivatized with trimethylsilyl, benzyldimethylsilyl and dimethylsilyl(ferrocene) groups by performing a post-synthetic grafting reaction with the corresponding chlorosilane precursors. The success of the grafting procedure was demonstrated by transmission FT-IR spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and (13)C and (29)Si magic-angle spinning (MAS) NMR spectroscopy. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and N2 adsorption data for the modified materials indicated preservation of the mesostructure as well as the molecular-scale periodicity in the pore walls. Ferrocene and the ferrocenyl-modified periodic mesoporous organosilica (PMO) were employed in the catalytic oxidation of styrene at 55 °C using either hydrogen peroxide or tert-butylhydroperoxide as an oxidant. The main reaction product was always benzaldehyde (BzCHO), and other products included styrene oxide, benzoic acid and 2-hydroxyacetophenone. Using a styrene:H2O2 molar ratio of 1:5, the highest BzCHO yields at 24 h were 65% (85% selectivity) for ferrocene (semibatch conditions involving stepwise addition of H2O2, 1 mol% Fe) and 34% (83% selectivity) for the modified PMO (batch conditions, 0.06 mol% Fe). The modified PMO could be recovered and reused, albeit with a drop in catalytic activity due to partial metal leaching during the first catalytic run.

Design of nanocrystalline mixed oxides with improved oxygen mobility: a simple non-aqueous route to nano-LaFeO3 and the consequences on the catalytic oxidation performances.

LaFeO3 nanoparticles, with improved oxygen mobility, leading to enhanced catalytic oxidation activities, are obtained through a simple nonaqueous route.

Design of nanocatalysts for green hydrogen production from bioethanol.

Bioethanol is an interesting feedstock that may be used for hydrogen production by steam or autothermal reforming. However, the impurities (heavy alcohols, esters, acids, N compounds) contained in the raw feedstock require a costly purification, as they have a dramatic impact on catalyst activity and stability. Thus, a method that can utilize the raw feedstock without severe degradation of the catalyst would be desirable. In this Minireview, the composition of bioethanol from first and second generation biomass, the reactions involved in the catalytic ethanol steam reforming process and the design of catalysts adapted for hydrogen production from a real bioethanol feed are surveyed.

Sulfonic acid functionalized crystal-like mesoporous benzene-silica as a remarkable water-tolerant catalyst.

Here we report that sulfonated crystal-like benzene-silica is much more robust and active than conventionally used periodic mesoporous silica for catalyzing aqueous organic reactions.

Improved oxygen mobility in nanosized mixed-oxide particles synthesized using a simple nanocasting route.

This work reports the synthesis of homogeneously dispersed mixed-oxide nanoparticles (<5 nm) exhibiting improved lattice oxygen mobility (ca. two times higher than on bulk samples), using a novel synthesis procedure of nanocasting in mesoporous silica host support.