Al-doped Fe2O3 as a support for molybdenum oxide methanol oxidation catalysts

We have made high surface area catalysts for the selective oxidation of methanol to formaldehyde. This is done in two ways – (i) by doping haematite with Al ions, to increase the surface area of the material, but which itself is unselective and (ii) by surface coating with Mo which induces high selectivity. Temperature programmed desorption (TPD) of methanol shows little difference in surface chemistry of the doped haematite from the undoped material, with the main products being CO2 and CO, but shifted to somewhat higher desorption temperature. However, when Mo is dosed onto the haematite surface, the chemistry changes completely to show mainly the selective product, formaldehyde, with no CO2 production, and this is little changed up to 10% Al loading. But at 15 wt% Al, the chemistry changes to indicate the presence of a strongly acidic function at the surface, with additional dimethyl ether and CO/CO2 production characteristic of the presence of alumina. Structurally, X-ray diffraction (XRD) shows little change over the range 0–20% Al doping, except for some small lattice contraction, while the surface area increases from around 20 to 100 m2 g−1. Using X-ray absorption spectroscopy (XAS) it is clear that, at 5% loading, the Al is incorporated into the Fe2O3 corundum lattice, which has the same structure as α-alumina. By 10% loading then it appears that the alumina starts to nano-crystallise within the haematite lattice into the γ form. At higher loadings, there is evidence of phase separation into separate Al-doped haematite and γ-alumina. If we add 1 monolayer equivalent of Mo to the surface there is already high selectivity to formaldehyde, but little change in structure, because that monolayer is isolated at the surface. However, when three monolayers equivalent of Mo is added, we then see aluminium molybdate type signatures in the XANES spectra at 5% Al loading and above. These appear to be in a sub-surface layer with Fe molybdate, which we interpret as due to Al substitution into ferric molybdate layers immediately beneath the topmost surface layer of molybdena. It seems like the separate γ-alumina phase is not covered by molybdena and is responsible for the appearance of the acid function products in the TPD

Chemo-enzymatic one-pot oxidation of cyclohexane via in-situ H2O2 production over supported AuPdPt catalysts

The introduction of dopant concentrations of Pt into supported AuPd nanoparticles, when used in conjunction with an evolved unspecific peroxygenase (UPO) from Agrocybe aegerita (PaDa‐I) is demonstrated to offer high efficacy towards the one‐pot selective oxidation of cyclohexane to KA oil (cyclohexanol and cyclohexanone), via the in‐situ synthesis of H2O2. The optimised AuPdPt/TiO2/PaDa‐I system achieves significant improvements over analogous AuPd or Pd‐only formulations or the use of commercially available H2O2, with this attributed to the increased rate of H2O2 production by the chemo‐catalyst, which results from the electronic modification of Pd species via Pt incorporation, upon the formation of trimetallic nanoalloys

Selective Ammoximation of Ketones via In Situ H2O2 Synthesis

The ammoximation of ketones to the corresponding oxime via the in situ production of H2O2 offers a viable alternative to the current means of industrial-scale production, in particular for the synthesis of cyclohexanone oxime, a key precursor to Nylon-6. Herein, we demonstrate that using a bifunctional catalyst, consisting of Pd-based bimetallic nanoparticles immobilized onto a TS-1 carrier, it is possible to bridge the considerable condition gap that exists between the two key distinct reaction pathways that constitute an in-situ approach (i.e., the direct synthesis of H2O2 and ketone ammoximation). The formation of PdAu nanoalloys is found to be crucial in achieving high reactivity and in promoting catalytic stability, with the optimal formulation significantly outperforming both alternative Pd-based materials and the monometallic Pd analogue

2023 EELS field tests at Athabasca Glacier as an icy moon analogue environment

JPL is developing a versatile and highly intelligent Exobiology Extant Life Surveyor (EELS) robot that would enable access to subsurface oceans and near-surface liquid reservoirs through existing conduits, such as the vents at the south pole of Enceladus or the putative geysers on Europa. A key mobility requirement for future vent exploration missions will be the ability to carefully descend and hold position in the vent to collect and analyze samples while withstanding plume forces without human intervention. Furthermore, this must be accomplished in a highly uncertain environment, requiring versatile hardware and intelligent autonomy. To work towards that goal, we have prototyped the EELS 1.0 and EELS 1.5 robots for horizontal and vertical mobility, respectively, in icy terrain. Autonomous surface mobility of EELS 1.0 was previously validated in a variety of terrain, including snowy mountains, ice rinks, and desert sand. Vertical mobility of EELS 1.5 was developed on laboratory ice walls. This paper presents the first mobility trials for both robots on large-scale, natural icy terrain: the Athabasca Glacier located in Alberta, Canada, a terrestrial analogue to the surfaces and subsurfaces of icy moons. This paper provides a preliminary written record of the test campaign’s four major trials: 1) surface mobility with EELS 1.0, 2) vertical mobility with EELS 1.5, 3) science instrument validation, and 4) terramechanics experiments. During this campaign, EELS 1.5 successfully held position and descended ~1.5 m vertically in an icy conduit and EELS 1.0 demonstrated surface mobility on icy surfaces with undulations and slopes. A miniaturized capillary electrophoresis (CE) instrument built to the form factor of an EELS module was tested in flowing water on the glacier and successfully demonstrated automated sampling and in-situ analysis. Terramechanics experiments designed to better understand the interaction between different ice properties and the screws that propel the robot forwards were performed on horizontal and vertical surfaces. In this paper we report the outcomes of the four tests and discuss their implications for potential future icy missions. The field test also demonstrated EELS’s ability to support Earth science missions. Another potential near-term follow-on could be a technology demonstration on the Moon. This paper is a high level report on the execution of the field test. Data and results will be detailed in subsequent publications