Towards the selective hydrodeoxygenation and hydrogenation of levoglucosenone using base metal heterogeneous catalysts modified by atomic layer deposition

Informazioni relative al progetto

TAILORCAT

ID dell’accordo di sovvenzione: 701028

DOI

10.3030/701028

Progetto chiuso

Data della firma CE 9 Settembre 2016

Data di avvio 15 Giugno 2017

Data di completamento 14 Giugno 2020

Finanziato da

• EXCELLENT SCIENCE - Marie Skłodowska-Curie Actions

Costo totale

€ 260 929,80

Contributo UE

€ 260 929,80

Coordinato da

UNIVERSITEIT UTRECHT
Netherlands

Periodic Reporting for period 2 - TAILORCAT (Towards the selective hydrodeoxygenation and hydrogenation of levoglucosenone using base metal heterogeneous catalysts modified by atomic layer deposition)

Periodo di rendicontazione: 2019-06-15 al 2020-06-14

Sintesi del contesto e degli obiettivi generali del progetto

The TAILORCAT project was concerned with the development of catalytically active and non-leaching heterogeneous base metal catalysts (e.g. copper, iron, nickel), which could be used in an aqueous reaction medium. This was a challenging objective as base metals tend to leach (disappear) easily during any aqueous phase reaction therewith rendering the catalyst inactive. To achieve this aim, it was proposed to stabilize or even encapsulate the supported base metal nanoparticles with oxides or oxide layers. This was expected to contain the base metal leaching but also to enhance the activity & selectivity of the catalysts. The ability to use base metal catalysts over noble metal catalysts is important to society while noble metals (e.g. platinum, palladium) are becoming ever scarcer. The scarcity of noble metals reflects itself already in ever increasing raw material prices. Generally spoken base metals are significantly cheaper and much more abundantly available.

Lavoro eseguito dall’inizio del progetto fino alla fine del periodo coperto dalla relazione e principali risultati finora ottenuti

In a first instance the TAILORCAT project focused on the use of copper as a hydrogenation catalyst, while copper is one of the cheapest base metals and readily available in large quantities. After a first general screening process, copper supported on layered double hydroxide (a type of clay also known as hydrotalcite) was found to hold the best cards in terms of catalytic activity. Gratifyingly, this catalyst was found free of copper leaching and this without the application of protective oxide layers onto the supported copper nanoparticles. Equally surprising this catalyst displayed markedly different activity levels in flow and batch reactors. This was found to relate to an inherent and unexpected acidity of the starting reaction mixture. As a result, a continuous loss of very small amounts of magnesium from the supporting clay material was observed. This work was published in the journal of Green Chemistry and bestowed hot article status: Green Chem., 2019, 21, 5000-5007 (DOI: 10.1039/C9GC00564A). Finally, using a combination of XRD and in situ UV-VIS, it could be shown that Cu(I) species play an important role.

Progressi oltre lo stato dell’arte e potenziale impatto previsto (incluso l’impatto socioeconomico e le implicazioni sociali più ampie del progetto fino ad ora)

With the discovery of a non-copper leaching heterogeneous catalyst capable of doing hydrogenation reactions in water, the TAILORCAT project has ventured into uncharted territory. Indeed, to date no real non-copper-leaching heterogeneous catalyst exists that can operate in aqueous medium. It is further also noteworthy that the invented copper catalyst can operate at temperatures as low as 333 K which is very unusual. Presently the TAILORCAT project has been focusing on the making of levoglucosanol. The latter compound is of significant importance while it can be further transformed into (bio-derived) 1,2,6-hexanetriol and 1,6-hexanediol – two very important commodity chemicals! With a view on the future, it is expected that the application range of this catalyst will increase further as we gain more knowledge on the why and how of the non-leaching character of the copper metal.

Graphical abstract for the Green Chemistry paper on Cu/LDH

TOC graphic for the polyboronate paper

Graphical abstract for the Cyrene/Cyrene hydrate (Cyrene's geminal diol) paper