The ACS Catalysis Virtual Special Issue highlights the leading role of The Netherlands in international catalysis research which according to the four guest editors can be attributed not only to the large chemical 'ecosystem' in the region (Dutch chemical industry has a turnover of €60 billion and accounts for 8% of GDP) but also to the collaborative, multidisciplinary nature of Dutch catalysis research and to the Dutch tradition of research schools established within large-scale R&D groups at Dutch universities. Furthermore, through the rather unique synergy between industrial and academic chemistry in The Netherlands the horizons of fundamental academic catalysis research are extended into real-world industrial challenges.

The ACS Catalysis Virtual Special Issue underpins the strength and broad scope of the Dutch catalysis research in 2 Perspectives, 1 Review, 2 Letters, and 19 Articles, with topics spanning from advanced heterogeneous and homogeneous catalyst design, to theory and mechanistic studies, as well as photo-, electro-, and biocatalysis. All submissions have undergone rigorous peer-review against the high standard required for publication in ACS Catalysis.

Publications with contributions of HIMS researchers in this Virtual Special Issue:

Review: Synthetic strategies and catalytic applications  of lanthanide-based Metal Organic Frameworks

(Heterogeneous Catalysis & Sustainable Chemistry Group)

This short critical review outlines the main synthetic strategies used in the designed synthesis of lanthanide-based metal organic frameworks (Ln-MOFs). It explains the impact of the choice of organic linker on the final network topology, and it highlights the applications of Ln-MOFs in the catalysis of organic reactions.

• Céline Pagis, Marilena Ferbinteanu, Gadi Rothenberg, and Stefania Tanase: Lanthanide-Based Metal Organic Frameworks: Synthetic Strategies and Catalytic Applications ACS Catal., 2016, 6 (9), pp 6063–6072 DOI: 10.1021/acscatal.6b01935

Letter: Developing a bimetallic anode catalyst for solid oxide fuel cells

(Heterogeneous Catalysis & Sustainable Chemistry Group)

The development is reported of a novel Co–W bimetallic anode catalyst for solid oxide fuel cells (SOFCs) via a facile infiltration-annealing process. Using various microscopic and spectroscopic measurements it is established that the formed intermetallic nanoparticles are highly thermally stable up to 900 °C and show good coking resistance in methane. In particular, a fuel cell fitted with Co₃W anode shows comparable activity (relative to Co) in the electro-oxidation of hydrogen and methane at 900 °C without suffering significant degradation during a longevity test.

• Ning Yan, Jay Pandey, Yimin Zeng, Babak S. Amirkhiz, Bin Hua, Norbert J. Geels, Jing-Li Luo, and Gadi Rothenberg: Developing a Thermal- and Coking-Resistant Cobalt–Tungsten Bimetallic Anode Catalyst for Solid Oxide Fuel Cells ACS Catal., 2016, 6 (7), pp 4630–4634 DOI: 10.1021/acscatal.6b01197

Article: A self-assembled molecular cage for substrate-selective epoxidation in aqueous media

(Homogeneous, Bio-Inspired & Supramolecular Catalysis Group)

Encapsulation of a manganese porphyrin in a self-assembled molecular cage allows catalytic epoxidation of various substrates in 1:1 water/acetonitrile mixtures. The cage acts as a phase-transfer catalyst and creates a protective environment for the catalyst improving the stability. The encapsulated catalyst also allows discrimination between styrene derivatives of various sizes. In a direct competition experiment, the selectivity of the epoxidation reaction could be inverted with respect to a benchmark catalyst.

• Petrus F. Kuijpers, Matthias Otte, Maximilian Dürr, Ivana Ivanović-Burmazović, Joost N. H. Reek, and Bas de Bruin: A Self-Assembled Molecular Cage for Substrate-Selective Epoxidation Reactions in Aqueous Media ACS Catal., 2016, 6 (5), pp 3106–3112 DOI: 10.1021/acscatal.6b00283

Article: Reaction Progress Kinetic Analysis as a Tool To Reveal Ligand Effects

(Homogeneous, Bio-Inspired & Supramolecular Catalysis Group)

A series of iridium-based complexes have been evaluated in Ce(IV)-driven water oxidation catalysis. Detailed kinetic data have been obtained from UV–vis stopped-flow experiments, and these data have been analyzed using reaction progress kinetic analysis. The graphical plots show that there are three clear phases in the reaction: catalyst activation, water oxidation catalysis, and cerium concentration controlled catalysis at the end of the reaction. The ligand attached to the IrCp* complex has a clear influence on both the activation as well as the catalysis. Some bidentate ligands result in relatively slow catalysis, and the first-order in iridium supports the presence of mononuclear active species; however, other bidentates form the more active dinuclear species. Monodentate ligands allow the formation of bis-μ-oxo bridged dimeric species, supported by kinetics displaying 1.6-order in [Ir], leading to high reaction rates.

• Jacobus M. Koelewijn, Martin Lutz, Wojciech I. Dzik, Remko J. Detz, and Joost N. H. Reek: Reaction Progress Kinetic Analysis as a Tool To Reveal Ligand Effects in Ce(IV)-Driven IrCp*-Catalyzed Water Oxidation ACS Catal., 2016, 6 (6), pp 3418–3427 DOI: 10.1021/acscatal.6b00297

Article: A Biocatalytic Aza-Achmatowicz Reaction

(Biocatalysis Group)

A catalytic, enzyme-initiated (aza-) Achmatowicz reaction is presented. The involvement of a robust vanadium-dependent peroxidase from Curvularia inaequalis allows the simple use of H₂O₂ and catalytic amounts of bromide.

• Elena Fernández-Fueyo, Sabry H. H. Younes, Stefan van Rootselaar, René W. M. Aben, Rokus Renirie, Ron Wever, Dirk Holtmann, Floris P. J. T. Rutjes, and Frank Hollmann: A Biocatalytic Aza-Achmatowicz Reaction ACS Catal., 2016, 6 (9), pp 5904–5907 DOI: 10.1021/acscatal.6b01636