Isolated Fe(III)–O Sites Catalyze the Hydrogenation of Acetylene in Ethylene Flows under Front-End Industrial Conditions

Abstract

The search for simple, earth-abundant, cheap, and nontoxic metal catalysts able to perform industrial hydrogenations is a topic of interest, transversal to many catalytic processes. Here, we show that isolated Fe-O sites on solids are able to dissociate and chemoselectively transfer H to acetylene in an industrial process. For that, a novel, robust, and highly crystalline metal-organic framework (MOF), embedding Fe-OH single sites within its pores, was prepared in multigram scale and used as an efficient catalyst for the hydrogenation of 1% acetylene in ethylene streams under front-end conditions. Cutting-edge X-ray crystallography allowed the resolution of the crystal structure and snapshotted the single-atom nature of the catalytic Fe-O site. Translation of the active site concept to even more robust and inexpensive titania and zirconia supports enabled the industrially relevant hydrogenation of acetylene with similar activity to the Pd-catalyzed process.

Anchoring Cu1 species over nanodiamond-graphene for semi-hydrogenation of acetylene

“…Although the Pd-Ag catalyst prevents the usage of toxic promoters such as lead or sulfur (Lindlar catalyst) 5 , the extremely high cost of Pd leaves ample room for improving the cost-effectiveness in catalyst design. In an effort to develop environment-friendly and cost-effective catalysts, various approaches have been pursued, including (i) reducing the amount of noble metals by “site-isolation” strategy or engineering a minimal ensemble 6–11 and (ii) developing non-noble metals/metal oxides catalysts 12–18 .…”

“…Owing to limited H 2 activation ability 29 , semihydrogenation of alkynes over these oxide catalysts normally required a relatively high-operating temperature. In an elegant work recently, Pardo et al reported a metal–organic framework-based Fe(III)-O catalyst 18 . This single-site cationic species was active for acetylene hydrogenation at up to 150 °C, which is an important advance in non-noble metal catalyst for this reaction.…”

High‐Performance Catalysts Derived from Cupric Subcarbonate for Selective Hydrogenation of Acetylene in an Ethylene Stream

“…However, Ni‐based catalysts deactivate quickly during the acetylene hydrogenation due to the vigorous formation of oligomers [32,33] . In addition, Fe‐based, [34,35] Cu‐based [36–38] and CeO 2 ‐based [39–41] catalysts were also reported to perform well in selective hydrogenation of acetylene. For example, Cu catalysts were intrinsically selective to alkene in alkyne hydrogenation due to the marked difference of adsorption energy between alkyne and the corresponding alkene [7,42,43] .…”

Crystallographic Visualization of a Double Water Molecule Addition on a Pt1‐MOF during the Low‐temperature Water‐Gas Shift Reaction

“…In this context, we recently reported [18] the postsynthetic [19–24] preparation and structural characterization of well‐defined Pt 1 1+ single atom catalysts (SACs) supported, stabilized and homogeneously distributed within the pores of a robust metal‐organic framework [25–30] (MOF). This hybrid material, with formula [Pt 2+ 2 (μ‐O)(OH) 2 (NH 3 ) 4 ] 0.5 Pt 1+ 1 @Na 3 {Ni 2+ 4 [Cu 2+ 2 (Me 3 mpba) 2 ] 3 } ⋅ 79H 2 O ( 1 ), [18] was characterized, in detail, by single crystal X‐ray diffraction [31,32] and exhibited good catalytic activity for the WGSR at low‐temperature.…”