Lucky Number 13: A 13-Layer Polytype of the Alkyne Hydrogenation Catalyst CaGaGe.

Polytypism, the ability of materials to form crystal structures with different stacking sequences, occasionally causes materials with the same stoichiometry and similar local structures to have profoundly different properties. Herein, we discover a metastable 13-layer trigonal (13T) polytype of CaGaGe, a layered intermetallic phase comprised of [GaGe]2- honeycombs separated by Ca2+. 13T-CaGaGe is synthesized from arc-melting the elements, and its structure is elucidated via neutron powder diffraction. Air-stable 13T-CaGaGe has one misaligned [GaGe]2- layer for every 13 and transforms into the more stable 4-layer hexagonal (4H) CaGaGe polytype after annealing at 500 °C. Transition-metal-free 13T-CaGaGe shows remarkable activity in the catalytic hydrogenation of phenylacetylene to styrene and ethylbenzene, much higher than the 4H polytype. This work identifies the first 13-layer polytype for any crystal structure and further establishes the influence of polytypism on catalysis.

Transition Metal-Free Alkyne Hydrogenation Catalysis with BaGa2, a Hydrogen Absorbing Layered Zintl Phase.

Inexpensive, transition metal-free intermetallic compounds have received almost no attention as heterogeneous catalysts. Here, we show that BaGa2, a Zintl-Klemm compound composed of honeycomb sheets of Ga- anions separated by Ba2+ cations and known to react with H2 under moderate conditions to form a layered polyanionic hydride BaGa2H2, effectively catalyzes the hydrogenation of phenylacetylene into styrene and ethylbenzene under modest conditions (1-50 bar H2, 40-100 °C). Remarkably, the catalytic activity of BaGa2 (surface specific activities up to 8390 h-1) is on the same order of magnitude as commercial Pd-based catalysts. In contrast, BaGa2H2 shows negligible catalytic activity, thereby indicating that the unsaturated Ga- framework is necessary for phenylacetylene and styrene adsorption. These findings open up future explorations of utilizing and optimizing the long-term stability of transition metal-free intermetallic hydrogen absorbing compounds for hydrogen-based catalysis.

Alkyne Hydrogenation Catalysis across a Family of Ga/In Layered Zintl Phases.

Transition-metal-free Zintl-Klemm phases have received little attention as heterogeneous catalysis. Here, we show that a large family of structurally and electronically similar layered Zintl-Klemm phases built from honeycomb layers of group 13 triel (Tr) or group 14 tetrel (Tt) networks separated by electropositive cations (A) and having a stoichiometry of ATr2 or ATrTt (A = Ca, Ba, Y, La, Eu; Tr = Ga, In; Tt = Si, Ge) exhibit varying degrees of activity for the hydrogenation of phenylacetylene to styrene and ethylbenzene at 51 bar H2 and 40-100 °C across a variety of solvents. The most active catalysts contain Ga with, formally, a half-filled pz orbital, and minimal bonding between neighboring Tr2 or TrTt layers. A 13-layer trigonal polytype of CaGaGe (13T-CaGaGe) was the most active, cyclable, and robust catalyst and under modest conditions (1 atm H2, 40 °C) had a surface specific activity (590 h-1) comparable to a commercial Lindlar's catalyst. Additionally, 13T-CaGaGe maintained 100% conversion of phenylacetylene to styrene at 51 bar H2, even after 5 months of air exposure. This work reveals the structural design elements that lead to particularly high catalytic activity in Zintl-Klemm phases, further establishing them as a promising materials platform for hydrogen-based heterogeneous catalysis.