Communication
Cite This: J. Am. Chem. Soc. 2019, 141, 19969−19972 pubs.acs.org/JACS
Transition Metal-Free Alkyne Hydrogenation Catalysis with BaGa2, a
Hydrogen Absorbing Layered Zintl Phase
Kelsey L. Hodge and Joshua E. Goldberger*
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States
*
S Supporting Information
ABSTRACT: Inexpensive, transition metal-free interme-
tallic compounds have received almost no attention as
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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 hydro-
gen-based catalysis.
T he discovery of new heterogeneous catalysts has come a
long way from the random screening of solid-state
compounds. The most common platforms for heterogeneous
hydrogenations are supported transition metal nanostructures
such as Lindlar’s Pb-coated Pd catalysts on CaCO3 for alkyne
semihydrogenation,1 reduced Fe3O4 on calcium alumina
silicates,2 or Ru on graphite for NH3 production.3 In almost
all catalysts, the transition metals on the surface are thought to
serve as the active sites, enabling the binding of different
reactants and intermediates because of their ability to
accommodate various redox states and coordination environ-
ments. The support has a variety of roles including limiting
catalyst deactivation from sintering and influencing reactivity
via spillover.4 The need to limit precious metal usage has
resulted in strategies to improve the catalytic activity and
selectivity per mass of active metal. These include diluting the
active metal and tuning the electronic structure via alloying
with a second element5−7 or achieving higher surface area to
mass ratios via nanostructuring.8−11 For instance, unsupported
PdGa, Pd3Ga7, Pd2Ga, and even Al13Fe4 all exhibit much
higher selectivity in acetylene semihydrogenation while
maintaining similar activities as Pd on Al2O3.5,6 Additionally,
computational screening methods that determine the relative
binding affinity of substrates to a catalyst surface have been
fruitful for discovering new heterogeneous catalysts.12 For
example, initial predictions of selective alkyne semihydrogena-
© 2019 American Chemical Society
tion with NiGa and NiSn12 led to the observation of catalysis
in Ni3Ga and Ni3Sn2 nanocrystals.13 A final approach is to
identify solids with particular electronic structures that are
considered to exhibit high catalytic activity.14,15 Examples of
this include solid-state electrides that have low work functions
and readily dissociate H2.16−18 For instance, LaCu0.67Si1.33 was
reported to be a stable, solid-state electride with activity for
nitroarene hydrogenation.18 Still, to the best of our knowledge,
there are no known reports of transition metal-free
heterogeneous hydrogenation catalysts.
We sought a different strategy to discover unexpected
families of heterogeneous hydrogenation catalysts, on the basis
of the propensity of materials to cleave and absorb H2 into
their lattice under moderate conditions (<200 °C, 50 bar
H2).19 One of the key steps in most hydrogenation
mechanisms is the dissociative adsorption of H2 onto a
surface. We hypothesize that solids that readily form hydride
phases likely have low barriers for this dissociative surface
adsorption. Some of the aforementioned catalysts readily form
bulk hydrides. Whether the internally absorbed hydrogen plays
a role in catalysis depends on the catalyst and the reaction. Pd,
one of the best hydrogen absorbing metals, incorporates 0.7
eqiv of H at 1 atm.20 This bulk hydrogen promotes alkyne
overhydrogenation to the alkane.21−24 In contrast, La-
Cu0.67Si1.33 also forms a hydride (LaCu0.67Si1.33H0.3) with
suppressed catalytic activity.18
Here, we report that BaGa2, a transition metal-free, layered
Zintl phase that absorbs hydrogen at elevated temperatures
and pressures to form BaGa2H2,25 is a highly efficient catalyst
for alkyne hydrogenation. Using phenylacetylene as a substrate,
we observed semihydrogenation surface specific activities
(SSAs) of >400 h−1 with mild conditions (40 °C, 1 bar H2,
4 mol % catalyst, dimethylformamide (DMF)) as well as a
much higher SSA (>8390 h−1) at elevated H2 pressures (51 bar
H2). These values represent the lower bounds of the turnover
frequency, as they assume every surface Ga atom is catalytically
active. BaGa2H2 shows no appreciable catalytic activity,
indicating that hydrogen inside the Zintl phase does not
participate in catalysis. Despite the high activity, the BaGa2
surface is prone to oxidation in H2O, suppressing catalytic
activity. This work shows that outstanding catalytic activity can
be achieved in main group Zintl phases, which are a completely
unexplored class of compounds for catalysis.
The BaGa2 crystal structure consists of planar honeycomb
networks of Ga− anions separated by Ba2+ cations (Figure 1a).
Received: September 11, 2019
Published: December 9, 2019
19969 DOI: 10.1021/jacs.9b09856
J. Am. Chem. Soc. 2019, 141, 19969−19972
Journal of the American Chemical Society
Figure 1. (a) Diagram showing conversion of BaGa2 to BaGa2H2.
Blue, red, and green spheres correspond to Ga, Ba, and H,
respectively. (b) X-ray diffraction of BaGa2H2 (red) and BaGa2
(blue). (c) Secondary electron micrograph of BaGa2 powder.
This structure is isoelectronic to MgB2 or graphite, suggesting
that the Ga networks have appreciable π-bonding. Ga π-
bonding is considerably weaker than in the first row elements.
Consequently, under moderate conditions (50 bar H2, 170
°C), BaGa2 reacts with H2 to form BaGa2H2.25 The
polyanionic gallium hydride layer retains the honeycomb
configuration but puckers, indicative of Ga sp3-hybridization.
We synthesized BaGa2 from the elements in a sealed tube
synthesis. Figure 1b shows the powder X-ray diffraction (XRD)
pattern of the BaGa2 product. Rietveld analysis confirms that
BaGa2 is >97% phase pure and crystallizes into a P6/mmm
space group with a = 4.4320(3) Å and c = 5.0731(2) Å (Figure
S1, Tables S1 and S2). Due to the peritectic nature of BaGa2,26
trace quantities of BaGa4 form under a wide range of synthetic
conditions. Therefore, we synthesized pure BaGa4 to compare
its activity as a potential catalytic impurity (Figure S2). Also,
we confirmed that the majority of the BaGa2 phase is
transformed into BaGa2H2 upon annealing for 7 days at 170
°C under 50 bar H2. Figure 1b also shows the XRD pattern of
our hydrogenated sample, showing a majority of the BaGa2H2
phase. Rietveld analysis (Figure S3, Tables S3 and S4)
confirms that the majority (84.7 wt %) transforms into a
P3̅m1 space group with a = 4.530(8) Å and c = 4.910(9) Å,
with 11.6% unreacted BaGa2, and ∼3.7 wt % is BaGa4.
Secondary electron microscopy (SEM) images of the ground
BaGa2 powders show particles with dimensions ranging from
320 nm to 13 μm (Figure 1c).
Preliminary hydrogenation experiments were conducted
using phenylacetylene as a substrate to evaluate the catalytic
semihydrogenation to styrene and full hydrogenation to
ethylbenzene (Figure 2a). Using 1 bar H2 and only 0.5−5
mol % BaGa2, we found that the dried, freshly distilled, and
degassed solvents DMF (40 °C) and n-butanol (70 °C) had
the highest conversion of phenylacetylene to styrene and
ethylbenzene (15−40%, 24 h). Other solvents including THF
and MeOH had much less conversion of phenylacetylene (5−
10%, 24 h). As shown in Figure 2b, 80% conversion of
phenylacetylene to styrene and ethylbenzene was observed
after 48 h in DMF, 1 bar H2, and 4.7 mol % BaGa2. Longer
reaction times did not lead to 100% conversion, which we
attribute to catalyst deactivation via partial oxidation caused by
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Figure 2. (a) BaGa2 catalyzed hydrogenation of phenylacetylene
(red) to styrene (blue) and ethylbenzene (green). (b) Time
dependent conversion products using 1 bar H2, 40 °C, 2.4 mL of
DMF, 0.87 mmol of phenylacetylene, and 0.043 mmol of BaGa2. (c)
Time dependent conversion products using 51 bar H2, 40 °C, 2.4 mL
of DMF, 1.03 mmol of phenylacetylene, and 0.060 mmol of BaGa2.
The lines are fit kinetic traces assuming semihydrogenation, and full
hydrogenation reactions are both first order in phenylacetylene and
styrene, respectively.
air exposure during sampling. No other products other than
ethylbenzene or styrene were detected via 1H NMR or HPLC.
Additionally, BaGa4 and BaGa2H2 controls showed minimal
catalytic activity even at 51 bar H2 (<10% conversion, 20 h) for
all reactions. BaGa4 consists of layers of 2D tetrahedrally
coordinated Ga42− sheets. The lack of activity using BaGa4
implies that the unsaturated π-bonding honeycomb network is
essential for activity. We hypothesize that, when the Ga atoms
are coordinatively saturated upon forming BaGa2H2, catalysis is
disrupted via blocking substrate adsorption upon elimination
of the π-network. This loss of activity in the hydrogenated
phase is consistent with the loss of catalytic activity in
LaCu0.67Si1.33H0.3.18 Finally, once the BaGa2 catalyst is
removed by filtering in a glovebox, the activity is eliminated,
indicating the absence of a trace homogeneous catalytic
impurity being responsible for catalysis. Further confirming
this, inductively coupled plasma optical emission spectroscopy
of the n-butanol supernatant after a 24 h reaction shows <1
ppm of dissolved Ga. The XRD pattern of the removed BaGa2
shows minimal changes (Figure S6).
DOI: 10.1021/jacs.9b09856
J. Am. Chem. Soc. 2019, 141, 19969−19972
Journal of the American Chemical Society
The SSA was calculated by measuring the surface area per
gram of the BaGa2 catalyst via Kr Braunauer-Emmett-Teller
(BET) measurements, along with the conversion vs time
(Supporting Information methods). The average surface area
of BaGa2 powder was determined to be 0.272 m2g−1 (Figures
S4 and S5). The SSA at 1 bar H2 is estimated to be 425 h−1.
This makes BaGa2 the most active Pt/Pd-free heterogeneous
catalyst for phenylacetylene hydrogenation and is within 1−2
orders of magnitude of Pt/Pd catalysts under similar
conditions (Table S5).
Additional hydrogenation experiments were performed
under elevated pressure using the solvents with the best
activity, DMF and n-butanol. In DMF, phenylacetylene is
completely converted to styrene and ethylbenzene within 2 h
at 40 °C using 51 bar H2 and 5.5 mol % catalyst (Figure 2c).
Within 15 h, the styrene is completely hydrogenated to
ethylbenzene. The maximum SSA for this catalyst is ∼8390
h−1. We modeled the kinetic traces at both low and high H2
pressure to consecutive reactions that both exhibit first order
reaction kinetics to their respective substrates. At 1 bar H2, the
first order rate constant of phenylacetylene to styrene fits to k1
= 0.035(4) h−1, and the first order rate constant of styrene to
ethylbenzene fits to k2 = 0.035(7) h−1. The slower onset of
conversion from phenylacetylene to styrene is indicative of an
induction period in this BaGa2 sample. An induction period is
not always observed. Figure S7 shows a kinetic trace using a
second BaGa2 catalyst under the same conditions as Figure 2b,
exhibiting no induction period. Future studies are needed to
elucidate the origin of the induction period when present. At
51 bar H2, the rate constants are still first order and much
faster, with k1 = 1.16(19) h−1 and k2 = 0.337(23) h−1. These
differences with respect to H2 pressure indicate the phenyl-
acetylene to styrene conversion reaction approaches first order
in H2, and the styrene to ethylbenzene conversion approaches
1/2 order in H2. It has been well-established, in the conversion
of ethylene to ethane, that the rate law with respect to H2
varies from 1/2 to first order depending on the catalyst and
conditions.27 In the conversion of acetylene to ethylene, most
metals show first order kinetics with respect to H2, comparable
to our observations with phenylacetylene.
In n-butanol, the conversion rate was slower than DMF,
giving 95% phenylacetylene conversion at 100 °C after 20 h
(Figure 3a). Figure 3a also demonstrates the reusability of the
catalyst. The same catalyst retains greater than 50% conversion
after four 20 h cycles. The decreased activity over time is
attributed to the formation of a surface oxide. Figure 3b shows
the Ga 2p region of the X-ray photoelectron spectra (XPS) of
Figure 3. (a) Catalyst recycling experiments (51 bar H2, 100 °C, 20 h,
0.058 mmol of BaGa2, 1.1 mmol of phenylacetylene, 2.4 mL of n-
butanol solvent). (b) XPS spectra of the Ga 2p3/2 and 2p1/2 peaks of
BaGa2 before (red) and after (blue) exposure to air. (*) corresponds
to the nonoxidized BaGa2.
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two different BaGa2 catalysts: one that has been exposed to air
and one that has only been exposed to an Ar-filled glovebox.
After the BaGa2 catalyst is exposed to air, the 2p3/2 and 2p1/2
peaks appear at 1117.90 and 1144.55 eV, indicating an
oxidized Ga3+.28 BaGa2 that has been solely handled in a
glovebox has a surface that is still partially oxidized. However,
the presence of Ga 2p3/2 and 2p1/2 shoulders at 1115.70 and
1142.69 eV are indicative of a reduced anionic Ga surface
species, as would be expected in BaGa2. Further confirming
that surface oxidation inhibits catalysis, the exposure of BaGa2
to either undistilled solvents or air/H 2O immediately
eliminates all catalytic activity. The XPS of a catalyst that has
lost activity over long reaction times shows only the oxidized
Ga 2p3/2 and 2p1/2 peaks at 1117.90 and 1144.55 eV (Figure
S8). Annealing air-exposed BaGa2 at 600−800 °C restores the
activity, and the 1115.70 eV Ga 2p3/2 shoulder re-emerges in
the XPS (Figure S8). Thus, the nonoxidized surface species is
regenerated at these high temperatures. It is not unexpected
that this Ga containing compound is prone to deactivation via
oxidation, as even catalytic activity in PdGa, Pd2Ga, and
Pd3Ga7 is significantly reduced upon oxidation.29−31 Future
explorations will determine whether the surface oxide can be
removed in nonaqueous solution conditions by exploiting the
amphoteric nature of Ga.
Taken together, we have shown for the first time that BaGa2,
a transition metal-free intermetallic Zintl phase, has an
extremely high catalytic activity for alkyne hydrogenation. In
the conversion of phenylacetylene to styrene, the SSAs are
among the highest for Pd/Pt-free catalysts. The exploration of
these materials for catalysis is in its infancy, and future efforts
are needed to achieve long-term oxidative stability, substrate
selectivity, and a mechanistic understanding. BaGa2 is one
member of a large family of hydrogen-absorbing layered Zintl
phases, all likely to have complementary catalytic properties.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.9b09856.
Experimental methods, Rietveld analysis of all XRD,
crystallographic data, atomic coordinates and displace-
ment parameters, powder XRD patterns, Kr adsorption
isotherm, BET measurements and analysis, time depend-
ent conversion products, X-ray photoelectron spectros-
copy, and comparison of the catalytic activities of
phenylacetylene to styrene with different catalysts
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
*goldberger.4@osu.edu
ORCID
Joshua E. Goldberger: 0000-0003-4284-604X
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
K.L.H. and J.E.G. gratefully acknowledge Caitlin Bien and
Casey Wade for BET measurements and Daniel Weber for
SEM measurements. Primary support for this work (K.L.H.)
was provided by the Center for Emergent Materials: an NSF
DOI: 10.1021/jacs.9b09856
J. Am. Chem. Soc. 2019, 141, 19969−19972
Journal of the American Chemical Society
MRSEC under Award DMR-1420451. J.E.G. acknowledges the
Camille and Henry Dreyfus Foundation for partial support.
■
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DOI: 10.1021/jacs.9b09856
J. Am. Chem. Soc. 2019, 141, 19969−19972