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Research Article
pubs.acs.org/acscatalysis

Concerted Chemoselective Hydrogenation of Acrolein on Secondary
Phosphine Oxide Decorated Gold Nanoparticles
Neyvis Almora-Barrios,† Israel Cano,‡ Piet W. N. M. van Leeuwen,‡ and Núria López*,†
†

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Institute of Chemical Research of Catalonia, ICIQ, The Barcelona Institute of Science and Technology, Av. Països Catalans, 16,
43007, Tarragona, Spain
‡
Laboratoire de Physique et Chimie des Nano-Objets, LPCNO, UMR5215 INSA-UPS-CNRS, Institut National des Sciences
Appliquées, 135 Avenue de Rangueil, 31077 Toulouse, France
S
* Supporting Information

ABSTRACT: Secondary phosphine oxides (SPOs) can be used as ligands to
stabilize catalytically active gold nanoparticles (AuNPs). These materials are
active and very selective in the chemoselective hydrogenation of acrolein and
other α,β-unsaturated aldehydes, but the origin of the activity remains elusive.
Here, by means of density functional theory, we identify a cooperative eﬀect at
the AuNP−SPO interface that enables the heterolytic cleavage of the H2
molecule and its kinetically favorable concerted addition to the CO bond
(in a transfer hydrogenation-like mode) to form the corresponding allyl alcohol.
From the mechanism it is possible to identify the descriptors that explain the
activity for a family of SPO-stabilized AuNPs and a set of unsaturated aldehydes.
The activity depends on the basicity diﬀerence between ligand and reactant and
the sites available on the nanoparticle.
KEYWORDS: gold nanoparticle, concerted, density functional theory, hydrogen activation, chemoselectivity

1. INTRODUCTION
The uses of ligand decorated metal nanoparticles (MNPs) are
exponentially growing, as they combine the advantages of
heterogeneous catalysts with the selectivity provided by
homogeneous catalysts.1−12 Ligands serve as capping agents,
limiting the growth, and thus help to maintain well-dispersed
and small size MNPs, even with very well-deﬁned stoichiometries. However, as ligands are chemically bonded to the metals,
they can aﬀect the catalytic properties,13−19 either by blocking
the active metal sites20 or altering the properties at the metal/
ligand interface.15,21,22 While detailed structural studies of these
nanoparticles exist,23 the role of the ligands when employed as
catalysts is still not fully understood.
The hydrogenation with high chemoselectivity of imines,
ketones, and α,β-unsaturated aldehydes catalyzed by MNPs has
been reported.24−26 Particularly, the chemoselective hydrogenation of α,β-unsaturated aldehydes can produce unsaturated
alcohols, compounds widely employed in the pharmaceutical
and ﬁne chemical industries.27 Nevertheless, these products are
diﬃcult to obtain because the hydrogenation of CC bonds is
thermodynamically preferred (Scheme 1).28,29 To drive the
selective hydrogenation of CO bonds in the presence of
other unsaturations remains a challenge for heterogeneous
catalysts.30
Gold has attracted growing interest as catalyst due to its
intrinsic selectivity in various reactions.31 Gold nanoparticles
(AuNPs) perform the selective hydrogenation of acrolein to
allyl alcohol, but the reported activities were low.32,33 The
© 2017 American Chemical Society

Scheme 1. Partial Hydrogenation of Acrolein and Reaction
Energies with Respect to Acrolein in the Gas-Phase

activity of gold can be improved by ligand control. For instance,
thiol-modiﬁed gold clusters (Au25(SR)18) were reported to
hydrogenate ketones with high activity and chemoselectivity
but for acrolein the selectivity was around 90%.34 Additionally,
van Leeuwen et al. described a set of secondary phosphine
oxides (SPOs) that can be used as ligands for the synthesis of
AuNPs with catalytic properties. The SPO-stabilized AuNPs are
highly chemoselective in the hydrogenation of a wide range of
substituted aldehydes.35,36 Typical conditions for this reaction
were 60 °C, 40 bar H2, and tetrahydrofuran (THF) as solvent.
The characterization showed that the diphenyl phosphine oxide
(Ph2PO) ligand covers the surface of the small AuNP (size 1.61
± 0.16 nm, corresponding stoichiometry ∼55-atoms) with a
Received: February 2, 2017
Revised: April 24, 2017
Published: April 26, 2017
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ing to 1.56:1 ratio), in agreement with a metal−ligand ratio in
the range 1.32:1−1.84:1 found in the experiments.35 The
adsorption energy was calculated as Eads = Emol+cat − Ecat −
Emol., where Emol+cat is the energy of the Au55(Ph2PO)27
nanoparticle with the adsorbed molecule, Ecat is the energy of
the simulation of the Au55 nanoparticle with adsorbed 27
Ph2PO species (Au55(Ph2PO)27), and Emol is the energy of the
adsorbed molecule in gas phase or in liquid phase. The
solvation contribution for the adsorbed molecules in the liquid
phase was calculated using the Multigrid Continuum Model
(MGCM) methodology.45 We considered a variety of diﬀerent
adsorption geometries to identify the energetically most
favorable location. Transition states and barriers were obtained
using the Climbing Image version of the Nudged Elastic Band
(NEB) algorithm.46 The determined transition states were
veriﬁed by having only one imaginary frequency.

metal−ligand ratio around 1.3:1. The reaction mechanism and
the factors controlling activity and chemoselectivity have not
been identiﬁed. We have addressed them by ﬁrst-principles
simulations, identifying that the combination of bulky SPO
ligands and a Au nanoparticle core produces a Frustrated Lewis
Pair (FLP)24,37 that induces the heterolytic cleavage of H2. The
resulting H2-ion pair can be selectively transferred only to the
CO moiety through a concerted mechanism responsible for
the unique chemoselectivity observed.

2. COMPUTATIONAL DETAILS
To investigate how activity and chemoselectivity are produced
by the SPO−AuNP, we have used dispersion-corrected density
functional theory with the the Vienna ab initio simulation
package (VASP),38,39 which implements the projector
augmented wave method (PAW).40 The wave function was
determined by expansion of the valence electrons with plane
waves with kinetic energies up to 450 eV, and the Γ point was
used to sample the k space. Total energies and electron
densities were computed with the Perdew−Burke−Ernzerhof
(PBE) functional41 complemented by the dispersion D2 term
as presented by Grimme42,43 with our values for the metals.44
First, we have investigated the structure of the SPO coated
AuNPs. The pentavalent phosphine oxide interacts with gold
and forms the deprotonated phosphinito anion, generating the
Au-SPO nanoparticle. The AuNP was considered as an
icosahedral structure, containing 55 Au atoms with a diameter
of 1.16 nm and modeled as a hexagonal box with dimensions of
22 × 22 × 22 Å3. The model of the catalyst (SPO-AuNP) was
derived from ref 9. The structure was modiﬁed with the
Materials Studio version 6.1 package, and the ﬁnal simulation
system consisted of a Au55 nanoparticle capped with 27 Ph2PO
ligand molecules placed in a box of 30 × 30 × 30 Å3 size. Upon
optimization (Figure 1), the phosphorus atoms sit at an average
Au−P distance of 2.602 Å, and the oxygen atoms at a Au−O
distance at around 2.9 Å. This structure consists of a very
densely packed ligand layer on the AuNP surface (correspond-

3. RESULTS AND DISCUSSION
Gold possesses a very limited capacity for hydrogen
adsorption.24,26,47 H2 homolytic dissociation (H2+2* → 2H*)
on the Au(111) surface is endothermic by 66.6 kJ mol−1, and
the barrier is very high, 139.9 kJ mol−1.37 On the naked Au55
nanoparticle, the energy barrier for dissociation is lower (75.3
kJ mol−1) and the reaction is endothermic by 10.1 kJ mol−1
(orange line in Figure 2). Thus, even for Au55 the barrier is too
high to aﬀord an active catalyst, in agreement with the
experimental observations.

Figure 2. Reaction energy proﬁle for the H2 dissociation on bare Au55
and Lewis bases: acetone, acrolein, and SPO ligands. Color codes:
orange: bare Au55, light red short dot: acrolein, red short dash:
acetone, and wine SPOs.

This contrasts with the AuNP-SPO model, for which the
dissociation of the H2 molecule is exothermic by 61.8 kJ mol−1
and shows a barrier of 52.1 kJ mol−1 (not ZPVE corrected; see
Figure 2 and Supporting Information, Section 1). More
importantly, the dissociation is not homolytic, but takes place
through a heterolytic path in which the ﬁnal product is a tight
ion pair H2 + 2* → H+ + H−. The hydride, H−, is adsorbed on
the metal site (Au−H−), and the proton, H+, binds to the
oxygen atom of the ligand (Ph2PO−H+). Electrostatic forces
stabilize these ions, yielding H+−H− contacts of 2.11 Å and
Bader charges +0.69 and −0.03 |e−|. The AuNP−SPO interface
is a Lewis acid−base adduct that fulﬁlls the requirements
established by Guo for the formation of Frustrated Lewis

Figure 1. DFT adsorption conﬁguration of 27 Ph2PO ligands on Au55,
corresponding to a metal−ligand ratio of 1.56:1 in the range of the
experimental results.35 Yellow spheres represent Au atoms, and the
stick models represent the adsorbed (Ph2PO). Color codes: P in pink,
O in red, C in gray, and H in white.
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−1

24,37,48

exothermic by 38.6 kJ mol . Propanal desorption is
endothermic by 45.3 kJ mol−1.
The competitive formation of desired alcohol takes place
through a concerted step, resulting in the addition of the H2
pair to the CO bond. The non-ZPVE corrected barrier is
52.1 kJ mol−1 and, thus, 8 kJ mol−1 smaller than that of the
hydrogenation of the CC bond. The concerted transition
state shown in Figure 4 is stabilized by dipolar interactions in a

Pairs.
Additionally, we have investigated the role of
reactants (acrolein or acetone) during the H2 dissociation on
bare Au55 (see Figure 2 and Supporting Information, Section
1). In both cases, the H2 molecule dissociates heterolytically,
entailing the formation of a hydride on the surface and a proton
which bonds to the carbonyl oxygen. This step has an energy
barrier similar to that of the same step on AuNP-SPO (Figure
2), but the main diﬀerence resides in the adsorption energies of
acrolein, acetone, and SPO on Au55. The adsorption energy for
one SPO ligand is −84.9 kJ mol−1 per Ph2PO molecule, but the
27 Ph2PO ligands interact with the AuNP by −6.35 kJ mol−1
per Ph2PO molecule. The adsorption of SPO molecules is
favored in comparison to acrolein or acetone because the SPO
ligand can be stabilized and, in addition, aﬀects the electronic
structure of the AuNP, thus leading to a more eﬀective
promotion of the reaction.9
When Au55 is decorated with phosphine oxide ligands
(AuNP-SPO), the adsorption energy of acrolein (−23.2 kJ
mol−1) is similar to that of bare Au55, but it is weaker than the
adsorption energy of prop-2-en-1-ol (−45.3 kJ mol−1). This is
due to the hydrogen bond between the OH of prop-2-en-1-ol
and the O atom of the Ph2PO ligand at a distance of 1.399 Å.
The adsorption energy of propanal is similar to that of prop-2en-1-ol (−40.5 kJ mol−1). However, this molecule is at the
outer-surface region because the distance between the gold
atoms and the subtrate is around 2.5 Å. Notwithstanding, when
the hydrogen molecule is dissociated by the FLP, the
adsorption of acrolein is stronger due to formation of a Hbond between the carbonyl oxygen atom of acrolein and the
proton attached to the SPO ligand by −34.7 kJ mol−1 (Figure
S3, bottom). We have also studied an alternative model in
which the CC bond of acrolein is close to the proton and the
hydride, but the adsorption energy does not improve. From
these adsorbed structures, we investigated the mechanisms for
all possible paths for the competitive hydrogenation of CO
and CC bonds (Figure 3).
The route to propanal, the thermodynamically preferred
product, encompasses two steps. In the most favorable ﬁrst
step, the SPO-H proton is transferred to C3 of acrolein with a
barrier of 59.7 kJ mol−1, forming an intermediate lying at
−135.1 kJ mol−1. The transfer of the hydride to C2 is

Figure 4. Structure, distances (Å), and imaginary frequency (cm−1) for
the transition state corresponding to the concerted mechanism in the
hydrogenation of CO of acrolein on AuNP-SPO. The inset
highlights the four-membered ring formation and the distances. The
same color codes as in Figure 1.

four-membered ring structure formed by the hydride on the
gold surface (Au−H−), the proton bound to the oxygen atom
of the SPO ligand (Ph2PO-H+), and the O and C atoms
belonging to the carbonyl group of acrolein. The TS is
nonsynchronous because the O−H bond is 70% formed while
the C−H bond is 59% formed, following a geometric criterion
for the bond lengths.49 This thus resembles a transfer
hydrogenation mechanism.50 As for other H2 additions assisted
by FLP reported in the literature, these reactions are in
equilibrium.51 Prop-2-en-1-ol desorption is endothermic by
40.5 kJ mol−1. The concerted one-step mechanism observed
here for the heterogeneous chemoselective hydrogenation of
acrolein contrasts with the homogeneous Rh-SPO catalyst used
in the transfer hydrogenation of ketones in isopropanol, where
the seven-membered ring transition state along a concerted
outer-sphere pathway is generally preferred.52
Furthermore, we have considered the diﬀerence in rate
between aldehydes and ketones found for the AuNP-SPO
catalyst. Acetone interacts only weakly with the AuNP-SPO,
even when the hydrogen molecule is dissociated, with the
adsorption energy being as low as −2.9 kJ mol−1 (Figure 3 and
Table S5). In fact, the diﬀerent adsorption behaviors between
ketones and aldehydes on the AuNP-SPO can be explained by
the electrostatic interactions combined with steric eﬀects. The
Bader charge reveals that the CO group of the aldehydes is
slightly more negatively charged (∼0.03 |e−|) than the CO
group of analogous ketones (Table S6). In addition, the ketone
cannot be accommodated in the small cavity formed by the
dense coverage of bulky SPOs. Consequently, the ligand
imposes severe changes in the conformation and binding
geometries of the reactant. This behavior is similar to other
catalytic systems based on ligand-modiﬁed nanoparticles, for
which the ligands limit the accessibility to the active sites and
modify the properties of the ligand−metal interface.14,53 The
results are in line with the control of selectivity by high surface

Figure 3. Energy proﬁle for the selective hydrogenation of acrolein
and acetone over AuNP-SPO catalyst. Black solid line = heterolytic
dissociation of H2, wine dotted line = propanal, wine solid line = prop2-en-1-ol, and red dashed line = 2-propanol.
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coverage on Pd and Pt in the hydrogenation of α,β-unsaturated
aldehydes reported in ref 54.
The hydrogenation of ketones catalyzed by the cluster
Au25(SR)18 described in ref 26 presents some crucial diﬀerences. The outermost surface structure of Au25(SR)18 is very
open, and the heterolytic H2 dissociation occurs because the
CO group of the ketone is further stabilized by the protic
solvent (ethanol). The hydrogenation then proceeds sequentially, as we have found for the autocatalytic acrolein
hydrogenation (see Supporting Information, Section 1).
However, for the AuNP-SPO catalyst, the solvent was found
to aﬀect the adsorption and desorption of all reactants and
products signiﬁcantly. The presence of an important dipolar
interaction in both the adsorption and TS states also explains
the preference for apolar solvent.35,36 Indeed, the computed
solvation energies in THF are the lowest (Table S2), indicating
that the adsorption would be more favored. Moreover, the
AuNP-SPO catalyst is too crowded due to the presence of the
bulky ligands, and consequently, the solvent molecules cannot
be accommodated in the small cavity formed by the dense
coverage of SPOs. Therefore, the ligand−nanoparticle structure
determines the catalytic behavior, and the structure−activity/
selectivity relationships need to be addressed accordingly.
Once the reaction mechanism in the AuNP-SPO is
established, the performance for diﬀerent SPO ligands (L)
and reactants (R) can be rationalized. We have taken the
experimental results reported in ref 35 with the conditions: 60
°C, 40 bar H2, and THF (5 mL) as solvent. The conversion
after 18 h is taken as indicative of the reaction rate. Out of the
25 experiments performed, the rates of 18 experiments have
been correlated to two independent parameters representing
the ligand−-reactant pair and the catalyst (Figure 5). The
experiments for the hydrogenation of p-nitrobenzaldehyde were
discarded, since the conversion was quantitative and no rate
could be extracted. In addition, two points (R1-L5 and R2-L2)
were found to be outliers in our description and were

eliminated from the reaction pool. As we have seen in Figure
5, the key point for the activity corresponds to the balance
between the basicity of the PO bond in L and that of
substrate R. This diﬀerence drives the transfer hydrogenation. If
L is very basic, the adsorption of H2 in the form of the ion pair
is favored, but excessive stabilization would hamper H-transfer
to the CO bond. The simplest descriptor for the basicity
contribution is represented by the HOMO(L)-HOMO(R)
diﬀerence. The AuNPs described in ref 35 diﬀer in diameter
and Au:L ratio. The term representing the catalyst is more
diﬃcult to address but relates to the surface to volume S/V
exposed in the nanoparticles (Supporting Information, Section
4.2) and the ligand coverage of this surface. When these two
terms are multiplied, they constitute a measure of the fraction
of nonactive Au atoms. The multifactorial linear-scaling
relationship for the reactivity with electronic and geometric
contributions is shown in Figure 5. Technical details are
presented in the Supporting Information, Section 4.2, Tables
S7 and S8.
Figure 5 shows that the electronic (L-R) and geometric (AuL) terms present a similar contribution. The larger the
HOMO(L)-HOMO(R) term (Supporting Information, Table
S8), the higher the driving force for the transfer hydrogenation
is. In addition, the blocked Au atoms have a detrimental
contribution to the activity, so small diameters and low [Au:L]
ratios are preferred. The rule found can explain the reactivity
not only for relatively simple molecules but also for other more
complex ones. This is the case of cinnamaldehyde (R3), which
contains conjugated CO and CC bonds and an isolated
aromatic ring. In the ﬁtting, only the electronic eﬀect of the L-R
pair and the size-coverage of the nanoparticle are taken into
account. R3 possesses an extended π-system that can interact
through van der Waals interactions with the ligands.55,56 These
contributions are not included in the ﬁtting equation and would
result in larger interaction energies with the nanoparticles and
thus in longer residence times that would be an extra
contribution to activity. Therefore, the deviation in the rate
of the empty points corresponding to this substrate can be
attributed to the fact that the interaction of R3 is larger than
those of the other substrates due to van der Waals
contributions of the side chain, which increase the residence
time of the reactant and thus its conversion.

4. CONCLUSION
In summary, we have shown that SPOs acting as ligands for
AuNPs provide an eﬀective Frustrated Lewis Pair that allows
the heterolytic activation of H2, which can then be added via a
concerted mechanism to unsaturated aldehydes generating
valuable unsaturated alcohols. The electronic and geometric
terms that control the reaction have been identiﬁed and can
explain the hydrogenation of four compounds with ﬁve
diﬀerent SPO-stabilized AuNPs, showing its rationalization
via collective descriptors. The results obtained in this work may
provide a wide perspective to design new hybrid catalysts by
tuning the ligand.

Figure 5. Experimental conversion taken from ref 35 as a function of a
two-variable descriptor: the computed diﬀerential basicity HOMO(L)HOMO(R) (electronic) and the empty sites on the Au nanoparticle
surface obtained from the diameter of AuNP and the [Au/L] ratio
(geometric) from the experimental determination. The regression
coeﬃcient, r, is 0.94. Shapes stand for ligands (L), and colors stand for
reactants (R). The red line corresponds to the dependence for R3,
which needs an extra term in the ﬁtting equation that includes the
lateral chain interaction (dispersion).

■

ASSOCIATED CONTENT

* Supporting Information
S

The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.7b00355.
Calculated data for the H2 dissociation and autocatalytic
pathway of acrolein and acetone on Au55 nanoparticles;
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adsorption energies, as well as the solvation contribution;
reaction mechanism of formation of propanal, prop-2-en1-ol, and 2-propanol on AuNP-SPO and bader charge
analysis of aldehydes and ketones; collective descriptors
used to explain the activity for a family of SPO-stabilized
AuNPs and a set of unsaturated aldehydes. Finally the
structural models are in doi.org/10.19061/iochem-bd-125. (PDF)

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: nlopez@iciq.es.
ORCID

Neyvis Almora-Barrios: 0000-0001-5269-2705
Piet W. N. M. van Leeuwen: 0000-0002-2165-7090
Núria López: 0000-0001-9150-5941
Notes

The authors declare no competing ﬁnancial interest.

■

ACKNOWLEDGMENTS
The authors acknowledge the MINECO project (CTQ201568770-R) and grant FPDI-2013-16194 for ﬁnancial support.
P.v.L. thanks the Université Fédérale Toulouse Midi-Pyrénées
́
for an IDEX Chaire dAttractivité.

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3954

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