Surface-Plasmon-Mediated Hydrogenation of Carbonyls Catalyzed by Silver Nanocubes under Visible Light

Article abstract of DOI:10.1021/acscatal.7b02128

Plasmonic nanoparticles are exciting and promising candidates for light-activated catalysis. We report herein the use of plasmonic nanocubes for the activation of molecular hydrogen and the hydrogenation of ketones and aldehydes via visible light irradiation at 405 nm, corresponding to the position of the plasmon band of the nanocubes, at 80 °C. Only 1 atm of molecular hydrogen is required to access, using catalytic amounts of silver, primary, and secondary alcohols, with complete chemoselectivty for C=O over C=C reduction. The resulting catalytic system was studied over a scope of 12 compounds. Exposure to other wavelengths, or absence of light failed to provide activity, thus proving a direct positive impact of the plasmonic excitation to the catalytic activity. By varying the irradiation intensity, we studied the relationship between plasmon band excitation and catalytic activity and propose a potential reaction mechanism involving plasmon-activated hot electrons. This study expands the scope of reactions catalyzed by free-standing plasmonic particles and sheds light on H₂ activation by silver surfaces.

Full text of DOI:10.1021/acscatal.7b02128

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Article
Surface plasmon mediated hydrogenation of carbonyls
catalyzed by silver nanocubes under visible light
Michael Landry, Alexandra Gellé, Beryl Yu Meng, Christopher J Barrett, and Audrey Moores
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b02128 • Publication Date (Web): 09 Aug 2017
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Surface plasmon mediated hydrogenation of carbonyls catalyzed by
silver nanocubes under visible light
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Michael J. Landry, Alexandra Gellé, Beryl Y. Meng, Christopher J. Barrett, and Audrey Moores*
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montréal, QC, H3A 0B8, Canada
ABSTRACT: Plasmonic nanoparticles are exciting and promising candidates for lightꢀactivated catalysis. We report herein the use
of plasmonic nanocubes for the activation of molecular hydrogen and the hydrogenation of ketones and aldehydes via visible light
irradiation at 405 nm, corresponding to the position of the plasmon band of the nanocubes, at 80°C. Only 1 atmosphere of
molecular hydrogen is required to access, with catalytic amounts of silver, primary and secondary alcohols, with complete
chemoselectivty for C=O over C=C reduction. The resulting catalytic system was studied over a scope of 12 compounds. Exposure
to other wavelengths, or absence of light failed to provide activity, thus proving a direct positive impact of the plasmonic excitation
to the catalytic activity. By varying the irradiation intensity, we studied the relationship between plasmon band excitation and
catalytic activity and propose a potential reaction mechanism involving plasmonꢀactivated hot electrons. This study expands the
scope of reactions catalyzed by freeꢀstanding plasmonic particles and sheds light on H activation by silver surfaces.
2
KEYWORDS: photocatalysis, silver nanoparticles, hydrogenation, plasmonic catalysis, surface plasmon resonance
2
1,23,35–39
Energy consumption by the chemical industry is a significant
source of pollution via generation of greenhouse gases.
degradation.
SPRANP operate according to three
1–3
major schemes: their plasmon is enabled by visible light and
they either activate a metal oxide support, another metal, or act
as a catalyst on their own (Scheme 1). For instance, Au
nanoparticles (NPs) supported on oxides have been shown to
catalyze the oxidation of formaldehyde, alcohols,
amines to6,47imines,
Photochemical reactions have been investigated for over a
century, with the endꢀgoal of harvesting light as a renewable
4
energy source and converting it directly into chemical energy.
38
40–43
Photochemistry can also open routes to products which are not
and
5
44–46
accessible via thermal routes. Energy transfer is a key step in
C–C and amineꢀalkyneꢀaldehyde
4
46
being able to use light to do meaningful chemical work, and to
this end, several light harvesting systems have been
couplings,
hydroamination of alkynes,
of
oxidative
48
degradation
phenol,
oxidative aldehydeꢀamine
6
7–9
49
50–52
developed, including solar cell materials, photocatalysts,
condensation to amide, and hydroxylation of benzene.
supported SPRANP, oxidative reactions are mediated by
excited hot electrons from SPRANP which are transferred to
In
1
0
and photoꢀactivated materials, relying on materials such as
11,12
13,14
TiO2,
complexes,
porphyrin dyes,
ruthenium polypyridine
Lightꢀactivated catalytic
reactions have seen wide use in organic chemistry and also in
remediation and depollution of organic dyes and conjugated
1
5–17
18,19
21,38
or organic dyes.
the support where catalysis takes place (Scheme 1).
8
20
organic systems.
Recent efforts have allowed the
development of such photocatalysts with a focus on activation
21
with visible light.
Nanomaterials of Cu, Ag, and Au possess an optical and
electronic property called surface plasmon resonance (SPR),
which confers to them powerful absorptive properties in the
visible region. Conducting electrons in these materials
22–24
oscillate in resonance with the incoming light field,
causing three effects. 1) SPR causes strong light absorpt2i5o,2n6
and scattering translating into exciting optical properties.
2
) Strong field enhancement at the surface vicinity of these
materials allows them to enhance signals, and was exploited to
develop surface enhanced Raman spectroscopy (SERS) used
2
7–32
for detection with molecular sensitivity.
3) Field
enhancement also causes local heat generation and this has
2
7,33,34
been used in the development of nanomedicines.
In the
last 10 years, researchers have studied lightꢀmediated catalysis
using SPRꢀactive nanoparticles (SPRANP), including that for
water splitting, CO2 reduction, and organic pollutant
Scheme 1: General categories of plasmonic photocatalysts relying
on SPRANP.
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Researchers have looked into combining the catalytic activity prism particles observed. These cubes are monodisperse with
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of nonꢀplasmon active transition metals, such as Pt or Pd with
optical properties of SPRANP. For instance, alloys of plasmon
an average edge length of 126 ± 12 nm (counted over 120
cubes in TEM images). In STEM, the shell of protective PVP
polymer was clearly visible (Figure S4). Dynamic light
scattering (DLS) experiments were also performed and results
are consistent with SEM and TEM data (See supplementary
information). Energyꢀdispersive Xꢀray spectroscopy (EDS)
measurements were obtained on Ag NCs imaged by STEM to
probe their purity (Figure S5). Ag NCs were found to contain
only Ag, Cl, C, and O. Importantly no other noble metals (Pt,
Pd, and Ru), which could also lead to the expected reduction
chemistry, was detected. An EDS linescan was also performed
across a couple of AgNCs observed by high resolution STEM
(Figure S6). Carbon and oxygen were preeminent along the
edges of the cubes, revealing the surface coverage of the PVP
polymer. The presence of chlorine revealed by EDS was
consistent with the Ag NC synthesis, which relies on chloride
anions in order to direct the selective facet growth of the
cubes. Xꢀray photoelectron spectroscopy (XPS) confirmed the
presence of Ag, Cl, C, O, and N in the sample. Cl content
could be quantified against Ag and Cl and accounts for 8% of
the inorganic material (Figure S7). The 3 d5/2 band of silver,
centered at 368.3 eV is consistent with Ag(0). Xꢀray
diffraction (XRD) featured (111) and (200) peaks distinctive
4
6,53,54
and nonꢀplasmon metals were investigated.
Besides this,
Halas and coworkers unraveled the potential of a lessꢀexplored
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plasmonic metal: aluminium.
Coreꢀshell Al/Al O3
2
nanocrystals were used as supports for Pd NPs, for the
selective hydrogenation of acetylene to ethylene under whiteꢀ
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6
light illumination.
Typical reactions such as ethanol
dehydrogenation can be enhanced with such coreꢀshell
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7
particles. On the other end, freeꢀstanding, pure SPRANP can
also perform plasmonic photocatalysis, for instance in
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oxidative couplings,
activations of reagent gases, and
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reductive couplings.
The Scaiano group showed the
reduction of alcohol with hydrogen peroxide with unsupported
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2
Au NPs. The group of Linic looked at Cu NPs as SPRꢀ
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3
activated propylene oxidation catalysts. The same group
explored silver nanocubes (Ag NCs) harvesting light via SPR
to directly afford hot electrons and catalyze the epoxidation of
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3
ethylene. In an effort to explore more the scope of catalytic
processes available from pure silver as a plasmonic metal, we
wanted to look at their reductive chemistry in organic solvents.
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Hydrogenation is a reaction of high industrial relevance, for
which silver is typically a less active metal requiring high
74
hydrogen pressure; its limited ability to activate H compared
of a pure Ag(0) phase(Figure S9). The surface plasmon band
(SPB) was measured using UVꢀvis spectroscopy and was
determined to lie centered at 410 nm (Figure 2).
2
6
5
to other metals is well documentated. Still it affords
heterogeneous catalysts with excellent chemoselectivity for
65–69
the reduction of C=O over C=C bonds.
Au NPs, both in
the free and supported versions, are known to enable the
70,71
activation of molecular hydrogen via SPR,
but a similar
effect had not been shown yet for silver. Activating silver
towards H splitting can help reduce the high temperature and
2
pressure requirements for this reaction.
Herein, we report that plasmonic Ag NCs are able to drive
catalytic reduction reactions and direct activation of H2
through the absorption of visible light. This expands the use of
catalytic plasmonic nanoparticles to reductive organic
chemical transformations, where it has been less explored.
Figure 2: UVꢀvis spectrum of Ag NCs that demonstrates the
surface plasmon band ranging from 400 ꢀ 420 nm.
To establish catalytic activity, the Ag NCs were first tested for
the hydrogenation of camphor to the racemic mixture of
borneol and isoborneol, using a hydrogen pressure of 1
atmosphere for 24 hours (Figure 3). Camphor was selected as
model substrate for this reaction because, in the presence of
light, it does not form photoꢀradicals as other arylketones are
known to do. When this reaction was performed under one
atmosphere of H in the dark, at 40°C or 60°C, no conversion
Figure 1: TEM (left) and SEM (right) images of Ag NCs.
2
was measured after 24 hours. Further heating at 80°C or 100°C
afforded only trace or 6% conversions respectively under the
same conditions (Figure 3). This is consistent with past
accounts, as typically much higher pressures of molecular
hydrogen (i.e. 40 bars) are required to trigger hydrogenation
For this work, Ag NCs were selected for their enhanced SPR
7
2,73
properties arising from their sharp vertices.
These sharp
vertices are wellꢀknown to create “hot spots” where SPR is
23,35
greatly enhanced.
We synthesized Ag NCs following the
66,75
procedure already reported, using AgNO3 as a precursor,
polyvinylpyrrolidone (PVP) as a stabilizer, and HCl as an
with silver nanoparticles.
However when light from a 60
W lightbulb was introduced during the reaction, a promising
increase in yield of 17% was measured at 40°C. Upon raising
the temperature, the yields improved further and reached 57%
at 100°C. In order to further ascribe this activity enhancement
to the Ag NCs SPR properties, we employed a laser diode
53
etchant. Transmission electron microscopy (TEM) and
scanning electron microscopy (SEM) (Figures 1, S2, S3, and
S4) revealed that most of the synthesized nanoparticles
featured a cubic morphology, with occasionally a few rod or
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conditions. A mostly linear loss of camphor was observed,
emitting light precisely at 405 nm, a wavelength within their
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plasmon band. The typical experimental setup for this reaction
is described in Figure S1. A dramatic improvement of yield
was observed using the 405 nm laser, enhancing the yield to
87%, an increase of 45 points compared to the wideꢀspectrum
light bulb of similar intensity (Figure 3). A series of control
without induction period (Figure S12).
Unsupported SPRANP have been described to enable
plasmonically enhanced catalysis via 3 main mechanisms:
2
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i) the formation of hot electronꢀhole pairs at the surface of the
nanoparticle, followed by transfer of charge carriers to an
adsorbed substrate, ii) the photoꢀinduced increase of the
nanoparticle temperature and its thermal effects on the
reaction rate, iii) the photoꢀinduced local field enhancement
and its effect on other photoꢀactivated processes. The reaction
of hydrogenation with silver does not proceed via photo
excitation of an organic molecule involved, so a field
enhancement effect (iii) is unlikely. Also, since reaction with
Ag NCs in the dark was negligible across the range of
temperatures accessible in the liquid phase of dioxane, a
potential thermal effect of the SPR (ii) should not lead to
activity enhancement. Thermal effects are also typically
encountered with nanoparticles much smaller than the ones we
tests established that absence of H , absence of particles or
2
exposure to 532 nm or 633 nm laser light failed to afford
meaningful conversions, under the temperature spectrum
explored herein (Table S2).
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used. The dependence of the yield on the light intensity
before saturation is also in agreement with a linear
relationship, consistent with a “hotꢀelectron” process for low
77
intensity photoactivation. Recently, the group of Halas
demonstrated the activation of H by gold nanoparticles under
2
plasmonic activation, and proposed that hot electrons are
directly responsible for the splitting of the H molecule. Thus
we propose a similar mechanism in Scheme 2. When light is
absorbed by the Ag NCs, a transient electron/hole pair is
formed at its surface and the resulting hot electron is
transferred to an adsorbed H2 molecule. The rest of the
Figure 3: Yields observed for the hydrogenation of camphor
with Ag NCs as catalyst. Reaction conditions: 1 mg of Ag
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NCs, 1 mmol of camphor and 5 mL of dioxane, H pressure of
2
1 atm, 24 hours.
Now that a link between light and catalytic activity was
determined, a solvent screening was performed to understand
the impact of the polarity on the reaction. Dioxane, water,
ethanol, hexane, ethyl acetate, and dichloromethane were
78
proposed mechanism follows a PolanyiꢀHoruiti scheme.
Interestingly, it has been suggested by theoretical
investigations, that hydrides on silver surfaces may be directly
photoꢀactivated by SPR, which could participate as well in the
assessed under the newly optimized conditions (H pressure of
2
1 atm, 24 h) at their boiling point, or at 40°C. We correlated
the resulting yields (Table S3) with the solvent dielectric
constant, ε, a classic parameter used to measure polarity and
boiling temperature. Interestingly, a clear trend was observed,
where the more polar the solvent, the better the activity
79
process.
Moreover, AgCl and Ag@AgCl NCs have been reported by
others to be active photocatalysts in polymerization and
oxidation reactions and it was important to rule out the
possibility to have AgCl phases in asꢀsynthesized
(Figure S10 and S11). Dioxane and water performed the best,
80ꢀ82
nanocatalysts.
XRD did not show any sign of crystalline
achieving similar yields of near 80% at 100°C. The case of
dioxane is interesting: while this molecule has a dielectric
constant of zero because of its high symmetry, it possesses
polar bonds, which have a local polarizing effect on the
medium. Similar results have been reported by others, where
dioxane performed very well and similarly to polar solvents
AgCl phase, nor any typical UV signature between 200 and
00 nm (Figure 2).
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for C=O hydrogenation.
Ethanol only provided 30%
conversion at 78°C, a temperature at which dioxane afforded
the excellent yield of 87%. All other solvents, all apolar, gave
poor yields.
To probe further into the photocatalytic nature of this reaction,
a light intensity vs yield experiment was also conducted.
Under optimized reaction conditions (H pressure of 1 atm, 24
2
h, 80°C), the 405 nm laser was expanded to the size of the
2
reaction vessel, and used at its full intensity of 204 mW/cm ,
then also under reduced intensities stepwise by employing
various increasing optical density (OD) neutral density filters.
2
As shown in Figure 4, below 60 mW/cm the yield increased
2
Figure 4: Yield (%) vs laser intensity (mW/cm ) for the
hydrogenation of camphor with Ag NCs as catalyst in dioxane,
almost linearly, while after this value, a saturation was rapidly
established. This saturation can be explained potentially by
diffusion limitations in a solutionꢀbased catalytic process,
when yields exceed 50%. A kinetic study was also carried out
using camphor as the model reaction under hydrogen
with H pressure of 1 atm, 80 °C and for 24 hours.
2
With these results in hand, the scope of this reaction was
explored with other ketones and aldehydes (Scheme 3), setting
the temperature to 80°C and using the 405 nm laser as the
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irradiation source. Camphor (1), for which we optimized the
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reaction gives a yield of 87%. Other aliphatic ketones gave the
corresponding alcohol (2-3) in moderate yields in the 30s and
50s of %. Aliphatic aldehydes afforded contrasted results with
yields between 33% and 76% for (4) to (6). Moving to
conjugated carbonyl molecules, we observed better yields,
consistent with their known moreꢀreactive nature towards
hydrogenation. Benzophenone gives (7) with the best yields of
the series (92%) and good yields around 75% are seen for
benzylꢀalcohol (8) and its pꢀchloro counterpart (9). Perfect
selectivity for (9) shows the tolerance of the procedure for
chloroarene functionality. The diꢀmꢀtꢀbutyl benzylꢀalcohol
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(10) affords a low yield of 32% likely because of steric bulk
which can hinder access to the metal nanoparticle surface. In
the example of α,βꢀunsaturated aldehydes, we observe an
interesting selectivity for the C=O bond reduction over the
C=C bond, consistent with past accounts using Ag NPs for
7
5
hydrogenation. Citral is thus cleanly converted to geraniol
(11) at 79% yield. With cinnamaldehyde, 80% yield of
cinnamyl alcohol (12) was produced, along with 5% of
hydrocinnamyl alcohol.
Scheme 3: Scope of products obtained from SPRꢀenhanced
hydrogenation of ketones with Ag NCs.
To elucidate the potential leaching of soluble Ag species
during the reaction, ICPꢀMS measurements were performed on
the filtrate of the optimized hydrogenation reactions of
camphor, after Ag NC removal. 0.57 ppm of Ag was measured
in the product, which constitutes a negligible contamination
(see Supporting Information). In an effort to determine if such
leached soluble Ag species were responsible for catalytic
reactivity, we performed two distinct experiments: a hot
filtration and a blank test using AgNO as catalyst. For the hot
3
filtration, an optimized catalytic run was performed at 80°C,
with laser excitation. After 2 hours, the Ag NCs were filtered
off the reaction medium, and the run was further monitored for
activity, under the same conditions for 6 additional hours.
Before the separation, a yield of 21% conversion to borneol
was measured. At the end of the run, a similar yield of 23%
was obtained. We also performed a reaction using AgNO as
3
catalyst, added to the reaction at a concentration of 0.57 ppm.
This blank test afforded only trace conversion over the 24
hours along with the appearance of a silver mirror on the side
of the flask, characteristic of Ag(0). Homogenous Ag species
have been reported recently to be active for hydrogenation, but
require much higher loadings, H pressures, and electron
accepting ligands. These tests established that soluble species
can not account for the reactivity described in this study.
2
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In an effort to explore organic reactions catalyzed by SPR
activated Ag NCs, we also investigated the oxidation of
aldehydes and alcohols to carboxylic acids. Ag NCs are
known to activate O2 5 with SPR and enable gas phase
Scheme 2: Proposed mechanism for the hydrogenation of
carbonyl compounds with H catalyzed by Ag NCs.
2
3
epoxidation of alkenes. For this study, we explored the
oxidation of pꢀhydroxybenzaldehyde under air at atmospheric
pressure for 18 hour at 60°C. Under these conditions, the
corresponding carboxylic acid is produced at 95% under 405
nm laser irradiation, or using a light bulb, while in the dark
this value falls to 34%. A scope of 6 molecules was explored
and found yield values between 65% and 97% (Figure S13).
Similar conditions were also tested for the direct oxidation of
alcohols to carboxylic acids. Under the conditions we tested,
we did observe a small activity, but could not secure yields
beyond 11% (Figure S14).
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These results demonstrate that SPR can be harnessed to
activate silver towards hydrogenation of carbonyl compounds.
SPRꢀactivated silverꢀcatalyzed hydrogenation proceeded
ray spectroscopy, XRD – Xꢀray diffraction, XPS – Xꢀray
photoelectron spectroscopy, DLS – dynamic light scattering.
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REFERENCES
smoothly at 1 atm of H and 80°C, conditions much milder
2
than what is known for purely thermal silverꢀcatalyzed
processes. This reaction is the first example of SPRꢀactivated
reductive catalysis performed using pure, unmodified
plasmonic nanoparticles. This catalyst has been shown to
tolerate a wide variety of substrate scopes with moderate to
high yields, with complete selectivity for C=O vs C=C double
bond reduction. Kinetic studies, dose/response curves, solvent
dependence and complete Ag NCs characterization were
combined to propose a mechanism via lightꢀinduced hot
electron formation. This work is a proofꢀofꢀconcept of the use
of plasmonꢀactive nanocatalysts for important organic
transformation.
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audrey.moores@mcgill.ca
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20) Pelaez, M.; Nolan, N. T.; Pillai, S. C.; Seery, M. K.; Falaras, P.;
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Author Contributions
ML, CB and AM designed the project and experiments. ML
performed most experiments and drafted the manuscript. AG
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experiments, with assistance from BYM. CB and AM edited the
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We thank the Natural Science and Engineering Research Council
of Canada (NSERC) Discovery Grant program, the Canada
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UVꢀVis – Ultravioletꢀvisible, NPs – nanoparticles, SPR – surface
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Figure 1: TEM (left) and SEM (right) images of Ag NCs.
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Figure 2: UV-vis spectrum of Ag NCs that demonstrates the surface plasmon band ranging from 400 - 420
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Figure 3: Yields observed for the hydrogenation of camphor with Ag NCs as catalyst. Reaction conditions: 1
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Figure 4: Yield (%) vs laser intensity (mW/cm2) for the hydrogenation of camphor with Ag NCs as catalyst
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