Downloaded from https://iranpaper.

ir
https://www.tarjomano.com https://www.tarjomano.com

Catalysis
Science &
Technology
View Article Online
PAPER View Journal | View Issue

Improving the rate of the copper-catalyzed Henry

Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

Cite this: Catal. Sci. Technol., 2021,

reaction by surface plasmon excitation of gold
11, 7875 nanoparticles†
Léa Gimeno,a Gennaro Picardi,a Aurélien Planchat,a D. Andrew Knight, b
Marc Lamy de la Chapelle, c Bernard Humbert *d and Clémence Queffélec *a

Green LED plasmon excitation (525 nm) of colloidal gold nanoparticles (NPs), onto which a copperIJII)
complex was grafted, in the presence of nitrobenzaldehyde and nitromethane in DMF lead to the
formation of the corresponding nitroaldol with high efficiency. Kinetic studies using 1H NMR and Raman
spectroscopies showed that the reaction was faster under irradiation with green light, especially when in
Received 4th October 2021, close proximity to the NPs (ca. 100% conversion after 100 min). After reaction completion, it was possible
Accepted 7th November 2021
to recover the nanocatalyst and run two subsequent reactions. Green LED excitation of plasmonic
DOI: 10.1039/d1cy01788h
nanocatalyst is shown to be a straightforward and efficient method for accelerating the rate of the Henry
reaction with a lower energy demand and over a shorter reaction time when compared to the reaction
rsc.li/catalysis performed under classical conditions.

Introduction in the scientific community.6–8 As some reactions require

high temperature or an electron transfer to be initiated, both
Many metal NPs, especially gold nanoparticles (Au NPs), have effects can be exploited using plasmonic photocatalysis or
been reported as effective photocatalysts for organic plasmon-enhanced catalysis. As such, LSPR mediated catalytic
transformations due to the intense absorption band reactions can complement other methods for accelerating
possessed by Au NPs in the visible region of the spectrum.1 chemical reactions.1,9
Au NPs can be prepared with variety of shapes and sizes, are Mori et al.10 first described the enhancement of a catalytic
easy to functionalize using various anchoring groups2 and reaction (the oxidation of styrene) induced by LSP using an
display localized surface plasmon resonance (LSPR) under organometallic complex [RuIJbipy)3]2+ using a combination of
irradiation. LSPR is an interesting feature of metal gold and silver NPs. Trammell et al. reported LSPR enhanced
nanoparticles (NPs) and is generated via the interaction of an catalytic hydrolysis of the insecticide methyl parathion, using
incident electromagnetic wave with the conduction electrons a copperIJII) bipyridine complex covalently attached to 10 nm
on the surface of metal NPs.3,4 This LSPR phenomenon Au NPs via a Au–S bond.11,12 Subsequently, Forato et al.
imparts three main properties on plasmonic NPs which reported the preparation of Ag@TiO2 core–shell NPs in which
include the ability of the LSPR to cause localized heating, a CuIJI) bipyridine complex end-terminated with a phosphonic
local field enhancement, and provide charge carriers. All of acid anchoring group was grafted onto the oxide shell surface
these properties are relevant for photocatalytic reactions,1,5 and was found to be active for the Ullmann homocoupling
although the nature (thermal vs. non-thermal) and the effect reaction.13 Forato et al.14 also investigated copper oxidation
of plasmon interaction with organic molecules is still debated states in plasmonic nanomaterials using a combination of
XAS and Raman spectroscopy, which provided in situ
recording of XANES spectra for a specific catalytic reaction
a
CNRS, CEISAM UMR 6230, Université de Nantes, 2, Rue de la Houssinière, F-
and allowed the monitoring of copper oxidation states under
44000 Nantes, France. E-mail: [email protected]
b
Department of Biomedical & Chemical Engineering & Science, Florida Institute of
laser irradiation. Raman spectra were simultaneously
Technology, 150 West University Boulevard, Melbourne, Florida, 32901, USA recorded and revealed the structural evolution of the ligand-
c
CNRS, UMR 6283, Institut des Molécules et Matériaux du Mans (IMMM), complex. This data was used to propose a mechanism for
Université du Mans, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France plasmon-enhanced catalysis and the results demonstrated
d
CNRS, Institut des Matériaux Jean Rouxel, Université de Nantes, 2, Rue de la
the potential for plasmonic effects to improve the efficiency
Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
E-mail: [email protected]
of a catalytic reaction.
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ The Henry or nitroaldol reaction is considered a classical
d1cy01788h organic C–C bond-formation reaction. The reaction consists

This journal is © The Royal Society of Chemistry 2021 Catal. Sci. Technol., 2021, 11, 7875–7885 | 7875
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Paper Catalysis Science & Technology

of a coupling between a carbonyl group and an alkylnitro Exact mass spectrometry (MS) was performed using an
compound, under mild conditions, and leads to electrospray source (ES) and a tandem quadrupole-time of
β-nitroalcohol products, which are often used as key flight (Xevo G2-XS QTof, Waters) in negative mode as
auxiliaries in organic chemistry.15,16 Also, the development of analyzer.
the asymmetric version of this reaction is still widely studied
and most examples of the asymmetric Henry reaction involve Au NPs synthesis
catalysis via copper complexes or simple copper salts.17–22 The Au NPs was synthesized following the classic protocol
Heterogenized molecular catalysts have been developed and described by Sivaraman et al.32 Thus, sodium citrate solution
their recyclability assessed in the Henry reaction.23–28 Very (5.28 mM, 38.8 mg in 25 mL H2O) was heated to 105 °C. At
Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

few reports are known in which gold catalysts are used for the same time a solution of HAuCl4·xH2O 49% was prepared
the reaction. For example, bulk gold material29 or gold NPs (2.54 mM, 10 mg in 2.5 mL H2O) and adjusted to pH = 1.6.
(2–3 nm thus non-plasmonic)30 have been investigated. Then, the chloroauric solution was added quickly to the
We decided to develop a copperIJII) bipyridine complex boiling citrate solution. After 2 min, the solution turned
catalyst grafted onto Au NPs for studying the kinetic reddish or purplish red and reflux was maintained for 15
enhancement of the Henry reaction under irradiation. This min. Then, the solution was stored in the fridge at 4 °C and
exploits two synergistic mechanisms, the catalytic cycle itself is stable for months at this temperature.
and the plasmonic effect of the Au NPs. In that regard, we Au NPs were analyzed by transmission electron
recently developed a dithiolated bipyridine ligand31 and in microscopy to verify size distribution, and by UV-vis
this work, the ligand was used to graft a copperIJII) complex spectroscopy to confirm the position of the plasmon band.
onto a Au NPs surface. The nanomaterial provided a
nanocatalyst for the investigation of the plasmon enhanced CopperIJII) complex synthesis (C1)
Cu-catalyzed Henry reaction. The kinetics of this reaction
were evaluated by operando SERS experiments and 1H NMR. The synthesis of ligand 1 has been previously described.31
The synthesis of the copper complex C1 is shown in
Scheme 1.
Material and methods Under argon, CuIJOAc)2·H2O (0.065 mmol, 13 mg) and
General chemistry ligand 1 (0.065 mmol, 25 mg) were dissolved in 5 mL of
degassed ethanol. The solution was stirred for 2 days at room
All commercially available reagents and HPLC grade solvents
temperature. Then, the mixture was concentrated under
were purchased from Aldrich, Acros or Alfa Aesar and used as
vacuo and precipitated with a mixture of ethanol and
received, unless otherwise specified. Nitromethane was
petroleum ether. The resulting copper complex C1 was
purchased from TCI, 4-nitrobenzaldehyde was purchased
characterized by Raman (Fig. 3) and UV-visible spectroscopies
from Aldrich or Acros. HAuCl4·xH2O 49% was purchased from
(Fig. S1†).
Alfa Aesar. Citrate-stabilized Au colloids (nominally 40 nm
diameter) were obtained from Aldrich with an optical density
General procedure for Henry reaction
OD1 and ultra-pure Au colloids (nominally 10 nm diameter)
were obtained from Cytodiagnostics Inc. Silica gel (200–300 +Au NP. An aqueous solution (0.8 mL) of gold
mesh) was used for flash chromatography. nanoparticles was centrifuged at 8000 rpm for 30 minutes,
Solution-phase 1H spectra were recorded in deuterated then water was carefully removed via pipettor and 1.0 mL of
solvents on a Bruker Avance spectrometer operating at 300 DMF was added. The mixture was sonicated (30 s) and
MHz or at 400 MHz for 1H NMR, and 50 and 75 MHz for 13C nitrobenzaldehyde (NBA, 32.2 mg, 0.213 mmol) was added to
NMR. Chemical shifts for 1H NMR spectra are reported (in the NP solution followed by nitromethane (NM, 1.0 mL, 18.6
parts per million) relative to internal tetramethylsilane (Me4- mmol). The vial was closed and irradiated with a green LED
Si, δ = 0.00 ppm) with CDCl3 as a solvent or referenced to (525 nm, Fig. S4†). The distance from light source to the vial
residual CHCl3. was 0.3 cm without the use of any filters. The solution was
stirred at 900 rpm for the desired time. Then the mixture was
extracted with ethyl acetate, washed with water and brine,
Inductively coupled plasma-atomic emission spectroscopy dried over Na2SO4, filtered and concentrated under reduced
(ICP-AES) pressure to give the corresponding nitroaldol. A 1H NMR was
Precise determination of element concentrations was recorded on the crude product to determine the conversion
determined at the LPG UMR6112 using inductively coupled of the reaction via integration of the corresponding nitroaldol
plasma-atomic emission spectroscopy (ICP-AES) (Thermo protons. Then, purification by preparative thin layer
Scientific iCAP 6300 radial). Two multi-element solutions chromatography (ethyl acetate/petroleum ether (1/9, v/v))
(SQS01, SQS02, CHEMLAB) were used to determine the afforded the compound, and the yield of product
different elements present in the solutions. Mono-element determined.
solutions (1000 ppm, CHEMLAB) were used to calibrate and +AuNP-C1. An aqueous solution (0.8 mL) of gold
determine precisely the amount of element in each solution. nanoparticles was centrifuged at 8000 rpm for 30 minutes,

7876 | Catal. Sci. Technol., 2021, 11, 7875–7885 This journal is © The Royal Society of Chemistry 2021
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Catalysis Science & Technology Paper

Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

Scheme 1 Synthesis of the copper complex C1.

Fig. 1 Visible spectra of Au NPs in organic solvents after 1 day (left) and their evolution after 8 days (right).

Fig. 2 UV-visible spectra of Au NPs in DMF and Au NPs after the grafting of the CuIJII) complex in DMF and TEM images.

then water was carefully removed via pipettor and 1.0 mL of of the CuIJII) complex in DMF (1 mM) was added and the
DMF was added. The mixture was sonicated (30 s) and 20 μL corresponding solution was stirred at 900 rpm. After 20 min,

This journal is © The Royal Society of Chemistry 2021 Catal. Sci. Technol., 2021, 11, 7875–7885 | 7877
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Paper Catalysis Science & Technology

Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

Fig. 3 Raman spectra (633 nm excitation) for a) Raman spectrum of the cuIJII) complex C1 b) Raman spectrum of CuIJII) complex on Au colloid in
DMF and c) ligand grafted Au colloid in DMF dried onto a glass slide.

nitrobenzaldehyde (NBA, 32.2 mg, 0.213 mmol) was added Raman and SERS spectra were recorded with an InVia
to the NP solution followed by nitromethane (NM, 1.0 spectrometer from Renishaw LTD equipped with different
mL, 18.6 mmol). The vial was closed and irradiated with laser sources emitting at 514.5 nm, 632.8 nm and 785.0 nm.
a green LED (530 nm). The distance from light source to A 50×, 0.48 NA or 100×, 0.80 NA long working distance
the vial was 0.3 cm without the use of any filters. Fig. microscope objectives were used for illumination and
S4† shows the emission spectra of LEDs used for reaction collection in back scattering configuration. For the powder
irradiation. The solution was stirred at 900 rpm for the spectra, laser power at the sample was lower than 125 μW
desired time. Then the mixture was extracted with ethyl μm−2; typical acquisition time 20 s for 6 accumulations. At
acetate, washed with water and brine, dried over Na2SO4, least ten locations were measured for spectral reproducibility.
filtered and concentrated under reduced pressure to give For the SERS spectra, a droplet (10 μl) of the colloidal
the corresponding nitroaldol. A 1H NMR spectrum was solution with adsorbed molecules (0.2–0.1 μM) was
recorded on the crude mixture to determine the evaporated onto a glass slide. Laser power at the sample was
conversion of the reaction via integration of the in the range 100 μW to 50 μW. A minimum of twenty
corresponding nitroaldol protons. Then, purification by locations were measured.
preparative thin layer chromatography (ethyl acetate/ For the kinetic Raman monitoring, the reaction was
petroleum ether (1/9, v/v)) afforded the compound and the conducted in a quartz UV cuvette, stirred under LED
yield of product determined. 1H NMR spectra of irradiation or under dark conditions outside the Raman
nitrobenzaldehyde and the corresponding nitroaldol are spectrometer. For each given time point, the cuvette was
shown in Fig. S2 and S3.† located under the excitation laser on the Raman device stage
1
H NMR (CDCl3, 300 MHz) 8.27 ppm (d, J = 8.8 Hz, 2H, and spectra were recorded for 2 min and then placed back to
Ha), 7.63 ppm (d, J = 8.4 Hz, 2H, Hd), 5.61 ppm (m, 1H, Hb), continue stirring.
4.59 ppm (m, 2H, Hc), 3.24 ppm (s, 1H, OH). To obtain the different spectral sources (where spectral
HRMS (ES−) for C8H7N2O5 [M + H]−, m/z 211.0353 Da source = spectral fingerprints of each molecular intermediate
found, 211.0355 Da calc. taking into account their environment at a given time)
constituting the experimental spectra and to follow their
evolution over time, we applied either a curve resolution
Spectroscopic measurements method using all the spectral data or a principal component
Absorption spectra were recorded using a SPECORD 210 Plus analysis (PCA). For the curve resolution method, we used the
double-beam spectrometer from Analytik Jena. Bayesian positive source separation (BPSS) approach that was
Nanoparticle morphology was investigated by developed for spectral mixture analysis to provide an
transmission electron microscopy (TEM, 1230 Jeol) working estimation of the unknown component spectra and the
at a voltage of 120 keV, using holey carbon-coated copper relative concentrations of the underlying species.33 When
grids (300 mesh) to gain sufficient electronic contrast. spectroscopic techniques fail to resolve unknown or unstable

7878 | Catal. Sci. Technol., 2021, 11, 7875–7885 This journal is © The Royal Society of Chemistry 2021
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Catalysis Science & Technology Paper

individual constituents contained in multi-component 650–700 nm is a little bit broader, and for the ACN solution,
mixtures, vibrational spectroscopies combined with BPSS no absorption band was observed. Regarding the EtOH
treatment can offer a promising and efficient approach.34,35 suspension, no colour was observed associated with a
complete aggregation of the NPs and loss of the plasmon
Temperature measurement mapping band (Fig. 1). From these results, DMF was selected as the
The temperature was measured directly in the solution most suitable organic solvent for the work.
during LED illumination. A map of the temperature was
recorded on the whole surface of the solution with FLUKE CuIJII) complex grafting on the NPs and characterization of
TiR32 thermal camera. Thermal images were recorded the nanocatalyst (Ncat)
Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

continuously each 30 s for 15 minutes to be sure that the As mentioned in the introduction, a new plasmonic gold
solution had time to reach a thermal equilibrium. The nanocatalyst containing a terminal dithiol functionalized
temperature was then evaluated by averaging the bipyridyl copperIJII) complex was synthesized and tested in the
temperatures in the zone where the laser passes through the catalytic Henry reaction.31 Thus, after transferring Au NPs
solution. into DMF, a 1 mM solution of the CuIJII) complex in DMF was
added to the Au NP solution, and stirred for 30 min to yield
Results and discussion Ncat. The resulting colloidal solution was characterized using
Au NPs synthesis and stability in organic solvents UV-visible absorption and Raman spectroscopy, TEM and
ICP-AES. This analysis also allows determination of the
Gold NPs are used in a wide range of applications such as in
specific interactions taking place between the copper
nanomedicine, sensing, optoelectronics and catalysis.1,36–40
complex and the nanostructure. When the CuIJII) complex is
The classical synthesis in water is known as the “Turkevich”
grafted onto the surface of the Au NPs, the plasmon band is
synthesis, described for the first time in 1951,41 and allows
red-shifted from 530 to 533 nm, and broadens suggesting
the formation of citrate-stabilized Au NPs however this
some limited aggregation (Fig. 2).
method still suffers from lack of reproducibility and
To probe the grafted CuIJII) complex on Au NPs, Raman
predictability.42 Since then, this synthesis has been revisited
spectra were recorded at 633 nm excitation wavelength and
in term of temperature, reducing agent, etc.42–47 We thus
compared to the Raman spectrum of the CuIJII) complex (C1)
decided to adapt a protocol called the “reverse Turkevich”
prior to grafting (Fig. 3).
described by Sivaraman et al.32 wherein the chloroauric acid
Grafting of the complex to the NP surface will lead to
solution is added to the boiling citrate solution. Reddish
breaking of the dithiol S–S bond. The corresponding
spherical polydispersed Au NPs were obtained and we then
stretching mode observed near 509 cm−1 in the Raman
performed a statistical analysis of TEM images and DLS for
spectrum of C1 (spectrum a) is no longer observed for both
the size determination, and UV-visible spectroscopy to
the ligand (spectra c) and the grafted copper complex (spectra
determine the absorption maximum of the plasmonic band,
b). The formation of the copper complex is evidenced by the
that is correlated with the size of the NPs.48 In our case, the
strong scattering of the Cu–N band at 230 cm−1 and is
absorption maximum is centered around 524–526 nm and
enhanced by the presence of Au NPs. Additionally, one
the average size of the Au NPs is around 20–30 nm (Fig. S5†).
specific characteristic of the complexation of the ligand is the
It is important to point out that the synthesis can lead to
bipyridine ring breathing mode that is shifted from ca. 925
various color of colloids and UV-visible spectra (Fig. S6, A to
cm−1 to 1000 cm−1 upon binding to copperIJII). Finally, the
C†).
vibration band specific to the bipyridine ligand is found in
In order to perform the Henry reaction in organic
the range 1200–1800 cm−1.31
solvents, we found it necessary to transfer the colloids
Finally, to assess the Cu to Au atomic ratio, ICP-AES was
formed in water into organic solvents. In that regard, we
performed on the hybrid nanocatalyst. The measured
focussed our efforts on ethanol, acetonitrile (ACN) and
amounts of Au and Cu were 9.8 ppm and 0.009 ppm
dimethylformamide (DMF). The aqueous Au NPs were
respectively leading to a Au/Cu ratio of ca. 350. Assuming that
centrifuged for 30 min at 8000 rpm, the supernatant was
we have spherical NPs with a 30 nm diameter, we determined
removed and the chosen organic solvent was added. The
that the approximate number of copper complex molecules
organic colloidal Au NPs were sonicated and a UV-visible
adsorbed on individual nanoparticle is around ∼2500 and
spectrum of the colloidal solution was recorded directly after
that each molecule occupies an area of ∼1 nm2.
the transfer, and after 8 days to verify their stability with time
(Fig. 1). In EtOH and ACN, the organic colloids aggregate just
after the transfer as displayed by two absorption maxima Henry reaction
centered around 530 nm and 720 nm for EtOH, and around As mentioned in the introduction, the Henry reaction
530 nm followed by a broad shoulder for ACN, whereas for consists of a coupling between a carbonyl and an alkylnitro
DMF the spectrum is very similar to the one recorded in compound leading to a β-nitro alcohols product. We decided
water with a larger absorption around 650–700 nm. After 8 to begin our studies with 4-nitrobenzaldehyde and
days, for the DMF suspension, the absorption band around nitromethane as reactants. For a given time, the reaction was

This journal is © The Royal Society of Chemistry 2021 Catal. Sci. Technol., 2021, 11, 7875–7885 | 7879
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Paper Catalysis Science & Technology

Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

Fig. 4 Example of the 1H NMR spectral evolution of the Henry reaction vs. reaction time.

terminated, treated as described in the materials and corresponding aldehyde) in DMF (Table 1, entries 5 and 6),
methods section and 1H NMR recorded on the crude mixture the conversion of the reaction after 16 h was approximately
to evaluate the conversion into the corresponding nitroaldol the same compared to reaction in which the catalyst was
(Fig. 4). For this experiment, 0.009 mol% of copper complex used.
versus initial concentration of nitrobenzaldehyde was added The final control experiments were conducting the
in the mixture. reaction in DMF with only the Au NPs both with and without
As shown in Fig. 4, the disappearance of the NBA aldehyde irradiation. For these experiments, Au NPs were used
proton aldehyde (Ha) at 10.2 ppm over time can clearly be (represented in red in Fig. S5).† After 100 min, the reaction
observed, while the appearance of protons Hb and Hc from was almost complete with or without irradiation. From the
1
the NNBOH product are appearing. H NMR spectra, NMR yield was calculated by integrating the
We performed the reaction under different reaction protons as given in equation S1† and then conversion over
conditions (Table 1)20 including copper acetate + bipyridine time was plotted (Fig. 5) under irradiation (green curve) and
in ethanol or the pre-synthesized copper complex C1 in DMF under dark conditions (black curve). The initial rates for both
at room temperature under dark or under irradiation for 16 h conditions is similar. After 30 min in the dark the conversion
(see ESI† for experimental procedures). Both reactions were had already reached 73%, while under irradiation the
slow and presence of light did not improve the nitroaldol conversion is around 63%. Then the reaction reached ca.
conversion (Table 1, entries 1 and 2 for dark conditions and 100% conversion after 45 min in both cases. Finally, the
3 and 4 under irradiation). These results suggest that the reaction was also conducted with citrate alone (without Au
reaction is not photocatalyzed by the copper complex. When NPs, 3 mol%) and the conversion after 3 h was 95% (conv =
mixing only the two reagents (nitromethane and the 11% after 1 h). AuNP bound citrate concentration is

Table 1 Nitroaldol yield for the Henry reaction measured under different conditions

Entry Conditions Irradiation % NMR yield

1 CuIJOAc)2/bipyridine No 50 ± 5
2 Complex C1 No 45 ± 5
3 CuIJOAc)2/bipyridine Yes 55 ± 5
4 Complex C1 Yes 47 ± 5
5 No catalyst No 50 ± 5
6 No catalyst Yes 50 ± 5

7880 | Catal. Sci. Technol., 2021, 11, 7875–7885 This journal is © The Royal Society of Chemistry 2021
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Catalysis Science & Technology Paper

Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

Fig. 5 Conversion over time for the Henry reaction performed with Au NPs in DMF under dark conditions (black curve) and under green LED
irradiation (green curve).

extremely low compared to the bulk citrate reaction and (Fig. S7†). From the spectra, conversion was calculated by
therefore the contribution to the catalysis would be integrating the protons as given in equation S1† and
negligible. conversion over time was plotted (Fig. 6). With Ncat, the rate
From these results, it appears that both citrate and Au of the reaction appears to be similar for the first 15 min and
NPs catalyze the reaction and that green LED irradiation has then an increase both in the reaction rate, and in the
no influence on the kinetics of the reaction. In both conversion under irradiation, was observed compared to dark
conditions, the Henry reaction is much faster than with conditions. After 30 min, the conversion under irradiation
classical copper complexes (100% conversion after 45 min has reached 82% while under dark the conversion is around
compared to an average of 50% after 16 h). There are no 56%. The conversion reaches almost 100% after 150 min.
examples to our knowledge in the literature reporting Au NPs It appears that the copper complex grafted onto the gold
as a catalyst for the Henry reaction. nanoparticle surface might hinder the approach of reactants
Following the control experiments, we ran the reaction and subsequently inhibit the reaction. In that case, light is
with the nanocatalyst (Ncat) under green LED irradiation. absorbed by the Au NPs and the CuIJII) complex promotes the
The formation of nitroaldol was again assessed by 1H NMR Henry reaction. These conditions gave high conversion of the

Fig. 6 Conversion over time for the Henry reaction performed with Ncat in DMF under dark conditions (black curve) and under green LED
irradiation (green curve).

This journal is © The Royal Society of Chemistry 2021 Catal. Sci. Technol., 2021, 11, 7875–7885 | 7881
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Paper Catalysis Science & Technology

target product in a short period of time. Even though all our SERS, the rate of the reaction can be studied in close
attempts to obtain crystal of the copper complex failed, we proximity to the NP surface while with 1H NMR, as described
assume that the ligand coordinates to CuIJII) through the two above, the rate was determined for the bulk reaction in
nitrogen atoms of bipyridine and two acetate groups which solution. In this latter case, it is not possible to determine
are still present on the metallic center forming a four- the direct influence of the NP on the reaction whereas with
coordinate copper complex on a Au NP which is able to SERS, we have access to the first nanometer shell radius
activate the reaction between nitromethane and surrounding the NP and thus the evolution of the reaction in
nitrobenzaldehyde.17,49 One acetate group will be displayed the vicinity of the NP. Moreover, as the SERS spectrum is
by nitromethane while nitrobenzaldehyde will coordinate relevant for the molecular structure, it is then possible to also
Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

simultaneously to the copperIJII) ion in such a way as to monitor the structural modifications of the reactants or for
maximum substrate interaction, and we tentatively suggest the Cu catalyst as the reaction proceeds. SERS kinetics
that this step might be enhanced by either the LSPR of Au measurements were performed with Ncat both under dark
NPs or the Au NPs alone. Subsequently, the nucleophilic and under green irradiation. The recorded time for SERS
carbon of the nitronate ion formed in situ by the spectra was kept the lowest possible to avoid any further or
deprotonation of the nitromethane attacks the carbonyl additional reactions due to the Raman laser irradiation. It is
carbon of the aldehyde (Fig. 7). important to mention that we performed the SERS
Finally, we performed experiments to measure the experiments with the red-purple Au NPs (Fig. S6, b†). We
temperature of the solution using a thermal camera (Fig. chose those colloids because the rate is slower and it is more
S8†) for reactions in which NPs and Ncat were present or straightforward to record SERS spectra at different times and
omitted. When the NPs were present in DMF or when the follow the spectral evolution. With the red-purple Au NPs, the
Henry reaction was performed under green LED irradiation, conversion for the Henry reaction after 30 min, as measured
the solution temperature was limited to a few °C i.e. the by 1H NMR, was ca. 55%.
temperature increase is almost the same with and without By Raman spectroscopy, an essential difficulty of following
the NPs. This suggests that there is a temperature increase the kinetics of the chemical transformation of
due to DMF solvent heating mediated by the LED source, but nitrobenzaldehyde into nitroaldol species came from the very
no thermal plasmonic effect originating from the Au NPs intense signals of DMF and nitromethane which overlap with
(Fig. S9†). the signals of our molecules of interest at low concentration.
Thus, light absorption due to the LSPR of the Au NPs is Fig. 8 and S10† illustrate two examples of this problem.
playing an important role in enhancing the catalyst Only two narrow spectral zones are easily visible in order to
performance and in our case, it seems that the enhancement follow the decrease in nitrobenzaldehyde signals, the spectral
of the reaction rate could be assigned to the hot electron zone of the stretching mode of the CO bond (around 1715
mechanism rather than a thermal effect. cm−1) and the appearance of nitroaldol signals corresponding
to the symmetric stretching mode of NO2 (ca. 1355 cm−1).
Although the signals of the medium are very intense, it is
Kinetic studies using SERS possible to monitor qualitatively the decrease of the
To further understand the Henry reaction in the presence of concentration of the starting material. Fig. S11† shows
Ncat, we followed the reaction rate by Raman spectroscopy. monitoring of the Henry reaction over time using Raman
Although the relative concentration of copper complex is low, spectroscopy. The rate of the reaction under dark conditions
in the presence of the Au NPS we were able to follow the is slower that that under green LED irradiation.
signals assigned to the nitrobenzaldehyde and the Faced with the difficulty of spectral signal overlap, we
corresponding nitroaldol in solution. We compared those used the Bayesian positive source separation (BPSS) approach
spectra with those obtained without Au NPs and concluded to statistically treat all of the spectra, using the time
that the recorded signals were enhanced by a factor of parameter as the parameter of variability.
between 500 and 1500. Vide infra we will use the acronym Thus, the BPSS method was applied for all the spectra in
SERS for surface enhanced Raman spectroscopy when Raman order to separate the signals coming from the reaction
experiments in presence of Au NPs is described. By using medium and evolving positively or negatively. The BPSS
approach was performed on more than eight kinetic
evolutions, i.e. with ca. 50 spectra. Fig. 9 shows the two
source spectra (Fig. 9a and b) obtained by the BPSS process,
evolving with the reaction time and their respective
evolutions with Ncat, one under green irradiation (Fig. 9c)
(described in Fig. S6-b† where the kinetic is slower as
mentioned above) and the other under dark conditions
Fig. 7 Proposed intermediate for the CuIJII) catalyzed Henry reaction
(Fig. 9d). The previous qualitative estimations were retrieved
enhanced by LED plasmon excitation on gold NPs (based on ref. 17 quantitatively. The kinetics measured here using SERS exactly
and 46). agree with the NMR data.

7882 | Catal. Sci. Technol., 2021, 11, 7875–7885 This journal is © The Royal Society of Chemistry 2021
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Catalysis Science & Technology Paper

Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

Fig. 8 Monitoring of Raman spectra over time for the Henry reaction with Ncat under green irradiation (see UV-visible spectra of Fig. S6b† for the
Au NPs used in this experiment). Raman spectra between 1300 and 1800 cm−1 where the signals of nitrobenzaldehyde disappear (essentially the
CO stretching mode around 1715 cm−1) and the signal of nitroaldol appear (essentially at 1355 cm−1). The stars indicate the Raman signals for the
solvent medium (mixture of DMF with nitromethane). Blue: t = 0 min orange: t = 120 min reactions.

Fig. 9 Normalized conversion for the Henry reaction under green irradiation after BPSS treatment (red: disappearance of nitrobenzaldehyde, blue:
appearance of nitroaldol). (a) Blue: signals decreasing vs. time; (b) red: signals increasing vs. time, (c) example of monitoring of these two spectral
sources as a function of time for kinetics under green irradiation and (d) the same type of monitoring as a function of time under dark conditions.

The principal component analysis (PCA) analysis leads to spectral component which shows the decrease in signal at
the same type of interpretation (Fig. S12†) by displaying a 1710 cm−1 characteristic of the aldehyde group in favour of

This journal is © The Royal Society of Chemistry 2021 Catal. Sci. Technol., 2021, 11, 7875–7885 | 7883
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Paper Catalysis Science & Technology

Conclusions
In summary, a plasmonic process for the Henry reaction was
developed using a CuIJII) complex grafted onto Au NPs. This
nanocatalyst exhibited good catalytic performance and the
results showed that the conversion under green LED
irradiation after 30 min was 80% versus 60% in the dark.
Additionally it was demonstrated that the Au NPs also acted
as a catalysis the Henry reaction, which to the best of our
Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

knowledge has not been previously reported. In both cases

(Au NPs alone or the nanocatalyst), the reaction was much
faster than in the classic conditions (ca. 100% conversion
after 100 min versus ≈50% conversion after 16 h). The rate of
Fig. 10 Recycling experiments with Au NPs or with Ncat for the Henry
reaction after 30 min, both under dark conditions or under green LED the reaction was enhanced by the interaction of CuIJII)
irradiation. complex grafted onto Au colloidal NPs and the photoexcited
hot electrons, which in turn was driven by the LSPR effect on
the Au NP surface via green light adsorption. Temperature
the appearance of a signal at 1355 cm−1 assigned to the nitro measurements allowed us to estimate that thermal effects
group on the aldol. It can be noted that the BPSS analysis might be negligible under our conditions. Additionally, SERS
also shows the signals for the modes involving the nitro measurements were used to determine the kinetics of the
group (1375 cm−1) on the nitrobenzaldehyde which are reaction in close proximity the NPs. In the vicinity of the NP
hidden in the original spectra by the signals due to the surface, the reaction is faster under green light irradiation. In
solvent medium. depth investigations of the Raman signals gave more
Finally, conversions for the Henry reaction were consistent information on the chemical structure of the molecular
between Raman and NMR analysis for the reaction profiles. complexes adjacent to the NPs and on the mechanism
Additionally, in the vicinity of the nanoparticle surface, the occurring during the Henry reaction. However, further
rate of the reaction under dark conditions and green studies are still needed to better understand the mechanism
irradiation is much more noticeable than as observed by 1H of plasmonic copper-catalyzed Henry reaction and this will
NMR spectroscopy. Experimental Raman monitoring is a very be achieved by combining DFT calculations (currently in
interesting and straightforward analytical technique for progress) with spectroscopic data. This work will allow the
following catalytic evolution. design of molecular plasmonic catalysts that could be
efficient in various catalytic reactions and may offer a mild
route for plasmon mediated enantioselective reactions.
Recycling experiments
Recycling experiments are important in photocatalytic
reactions for studying the stability and evolution of Author contributions
nanostructures. After the plasmon-enhanced catalytic
Henry reaction of 4-nitrobenzaldehyde and nitromethane The manuscript was written through contributions of all
with Ncat or with only Au NPs, the reaction mixture authors. All authors have given approval to the final version
was centrifuged, the filtrate removed (for analysis) and of the manuscript.
the colloids were dispersed again in DMF. They were
then reused for the same reaction, under irradiation
and under dark conditions (Fig. 10). After three cycles, Conflicts of interest
the performance of Au NPs started to decrease under There are no conflicts to declare.
dark conditions or under irradiation. For Ncat under
irradiation after the second run, the conversion had
already dropped to 45% and after the third run to Acknowledgements
30%, suggesting the possibility of nanoparticle
aggregation under irradiation. Francois-Xavier Lefevre is thanked for assistance with the
Aggregation was confirmed by the different UV-vis spectra TEM measurements. Carole La from LPG-CNRS 6112
of the colloids after reaction under illumination or under (University of Nantes) is strongly acknowledged for her great
dark conditions. In all cases, the nanoparticles aggregated help in determination of elemental composition using ICP-
after the first re-cycle (Fig. S13 and S14†). At the end of the AES. Christophe Naveau is thanked for his help with the
first run, the solution was still reddish and the aggregation thermal measurements. The authors acknowledge financial
occurred when the reaction mixture was centrifuged to isolate support from the X-TREM project (Pari Scientifique Regional–
the filtrate from the colloids. Pays de la Loire, France).

7884 | Catal. Sci. Technol., 2021, 11, 7875–7885 This journal is © The Royal Society of Chemistry 2021
 Downloaded from https://iranpaper.ir
https://www.tarjomano.com View
https://www.tarjomano.com
Article Online

Catalysis Science & Technology Paper

References 25 N. Tahir, G. Wang, I. Onyshchenko, N. De Geyter, K. Leus, R.

Morent and P. Van Der Voort, J. Catal., 2019, 375, 242–248.
1 A. Gelle, T. Jin, L. de la Garza, G. D. Price, L. V. Besteiro and 26 C. Sappino, L. Primitivo, M. De Angelis, M. O. Domenici, A.
A. Moores, Chem. Rev., 2020, 120, 986–1041. Mastrodonato, I. B. Romdan, C. Tatangelo, L. Suber, L.
2 S. Talebzadeh, C. Queffélec and D. A. Knight, Nanoscale Adv., Pilloni, A. Ricelli and G. Righi, ACS Omega, 2019, 4,
2019, 1, 4578–4591. 21809–21817.
3 I. Kherbouche, Y. Luo, N. Félidj and C. Mangeney, Chem. 27 H.-C. Ma, C.-C. Zhao, G.-J. Chen and Y.-B. Dong, Nat.
Mater., 2020, 32, 5442–5454. Commun., 2019, 10, 3368.
4 N. Jiang, X. Zhuo and J. Wang, Chem. Rev., 2018, 118, 28 J. Gao, S. Wu, F. Tan, H. Tian, J. Liu and G. Q. M. Lu, Prog.
Published on 08 November 2021. Downloaded by TU Wien Bibliothek on 6/12/2025 1:34:35 AM.

3054–3099. Nat. Sci.: Mater. Int., 2018, 28, 242–245.

5 A. Gellé and A. Moores, Curr. Opin. Green Sustain. Chem., 29 A. Simion, N. Candu, S. M. Coman, A. Primo, I. Esteve-Adell,
2019, 15, 60–66. V. Michelet, V. I. Parvulescu and H. Garcia, Eur. J. Org.
6 O. Guselnikova, G. Audran, J.-P. Joly, A. Trelin, E. V. Chem., 2018, 2018, 6185–6190.
Tretyakov, V. Svorcik, O. Lyutakov, S. R. A. Marque and P. 30 G. Abdi and A. Alizadeh, Gold Bull., 2018, 51, 65–74.
Postnikov, Chem. Sci., 2021, 12, 4154–4161. 31 G. Picardi, B. Humbert, M. Lamy de la Chapelle and C.
7 G. Baffou, I. Bordacchini, A. Baldi and R. Quidant, Light: Sci. Queffelec, J. Phys. Chem. C, 2020, 124, 11902–11912.
Appl., 2020, 9, 108. 32 S. K. Sivaraman, S. Kumar and V. Santhanam, J. Colloid
8 T. P. Araujo, J. Quiroz, E. C. M. Barbosa and P. H. C. Interface Sci., 2011, 361, 543–547.
Camargo, Curr. Opin. Colloid Interface Sci., 2019, 39, 33 S. Moussaoui, D. Brie, C. Carteret and A. Mohammad-
110–122. Djafari, in Bayesian Inference and Maximum Entropy Methods
9 R. Wang, H. Liu, X. Wang, X. Li, X. Gu and Z. Zheng, Catal. in Science and Engineering, ed. R. Fischer, R. Preuss and U.
Sci. Technol., 2020, 10, 6483–6494. VonToussaint, Amer Inst Physics, Melville, 2004, vol. 735,
10 K. Mori, M. Kawashima, M. Che and H. Yamashita, Angew. pp. 237–244.
Chem., Int. Ed., 2010, 49, 8598–8601. 34 F. Quiles, C. Nguyen-Trung, C. Carteret and B. Humbert,
11 S. A. Trammell, R. Nita, M. Moore, D. Zabetakis, E. Chang Inorg. Chem., 2011, 50, 2811–2823.
and D. A. Knight, Chem. Commun., 2012, 48, 4121–4123. 35 C. Carteret, A. Dandeu, S. Moussaoui, H. Muhr, B. Humbert
12 S. A. Trammell, R. Nita, B. Martin, M. H. Moore, J. Fontana, and E. Plasari, Cryst. Growth Des., 2009, 9, 807–812.
S. Talebzadeh and D. A. Knight, RSC Adv., 2016, 6, 36 S. Zeng, D. Baillargeat, H.-P. Ho and K.-T. Yong, Chem. Soc.
41618–41621. Rev., 2014, 43, 3426–3452.
13 F. Forato, S. Talebzadeh, B. Bujoli, C. Queffelec, S. A. 37 C. Wang and D. Astruc, Chem. Soc. Rev., 2014, 43, 7188–7216.
Trammell and D. A. Knight, ChemistrySelect, 2017, 2, 38 O. S. Muddineti, B. Ghosh and S. Biswas, Int. J. Pharm.,
769–773. 2015, 484, 252–267.
14 C. Queffélec, F. Forato, B. Bujoli, D. A. Knight, E. Fonda and 39 S. E. Lohse and C. J. Murphy, J. Am. Chem. Soc., 2012, 134,
B. Humbert, Phys. Chem. Chem. Phys., 2020, 22, 2193–2199. 15607–15620.
15 F. A. Luzzio, Tetrahedron, 2001, 57, 915–945. 40 L. De Sio, T. Placido, R. Comparelli, M. Lucia Curri, M.
16 N. Ono, The Nitro Group in Organic Synthesis, John Wiley & Striccoli, N. Tabiryan and T. J. Bunning, Prog. Quantum
Sons, 2003. Electron., 2015, 41, 23–70.
17 L. Zhang, H. Wu, Z. Yang, X. Xu, H. Zhao, Y. Huang and Y. 41 J. Turkevich, P. C. Stevenson and J. Hillier, Discuss. Faraday
Wang, Tetrahedron, 2013, 69, 10644–10652. Soc., 1951, 11, 55–75.
18 D. Didier, C. Magnier-Bouvier and E. Schulz, Adv. Synth. 42 L. Shi, E. Buhler, F. Boué and F. Carn, J. Colloid Interface
Catal., 2011, 353, 1087–1095. Sci., 2017, 492, 191–198.
19 J. Cho, M. K. Chun, S. Nayab and J. H. Jeong, Appl. 43 J. Kimling, M. Maier, B. Okenve, V. Kotaidis, H. Ballot and A.
Organomet. Chem., 2019, 33, e4955. Plech, J. Phys. Chem. B, 2006, 110, 15700–15707.
20 E. Gao, M. Li, L. Duan, L. Li and Y.-M. Li, Tetrahedron, 44 H. Kim, Y. S. Seo, K. Kim, J. W. Han, Y. Park and S. Cho,
2019, 75, 130492. Nanoscale Res. Lett., 2016, 11, 230.
21 V. A. Larionov, L. V. Yashkina, M. G. Medvedev, A. F. 45 C. Daruich De Souza, B. Ribeiro Nogueira and M. E. C. M.
Smol'yakov, A. S. Peregudov, A. A. Pavlov, D. B. Eremin, T. F. Rostelato, J. Alloys Compd., 2019, 798, 714–740.
Savel'yeva, V. I. Maleev and Y. N. Belokon, Inorg. Chem., 46 L. Panariello, A. N. P. Radhakrishnan, I. Papakonstantinou,
2019, 58, 11051–11065. I. P. Parkin and A. Gavriilidis, J. Phys. Chem. C, 2020, 124,
22 A. Rossetti, S. Landoni, F. Meneghetti, C. Castellano, M. 27662–27672.
Mori, G. C. Dugoni and A. Sacchetti, New J. Chem., 2018, 42, 47 L. Freitas de Freitas, G. H. C. Varca, J. G. dos Santos Batista
12072–12081. and A. B. Lugão, Nanomaterials, 2018, 8, 939.
23 D. Didier and E. Schulz, Tetrahedron: Asymmetry, 2013, 24, 48 M. Shah, Front. Biosci., 2014, 19, 1320.
769–775. 49 D. A. Evans, D. Seidel, M. Rueping, H. W. Lam, J. T. Shaw
24 K. Dhahagani, J. Rajesh, R. Kannan and G. Rajagopal, and C. W. Downey, J. Am. Chem. Soc., 2003, 125,
Tetrahedron: Asymmetry, 2011, 22, 857–865. 12692–12693.

This journal is © The Royal Society of Chemistry 2021 Catal. Sci. Technol., 2021, 11, 7875–7885 | 7885