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Article
Synthesis of Water Soluble and Catalytically
Active Gold-decorated Cobalt Ferrite Nanoparticles
Alessandro Silvestri, Sara Mondini, Marcello Marelli, Valentina Pifferi,
Luigi Falciola, Alessandro Ponti, Anna Maria Ferretti, and Laura Polito
Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.6b01266 • Publication Date (Web): 22 Jun 2016
Downloaded from http://pubs.acs.org on July 1, 2016

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Synthesis of Water Dispersible and Catalytically
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12 Active Gold-decorated Cobalt Ferrite Nanoparticles
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17 Alessandro Silvestri†‡, Sara Mondini†‡, Marcello Marelli†, Valentina Pifferi‡, Luigi Falciola‡,
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19 Alessandro Ponti †, Anna Maria Ferretti*† and Laura Polito*†
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† Laboratorio di Nanotecnologie, Istituto di Scienze e Tecnologie Molecolari, Consiglio
24 Nazionale delle Ricerche, Via G. Fantoli 16/15, 20138 Milan, Italy
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26 ‡ Department of Chemistry, University of Milan, Via C. Golgi 19, 20133 Milan, Italy
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ABSTRACT. Hetero-nanoparticles represent an important family of composite nanomaterials
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35 that, in the last years, is attracting ever growing interest. Here, we report a new strategy for the
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37 synthesis of water dispersible cobalt ferrite nanoparticles (CoxFe3-xO4 NPs) decorated with
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40 ultrasmall (2-3 nm) gold nanoparticles (Au NPs). The synthetic procedure is based on the use of
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42 2,3-meso-dimercapto succinic acid (DMSA), which plays a double role. Firstly, it transfers
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44 cobalt ferrite NPs from the organic phase to aqueous media. Secondly, the DMSA reductive
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47 power promotes the in-situ nucleation of gold NPs in proximity of the magnetic NP surface.
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49 Following this procedure, we achieved a water dispersible nano-system (CoxFe3-xO4-DMSA-Au
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NPs) which combines the cobalt ferrite magnetic properties with the catalytic features of
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54 ultrasmall Au NPs. We showed that CoxFe3-xO4-DMSA-Au NPs act as an efficient nano-catalyst
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56 to reduce 4-nitrophenol to 4-aminophenol, and that they can be magnetically recovered and
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recycled. It is noteworthy that such nanosystem is more catalytically active than Au NPs with
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6 equal size. Finally, a complete structural and chemical characterization of the hetero-NPs is
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8 provided.
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12 1. INTRODUCTION
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One of the most compelling goals in the field of nanotechnology is the design and synthesis of
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18 hetero-nanoparticles, combining in a single entity the physical and chemical properties of the
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20 composing substances.1-5 In addition to this additive multi-functionality, hybrid nanostructures
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23 can synergistically enhance the capabilities of the individual component due to proximity effects
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25 or electronic coupling at the interface.6 By engineering at the nanoscale, it is possible to design
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27 and create new materials with improved and fascinating properties, which can be employed in
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30 many applications.1-5 Among a wide number of papers related to the production of hybrid nano-
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32 structures,1-7 a large focus has been placed on the synthesis of hybrid magnetic nanoparticles
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34 (NPs), mainly based on magnetite/maghemite (Fe3O4/γ-Fe2O3) and gold.8 These materials have
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37 been extensively studied and synthesized with different types of morphologies like core-shell,9-11
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39 inverted core-shell,12 and dumbbell.13-15 The reason for this huge interest resides in the large
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number of applications in which gold-coated magnetic NPs can be used. In fact, tailoring their
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44 features, these materials can be applied in the fields of nanomedicine,7,16 biosensors,16,17 cell
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46 separation16,17 and catalysis.18,19 The optical and catalytic activity of gold can be modulated by
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49 sizing and shaping the Au NP morphology or the hetero-nanoparticle geometry. For example, the
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51 plasmon resonance peak of Au could be shifted to the NIR region by increasing size or
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53 introducing branches on the NP surface.20 Furthermore an increase in the surface/volume ratio
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56 plays a fundamental role in the catalytic activity of nanometric gold.21,22 On the other hand,
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magnetic properties can be fine tuned controlling the size and composition of ferrite NPs. For
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6 instance, in comparison with magnetite/maghemite (Fe3O4/γ-Fe2O3), cobalt ferrite (CoFe2O4)
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8 NPs present improved magnetic properties due to their high relaxivity and magnetic
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anisotropy.23,24 Despite advantageous magnetic properties, few examples of hybrid systems
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13 comprising cobalt ferrites and gold have been described.25-28 Moreover, an inherent difficulty in
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15 the reproducible synthesis of these hetero-nanoparticles hamper their widespread exploitation.2
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18 Herein, we report a reliable synthetic strategy to obtain water dispersible cobalt ferrite NPs
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20 decorated with ultrasmall gold NPs (CoxFe3-xO4-DMSA-Au), by means of a facile protocol. The
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22 multistep strategy is based on the solvothermal synthesis of cobalt ferrite nanoparticles,
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25 stabilized by oleic acid and oleylamine (CoxFe3-xO4-OA) in organic solvent, followed by a ligand
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27 exchange procedure to bring the NPs in aqueous environment, by using 2,3-meso-dimercapto
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succinic acid (CoxFe3-xO4-DMSA). Next, the DMSA coating the magnetic NP surface was
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32 exploited to reduce AuCl4- and to induce an in situ nucleation of gold NPs exclusively in the
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34 proximity of the cobalt ferrite surface, without using any further reducing agents or preformed
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37 gold seeds. The presence of a wide available surface area of noble metal onto a nanosized
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39 magnetic support, makes this material a promising candidate to act as an efficient recyclable
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41 catalyst. Therefore, taking advantage of their water solubility and magnetization, we studied the
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44 catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), monitoring the reaction
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46 progress by UV-vis spectroscopy. The chance to reduce, at room temperature and in mild
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48 conditions, water pollutants is presently of crucial interest.29,30 Nitroaromatics, in fact, are an
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51 important class of environmentally toxic compounds widely employed in the production of
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53 explosives, pesticides, plastics and pharmaceuticals.29 Noteworthy, the molecule resulting from
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this reduction (4-AP) can find applications in many fields, underlying the opportunity to carry on
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new studies to continuously improve the reduction efficiency.29,30 The morphological, elemental
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6 and structural features of hetero-nanoparticles were evaluated by Transmission Electron
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8 Microscopy (TEM), Inductively Coupled Plasma-Optical Emission Spectrometers (ICP-OES),
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UV-Vis spectroscopy and Dynamic Light Scattering (DLS) analysis while the magnetic
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13 characterization was performed by a Quantum Design MPMS XL-5 SQUID magnetometer.
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18 2. EXPERIMENTAL SECTION
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21 2.1 Materials. All reagents, unless cited otherwise, were purchased from Sigma-Aldrich,
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23 and used without any further purification. HAuCl4•3H2O was stored as a 10 mM solution in
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26 MilliQ water, at 4 °C and protected from light. The glassware used for gold NPs synthesis were
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28 cleaned with aqua regia (HCl (37%) / HNO3 (65%) 3/1). Ultra-pure MilliQ water was used for
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the preparation of all the aqueous solutions. The concentration of water dispersible NPs was
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33 performed by means of Millipore Amicon® Ultra centrifugal filters with a 30 kDa cut-off for
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35 CoxFe3-xO4-DMSA NPs and CoxFe3-xO4-DMSA-Au NPs, and with a cut-off of 3 kDa for Au-
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38 DMSA NPs. The purification of NPs was performed by using dialysis tubes with a cut-off of 14
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40 kDa. The dropped addition of HAuCl4 to the reaction mixture was performed with the aid of a
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42 NE-1010 Higher Pressure Programmable Single Syringe Pump.
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46 2.2. Synthesis of CoxFe3-xO4-OA NPs. CoxFe3-xO4-OA NPs were synthesized according to a
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48 literature procedure.31 A solution of Fe(acac)3 (350 mg, 0.99 mmol), Co(acac)2 (128 mg, 0.495
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mmol), oleic acid (1 mL, 3.15 mmol), oleylamine (1 mL, 3.04 mmol), 1,2- hexadecanediol (1.15
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53 g, 4.45 mmol) in benzyl ether (25 mL) was warmed up to 120 °C under argon flow and kept at
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55 this temperature for 1 h. The mixture was first heated to 210 °C with a rate of 8 °C/min and
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maintained at this temperature for 2 h. Then, the temperature was raised to 300 °C with a rate of
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3 °C/min and maintained for 1 h. After cooling the reaction mixture to room temperature, the
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6 obtained NPs were collected by centrifugation (6000 rpm) after the addition of a mixture of
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8 ethanol/acetone 1/1 and then redissolved in hexane. This treatment was repeated two times. After
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the last precipitation, CoxFe3-xO4-OA NPs were stored dissolved in hexane (20 mL) and stored at
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13 room temperature.
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16 2.3. Synthesis of water dispersible CoxFe3-xO4-DMSA NPs. The ligand exchange procedure
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19 leading to the title product was performed in two steps. In the first step, 3 mL of hexane solution
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21 of CoxFe3-xO4-OA were precipitated by centrifugation (after adding 10 mL of ethanol/acetone 1/1
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23 mixture) and redissolved in 6 mL of toluene. A solution of DMSA (33 mg, 0.18 mmol) in DMSO
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26 (2 mL) was dropped into a round-bottom flask (immersed in a ultrasonic bath) containing the
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28 toluene dispersion of CoxFe3-xO4-OA NPs. The mixture was sonicated for 1 h and further
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magnetically stirred for 2 days. Afterwards, 4 mL of toluene were added to aid the precipitation
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33 of the CoxFe3-xO4-DMSA NPs. The NPs were magnetically recovered and washed consecutively
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35 three times with ethanol and two times with acetone, and finally suspended in MilliQ water (10
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38 mL). Then, to improve aqueous dispersion, the solution was basified to pH 10 (using aq. NaOH
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40 solution, 0.1 M) and subsequently brought back to pH 7 (using aq. HCl solution, 0.1 M).26 In the
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42 second step, a solution of DMSA (20 mg, 0.1 mmol) in water (10 mL) was added dropwise to the
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45 NP dispersion, and the mixture was sonicated for 1 h. Then the mixture was magnetically stirred
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47 for further 12 h and purified by dialyzing against MilliQ water for 72 h (changing water every 8-
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10 h). Finally, the recovered CoxFe3-xO4-DMSA NPs were stored as diluted aqueous solution
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52 (250 mL), with an iron concentration of 34 µg/mL. Such stock solution was stable for months at
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2.4. Synthesis of CoxFe3-xO4-DMSA-Au NPs. In a round-bottom flask, 10 mL of the stock
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6 solution of CoxFe3-xO4-DMSA NPs were stirred (750 rpm) under N2 atmosphere at room
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8 temperature. An aqueous solution of HAuCl4 (10 mL, 0.2 mM) was slowly dropped into the
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reaction mixture with the aid of a syringe pump (flow rate: 41.5 µL/min). After completing the
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13 addition, the mixture was stirred for an additional hour. The NPs were concentrated, dialyzed
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15 against MilliQ water for 48 h (changing water every 8-10 h) and stored as aqueous dispersion (2
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18 mL) with an iron concentration of 140 µg/mL (2.51 mM) and a gold concentration of 86 µg/ml
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20 (0.44 mM).
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23 2.5. Synthesis of Au-DMSA NPs. Au-DMSA NPs were synthesized following the method
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26 published by Negishi et al.32 DMSA (1.8 mg, 10 µmol) was dissolved in MilliQ water (0.5 mL)
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28 and added to an aqueous solution (5 mL) of HAuCl4 (1.7 mg, 5 µmol). The reaction mixture was
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stirred (750 rpm) for 10 min at room temperature, and the color of the solution changed from
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33 yellow to light brown. The NPs were washed five times with MilliQ water by centrifugation,
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35 using 3 kDa centrifugal filters units. The recovered Au-DMSA NPs were dissolved and stored in
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38 aqueous solution (4 mL) at a gold concentration of 240 µg/mL.
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41 2.6. Characterization of NPs. The morphology and size distribution of the NPs were evaluated
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43 using transmission electron microscopy by means of a Zeiss LIBRA 200FE microscope,
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46 equipped with a 200 kV FEG an in-column second-generation omega filter for energy selective
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48 spectroscopy, and a STEM facility with HAADF detector. Both TEM and STEM imaging modes
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were employed. Electron energy loss spectroscopy (EELS) and imaging (ESI), and energy
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53 dispersive X-ray spectroscopy (EDX, OXFORD X-Stream 2 and INCA software) were used to
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55 determine the elemental ratio and distribution inside the nanostructure. The samples for TEM
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analysis were prepared depositing a drop of NP dispersion on a carbon-coated copper grid (300
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mesh) and evaporating the solvent. The particle size distribution was obtained by measuring at
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6 least 500 nanoparticles, analyzing TEM images by the software Pebbles and Pebble Juggler.33
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8 UV-Vis spectra were recorded by means of an Agilent 8453 instrument. DLS and ζ-potential
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measurements were carried out by a 90 plus Particle Size Analyzer (Brookhaven Instrument
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13 Corporation) equipped with a solid state He–Ne laser (wavelength = 661 nm). Experiments were
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15 carried out at a scattering angle of 90° on diluted NP samples at 298 K. NP samples for DLS
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18 were filtered through 0.45 µm cellulose acetate syringe filters before measuring. Each sample
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20 was allowed to equilibrate for 3 min prior to starting the experiment. Ten independent
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22 measurements of 60 s duration were performed for each sample. The NP hydrodynamic
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25 diameters were calculated using Mie theory, considering absolute viscosity and refractive index
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27 values of the medium to be 0.911 cP and 1.334, respectively. The ζ-potential was calculated from
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the NP electrophoretic mobility using the Smoluchowski theory, assuming a medium viscosity of
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32 0.891 cP, medium dielectric constant of 78.6, and Henry function of 1.5. FTIR spectra were
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34 recorded by a Thermo Nicolet NEXUS 670 FTIR spectrometer, using KBr pellets. Gold, iron
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37 and cobalt content of NPs was determined via Inductively Coupled Plasma-Optical Emission
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39 Spectrometry (ICP-OES; iCAP 6300 Duo, Thermofisher). Samples were heated and acid
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41 digested with aqua regia (500 µL for 5 times); the residues were recovered with HCl 37% (500
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44 µL) and diluted with MilliQ water to a known volume. Multi-element standards containing the
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46 three metals were used to create the external calibration line. The magnetic characterization was
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performed by a Quantum Design MPMS XL-5 SQUID magnetometer. Weighted amounts of
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51 powdered samples were packed in Teflon ribbon. The temperature dependence of the
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53 magnetization was recorded in the temperature range T = 5 – 300 K using a measuring field
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56 Hmeas = 10 Oe in both zero-field cooling (ZFC) and FC (Hcool = 10 Oe) modes. Magnetization
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isotherms (hysteresis loops) were measured between +50 and –50 kOe at T = 5 K after cooling in
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6 zero field. All data were corrected for diamagnetic contributions.
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9 2.7. Catalytic reduction of 4-nitrophenol. The reaction was performed in a 3 mL quartz cell,
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12 equipped with a magnetic stirrer and a cap. CoxFe3-xO4-DMSA-Au NPs ([Au]=0.44 mM) were
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14 added to a solution of 4-nitrophenol (1.83 mL, 0.1 mM) in different mole percentages with
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16 respect to the substrate (44, 22 or 9 µL of NP dispersion, corresponding to 10, 5 and 2%
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19 Au:substrate molar ratio, respectively). Then, an aqueous solution of NaBH4 (330 µL, 500 mM)
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21 was added to the mixture (initial reaction time). The transformation ratio was followed
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23 monitoring the absorption at 400 nm and 550 nm (see SI) of the reaction mixture at intervals of 1
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26 minute. After each catalytic cycle, the NP catalyst was magnetically recovered by removal of the
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28 supernatant. The collected NPs were washed with water and fresh 4-nitrophenol and NaBH4
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solutions were introduced in the cell to start a new catalytic cycle. For the control reactions, the
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33 same procedure described above for the 10% molar ratio case was carried out, using CoxFe3-xO4-
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35 DMSA NPs (180 µL, [Fe]=0.6 mM) and Au-DMSA NPs (14 µL, [Au]=1.2 mM, 10% molar
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38 ratio) as catalyst.
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41 2.8 Electrochemical reduction of 4-nitrophenol. Electrochemical investigations were
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43 performed using an Autolab PG-Stat 12 (Ecochemie, The Netherlands) potentiostat/galvanostat,
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46 in a conventional three electrodes cell with a saturated calomel reference electrode and a
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48 platinum wire counter electrode. The working electrode was a glassy carbon one (AMEL, Italy, 3
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mm diameter), modified by drop casting with a Kartell micropipette 20 µL of a solution of the
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53 nanomaterials: CoxFe3-xO4-DMSA-Au NPs ([Au]=0.44 mM), CoxFe3-xO4-DMSA NPs ([Fe]=0.6
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55 mM), Au-DMSA NPs ([Au]=0.4 mM). Current densities were determined dividing the
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experimental currents by the electrode geometric area. Prior to modification, the GC support
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electrode surface was cleaned with synthetic diamond powder (Aldrich, diameter 1 µm, 99.9%)
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6 on a Struers DP Nap wet cloth and rinsed in water. 0.1 M NaClO4 (Sigma Aldrich) was used as
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8 supporting electrolyte in aqueous media (20 mL) and mixed with a saturated solution of 4-
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nitrophenol (60 µL).
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14 3. RESULTS AND DISCUSSION
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17 3.1. Synthesis of water dispersible cobalt ferrite. To produce hetero-NPs we tuned a multi-
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20 step protocol (Scheme 1).
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47 Scheme 1. Synthetic strategy for CoxFe3-xO4-DMSA-Au NPs.
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50 The initial step consisted in the synthesis of organic dispersible cobalt ferrite (CoxFe3-xO4-OA
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53 NPs), fabricated according to the procedure published by Zhu et al.31 by means of the
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55 solvothermal decomposition of iron(III) and cobalt(II) acetylacetonate precursors. This
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procedure allowed us to have an efficient control over the morphology of superparamagnetic NP
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synthesis. We slightly modified the literature protocol by employing 1,2-hexadecanediol as a
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6 mild reducing agent, that guarantees the monocrystallinity of cobalt ferrite nanocrystals.34 The
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8 obtained NPs had spheroidal shape (median equivalent diameter = 7.8 ± 1.2 nm, Figure 1a and
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Figure S1) and both the electron diffraction pattern and the HRTEM fringes (Figure S2)
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32 Figure 1. TEM images (scale bar = 50 nm) of a) CoxFe3-xO4-OA NPs, b) CoxFe3-xO4-DMSA NPs and c) CoxFe3-
33 xO4-DMSA-Au NPs with an expansion in the inset (bar 10 nm).
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38 The chemical composition of the NPs has been investigated by recording EELS spectra
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41 (Figure 2a) on a grid area of about 0.36 µm2. In the spectra the Fe-L2,3 edge (beginning at 708
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43 eV) and the Co-L2,3 edge (beginning at 779 eV) can be observed. To calculate the molar ratio
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between Fe and Co we fitted the spectra using the best-fit procedure implemented in the EELS
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48 Model 3.3 software,35 obtaining an atomic Fe:Co ratio equal to 2.7±0.9 (x=0.8±0.2). By the ESI
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50 maps (Figure 2c,d), which provide an image of the distribution of a specific element, it is evident
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53 that both metal ions are present in each NPs. Thus, we established that the two metals were
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55 homogeneously distributed in the sample. This finding, along with the diffraction data, showed
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57 that we truly obtained cobalt ferrite NPs and not a mixture of iron oxide NPs and cobalt oxide
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NPs. Moreover, using the independent spectroscopic technique EDX (figure S3), we measured
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6 the atomic percentage of Fe = 69.8% and Co = 30.2% that correspond to an atomic Fe:Co ratio
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8 of 2.31 (x = 0.91). This experiment was performed on a grid area of about 2.5 µm2, larger than
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11 that sampled in the EELS experiment. The Fe:Co ratio obtained by EELS and EDX are in a good
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13 agreement and show the quasi stoichiometric composition of the cobalt ferrite NPs with x ≅ 0.9.
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39 Figure 2. a) EELS spectrum of CoxFe3-xO4-OA NPs where the two edges starting at 708eV and 779eV, correspond
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41 red) and cobalt (d, green). The bars correspond to 50 nm.
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The second step was focused on the exchange of surfactants, to remove the long-chain
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49 hydrophobic ligands (oleic acid, oleylamine) which coated the metal oxides NPs and to bring
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51 them in water media. To accomplish the exchange, we chose to use 2,3-meso-dimercaptosuccinic
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54 acid (DMSA), a ligand well known in literature for its ability to transfer ferrite NPs from organic
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56 to aqueous media.36 The literature procedure was improved by adding a second exchange step.
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First, a solution of DMSA in DMSO was dropped into a toluene dispersion of CoxFe3-xO4-OA
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6 NPs. The substitution of OA with DMSA lets NPs to precipitate in toluene and then to be
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8 dispersed in water. During the second step, the aqueous NP dispersion was treated with an excess
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of DMSA, in order to improve its colloidal stability in water (Figure 1b and Figure S4-6). NPs
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13 treated with an excess of DMSA resulted in a decreased aggregation on the TEM grid (Figure
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15 S5), confirmed by the size distributions obtained by DLS (Figure S7). Figure S7, in fact, show a
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18 decreased hydrodynamic size and distribution from the first to the second step of the ligand
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20 exchange procedure, underlining the improvement in stability and dispersion. To evaluate the
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22 colloidal stability before and after the treatment with the excess of DMSA, we measured the
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25 variation of ζ-potential of NP solution, as a function of pH and ionic strength of the medium.37-39
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27 At a fixed ionic strength ([KCl]=1 mM), the pH of the NP dispersion was tuned in a range
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between 2 and 12 by adding aq. NaOH or aq. HCl (0.5 M) (Figure S8a), registering that the NP
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32 dispersion, obtained after the second addition of DMSA, had a slight increment of negative ζ-
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34 potential and thus an improved colloidal stability at pH > 3.5.37,39 At pH < 3.5, CoxFe3-xO4-
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37 DMSA NPs treated with the excess of DMSA displayed a rapid increase of ζ-potential that could
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39 be ascribed to the protonation of free carboxylic groups of DMSA (pK1 2.71, pK2 3.48). The
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41 influence of the ionic strength on the CoxFe3-xO4-DMSA NPs colloidal stability was evaluated
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44 increasing the concentration of KCl in a phosphate-buffered NP dispersion (PBS, pH=7). The
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46 data (Figure S8b) showed lower ζ-potential values for higher ionic strengths,38 as expected for
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48 charged NPs, and confirmed the improved stability of NPs obtained after the treatment with the
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51 excess of DMSA in a large range of ionic force. FT-IR spectra (Figure S9) are in agreement with
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53 the literature data,39 confirming the success of the ligand exchange procedure. By means of ICP-
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OES measurements (Figure S10), the atomic Fe:Co ratio in CoxFe3-xO4-DMSA NPs was
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established to be 71:29 (x = 0.87), confirming the result obtaining by EELS and EDX
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6 experiments on CoxFe3-xO4-OA NPs. Therefore, the “two-steps” ligand exchange procedure did
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8 not alter the chemical composition of the ferrite NPs.
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12 3.2. Synthesis of gold decorated cobalt ferrite. The obtained water dispersible CoxFe3-xO4-
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14 DMSA NPs were used as a substratum for the localized growth of ultrasmall gold NPs,
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16 exploiting the known reducing ability of DMSA for the production of nanometer sized gold
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19 nanoparticles.32 Recently, Carlà et al.26 described the production of core-shell CoFe2O4/Au
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21 composites, by using DMSA as stabilizing agent for CoFe2O4 NPs and a sonochemical process
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23 to achieve the reduction of gold salts. In another paper, Odio et al.40 took advantages of the
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26 ability of magnetite-DMSA NPs to adsorb gold ions from aqueous environments, recording the
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28 formation of reduced gold. Drawing inspiration from literature, we exploited the double role that
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DMSA can play to produce controlled and water dispersible cobalt ferrite/gold hetero-structured
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33 NPs (Scheme 1), by slowly dropping HAuCl4 in a CoxFe3-xO4-DMSA NP solution. In order to
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35 optimize the decoration step, we evaluated the influence of two main parameters: the Au3+
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38 amount and the rate of its addition. A solution of HAuCl4 (0.2 mM) was dropped (83 µL/min) in
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40 5 mL of CoxFe3-xO4-DMSA NP water dispersion ([Fe] = 34 µg/mL), supplying three different
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42 quantities (10-3 mmol, 2·10-3 mmol, 4·10-3 mmol). The addition of 10-3 mmol of Au3+ resulted in
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45 a low decoration level (1.8±1.2 Au NPs/ CoxFe3-xO4-DMSA NPs) with Au NPs having
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47 equivalent diameter < 3 nm (Figure S11a,d). The injection of 4·10-3 mmol of Au precursor led to
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a good decoration level (3.1±1.7 Au NPs/ CoxFe3-xO4-DMSA NPs) but also to the formation of
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52 undesired large gold NPs having equivalent diameter >20 nm (Figure S11c,f). The best
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54 compromise was achieved using 2·10-3 mmol of HAuCl4 resulted in 2.4±1.3 Au NPs/ CoxFe3-
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57 xO4-DMSA NPs with Au NPs having equivalent diameter < 3 nm (Figure S10b,e). To evaluate
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the role of the dropping rate in the decoration step, the optimized quantity of Au3+ (2·10-3 mmol)
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6 was slower added (flow rate = 41.5 µL/min) or rapid injected. By decreasing the Au3+ addition
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8 rate, the instantaneous DMSA/Au ratio in the mixture incremented, promoting the formation of
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11 small Au NPs (median diameter 2.7 ± 0.5 nm) with respect to the growth of the larger ones,41
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13 achieving a decoration of 2.9±1.7 Au NPs per CoxFe3-xO4-DMSA NP (Figure 4, S11g and S13-
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14). While, the sample obtained by the single injection present a low decoration degree (1.4±1.7
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18 Au NPs per CoxFe3-xO4-DMSA NP) and the presence of larger Au NPs with dmedian=28 ± 8 nm
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20 (Figure 4c and Figure S12).41 Moreover, comparing UV-vis spectra (Figure 3a), the surface
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23
plasmonic resonance (SPR) peak at 550 nm, correlated to the presence of large Au NPs, is
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25 evident only in the sample obtained by single injection.20,42 SPR peak is barely visible in the
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27 CoxFe3-xO4-DMSA-Au NP solution obtained by the dropped addiction, confirming the scarce
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30 presence of large Au NPs.
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46 Figure 3. a) UV-Vis spectra of the CoxFe3-xO4-DMSA NPs and CoxFe3-xO4-DMSA-Au NPs obtained by a single
47
injection or by a slow dropping (41.5 µL/min); b) STEM Image of CoxFe3-xO4-DMSA-Au NPs obtained by slow
48 dropping; c) STEM Image of CoxFe3-xO4-DMSA-Au NPs obtained by single injection. The scale bars correspond to
49 20 nm.
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TEM and STEM images confirmed the information obtained from UV-vis spectra (Figure 1c
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56 and Figure 3b,c). STEM images show the high degree and uniformity of decoration that can be
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obtained following the optimized synthetic strategy (Figure 3b and Figure S15). As expected, we
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6 identified in the electron diffraction of the CoxFe3-xO4-DMSA-Au NPs (Figure S16) the two
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8 patterns corresponding to Au and CoxFe3-xO4. The atomic ratio between Fe, Co and Au was
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quantified by ICP-OES measurement as Fe:Co:Au = 72:13:14. After gold decoration, a variation
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13 in the ratio between Fe and Co was detected, corresponding to a decrease in cobalt content26 (x ≅
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0.5) (Figure S17). This result is in agreement with the elemental composition measured using
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18 EDX spectroscopy (Figure S18). In summary, the best synthetic outcome – extensive decoration
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20 and minimization of the presence of large gold NPs – is achieved by slow injection (flow rate =
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41.5 µL/min) of 0.33 eq of gold precursor, calculated with respect to the iron content of the
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25 ferrite NPs.
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27 3.3. Magnetic properties of cobalt ferrite NPs.
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30 We investigated the magnetic properties of the cobalt ferrite nanocrystals before and after the
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32 gold decoration in order to study the effects of the decrease of the cobalt content (Figure 4 and
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34 Figure S19-S20). The main magnetic parameters are reported in Table 1.
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39 Table 1. Magnetic parameters of CoxFe3-xO4-DMSA and CoxFe3-xO4-DMSA-Au NPs
40 Sample Hc Ms Mr Ms/Mr Tmax Tder
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42
(kOe) (emu/g) (emu/g) (K) (K)
43 CoxFe3-xO4 DMSA 14.9 142 113 0.79 240 200
44 CoxFe3-xO4 DMSA-Au 14.5 107 84 0.78 270 230
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The isothermal magnetization M(H) of both samples presents a broad hysteresis loop with
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50 large coercive field typical of magnetically hard cobalt ferrite (Figure 4). The coercive field Hc of
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52 both samples is typical of cobalt ferrite NPs and smaller than the bulk value of 25.2 kOe.43 Hc is
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55 only slightly smaller after gold decoration despite the substantial Co loss (x decreases from 0.87
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57 to 0.46). It was however recently observed44 that in sub-stoichiometric CoxFe3-xO4 NPs the
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magnetic properties quickly change when x is small and level off about x = 0.5, in accordance
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6 with the present observation. The recorded hysteresis loops are almost, but not exactly, major
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8 loops and the saturation magnetization Ms values might therefore be slightly underestimated. MS
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decreases from 142 to 107 emu/g upon gold decoration. Both values are larger than the MS bulk
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13 value, (93 emu/g at 5K).43
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34 Figure 4. Hysteresis loops of the cobalt ferrite samples before and after gold decoration. Hollow circles: CoxFe3-
35 xO4-DMSA; solid circles: CoxFe3-xO4-DMSA-Au.The magnetization is given relative to the mass of cobalt ferrite.
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40 Such large values are difficult to interpret since electron diffraction excluded the presence of
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42 non-ferritic phases with larger magnetization. A similar effect has been observed in small (3 nm)
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44 stoichiometric cobalt ferrite NPs diluted in a silica matrix and ascribed to frozen canted spins
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47 located in a 0.3 nm thick surface shell of the ferrite nanocrystal.45 However, it is uncertain if this
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49 conclusion can also be drawn for our 7.8 nm sub-stoichiometric undiluted cobalt ferrite
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nanocrystals. The squareness ratio Mr/Ms is 0.79 and 0.78 for CoxFe3-xO4 DMSA and CoxFe3-xO4
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54 DMSA-Au respectively, close to the value predicted for non-interacting randomly-oriented
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56 Stoner-Wohlfahrt nanocrystals having cubic magnetocrystalline anisotropy.46,47 Such high values
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have already been observed in nanocomposites containing cobalt-ferrite NPs in a polyaniline
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6 matrix.48 We also measured the zero field cooling (ZFC) and field cooling (FC) magnetization
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8 curves of both samples as a function of the temperature (from 5 to 300 K) using a measuring
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field of 10 Oe (Figure S19-S20). These curves are typical of magnetic nanoparticles and clearly
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13 display the transition to the superparamagnetic regime at high temperature. In general, the
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15 behavior of both samples agrees with the prediction that cobalt ferrite nanoparticles having
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18 diameter < 10 nm are superparamagnetic at 300 K.49 Several proposals have been made to
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20 estimate the average blocking temperature from ZFC/FC curves. A popular choice is the
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22 temperature Tmax where MZFC reaches its maximum value. We observed Tmax = 240 and 270 K in
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25 the case of CoxFe3-xO4-DMSA and CoxFe3-xO4-DMSA-Au NPs, respectively. The latter value is
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27 in agreement with a literature value for ferrite NPs with similar cobalt content.44 A deeper insight
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into the blocking/unblocking behavior of the NPs can be achieved by computing the derivative
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32 −d(MFC −MZFC)/dT, which is an approximate representation of the distribution of the magnetic
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34 anisotropy energy barriers (Figure S19-S20).50 The most probable barrier is at Tder = 200 and 230
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37 K for CoxFe3-xO4-DMSA and CoxFe3-xO4-DMSA-Au NPs, respectively. Both estimates thus
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39 indicate that the blocking temperature increases by about 30 K upon loss of cobalt caused by the
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41 gold decoration. This is unexpected since (i) the cobalt ferrite size does not significantly change
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44 upon gold decoration and (ii) cobalt ions largely add to the global magnetic anisotropy due to the
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46 their strong single-ion anisotropy. At the moment we can only suggest that decoration with gold
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48 NPs modifies the interparticle interaction (e.g. the dipole-dipole interaction) in such a way that
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51 the cobalt ferrite nanocrystals are subject to a larger global magnetic anisotropy translating into a
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53 higher blocking temperature.
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3.4. Catalytic application of gold decorated cobalt ferrite. Taking advantage of the
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6 magnetic properties of the nanometric ferrite support and the catalytic potential of Au NPs, the
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8 produced CoxFe3-xO4-DMSA-Au NPs could be used as quasi-homogeneous and magnetically
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recyclable catalyst for red-ox reactions.19,21,22 In the present study the catalytic activity of
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13 optimally-decorated CoxFe3-xO4-DMSA-Au NPs has been investigated performing the reduction
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15 of 4-NP to 4-AP, monitoring the reaction by UV-vis spectroscopy and using NaBH4 as reducing
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18 agent (Figure 5).29 In the presence of an excess of NaBH4, 4-NP is converted into its sodium salt
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20 (4-nitrophenolate) which shows an intense absorption peak at 400 nm. Through monitoring the
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22 decreasing of the absorbance at 400 nm during the time, it is possible to follow the kinetics of the
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25 reaction (Figure 5).
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50 Figure 5. UV-vis spectra of 4-nitrophenol, sodium 4-nitrophenolate and sodium 4-aminophenolate
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53 To evaluate the catalytic efficiency (Figure 6a), three different CoxFe3-xO4-DMSA-Au NPs
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55 amounts have been tested (2, 5 and 10 % molar with respect to Au, as measured by ICP-OES).
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58 Furthermore, as negative control, the red-ox reactions were performed without addition of
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catalyst or by adding the colloidal water dispersion of cobalt ferrite (CoxFe3-xO4-DMSA NPs).
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6 Either without catalyst or with CoxFe3-xO4-DMSA NPs, no reaction occurred as expected,51
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8 indicating that the presence of the noble metal is required for catalysis. Instead, in the presence
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of CoxFe3-xO4-DMSA-Au NPs, the reaction was completed in a few minutes after an induction
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13 time dependent on the amount of the catalyst. According to the Langmuir–Hinshelwood (LH)29,52
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15 model (Figure S21) which describes the kinetics of this reaction, both reactants (4-NP and
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18 hydride) need to be adsorbed on the surface of the NPs to react. The observed induction period is
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20 then related to the slow restructuring of NP surfaces by the reactants,52,53 before the reaction
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22 starts. To confirm this hypothesis we performed two catalyzed reactions pre-incubating NPs with
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25 NaBH4 or with 4-NP: in both cases we still observed an induction time even if shorter (2-4 min
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27 vs 6-8 min, Figure S21-S22). The catalytic activity of the hetero-nanoparticles is excellent
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(Figure 6b and Table S24). For instance, when the catalyst is used at 2% mol (Au), the reaction
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32 proceeds with one of the highest rate reported in literature (knorm = 4.4 ·106 s-1mol-1) by using
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34 nanosized catalyst.19 Finally, to compare our catalytic system with a non-magnetically supported
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37 one, we synthesized Au-DMSA NPs with a median diameter of 2.1±0.4 nm following a literature
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39 procedure (Figure S25a-S26).32 Using 10% molar of Au-DMSA NPs with respect to 4-NP, the
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41 initial activation time was shorter but the reaction rate was drastically slower. In fact, kobs for Au-
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44 DMSA NPs was 6 times lower than that observed for the corresponding amount of CoxFe3-xO4-
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46 DMSA-Au NPs (Figure 6b and Table S24).
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22 Figure 6. a) The reduction efficiency of 4-NP by: ■ No catalyst; ● CoxFe3-xO4-DMSA NPs; ∆ 10% Au-DMSA NPs;
23 ▲ 10% CoxFe3-xO4-DMSA-Au NPs; □ 5% CoxFe3-xO4-DMSA-Au NPs; ○ 2% CoxFe3-xO4-DMSA-Au NPs.
24 Remaining Ratio is defined as the residual percentage of 4-nitrophenolate in the reaction solution, calculated from
25 the absorbance values as explained in SI. b) The observed kinetic constant kobs for 10% Au-DMSA NPs and 2%,
26 5% and 10% CoxFe3-xO4-DMSA-Au NPs.
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28 The higher catalytic activity of CoxFe3-xO4-DMSA-Au NPs respect to Au-DMSA NPs can be
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ascribed to the unique electronic features of hetero-nanoparticles. Even if the electronic behavior
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33 at the metallic interface is still unclear, in literature it is hypothesized that an electron flow from
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35 gold to ferrite NPs drives the remarkable improvement in catalytic activity of these kinds of
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38 hetero-nanoparticles.6,54,55 To deeper investigate their catalytic behavior, we carried out an
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40 electrochemical reduction of 4-NP. An electrocatalytic effect (100 mV peak shift towards less
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42 negative potentials) is observed for all the modified electrodes (Figure 7), testifying the catalytic
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45 properties of the investigated materials in the 4-NP reduction reaction. Moreover, in the case of
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47 CoxFe3-xO4 modified electrodes (with or without Au NPs) an increase in peak current densities
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50
(i.e. electrochemical reaction rate) is evident, ascribed to an increase of the surface area and thus
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52 of the available reactive sites of these materials. This result is in agreement with the previous
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54 experiment where kobs calculated for Au-DMSA NPs resulted lower than that observed for
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57 CoxFe3-xO4-DMSA-Au NPs (Figure 6).
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25 Figure 7. Cyclovoltammetric reduction patterns (0.1 V s-1 scan rate) of 4-NP (60 µL of a saturated aqueous solution
26 in 20 ml of 0.1 M NaClO4 aqueous solution) on the GC support and on three different modified electrodes.
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29 Interestingly, from the electrochemical results, it seems that Au NPs does not provide an extra
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32 contribute in the direct electrocatalytic reduction of 4-NP, since CoxFe3-xO4-DMSA NPs can
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34 efficiently catalyze the reaction. On the contrary, in our model reaction condition which exploits
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the use of NaBH4, CoxFe3-xO4-DMSA NPs are inactive while Au NPs presence is crucial to
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39 promote on their surface the absorption and oxidation of sodium borohydride.56 After this first
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41 step, the synergistic effect between Au NPs and cobalt ferrite transfer efficiently the electrons
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required for the reduction.52,57 This aspect, together with the increased surface active areas, can
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46 explain the better performance registered for CoxFe3-xO4-DMSA-Au NPs with respect to Au-
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48 DMSA NPs.
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51 Due to their magnetization, the hybrid NPs can be rapidly (few seconds) and easily
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53 recovered using a neodymium-based magnet (Figure S27) and re-dispersed in MilliQ water for
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55 further catalytic cycles. To verify the recycling efficiency of the CoxFe3-xO4-DMSA-Au NPs, we
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58 performed 5 consecutive catalytic cycles (Figure 8a). In the first cycle the induction time is not
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negligible, but it slowly diminishes with the repetition of the cycles, confirming the LH
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26 Figure 8. Reduction efficiency of 4-NP in the consecutive catalytic cycles (a) and the corresponding kobs calculated
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30 The observed rate constant was calculated for each recycle (Figure 8b). After the first cycle
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(kobs = 2.7·10-2 s-1), the kobs halved and maintained the value of 1.2·10-2 s-1 during the next four
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35 cycles. The high performance of the nano-catalyst was also proved by the fact that, even after 5
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37 catalytic cycles, the reduction of 4-NP was complete in less than 10 minutes.
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Figure 9. The concentration of Fe, Co and Au in: digestion blank, catalytic reaction supernatant, recovered
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After the first cycle’s completion, the amount of the metals was quantified by ICP-OES as in
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6 the recovered catalyst as in the supernatant solution and it was compared with those measured in
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8 the fresh catalyst and in the digestion blank (Figure 9). Noteworthy, no leaching was detected as
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the metal composition and concentration remained constant in the recovered and fresh catalyst.
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13 Moreover the metals abundance in the supernatant was comparable with that of the digestion
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15 blank. We performed an accurate characterization of the catalyst after the first cycle using
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18 electron microscopy. TEM (Figure 10 and Figure S28) and STEM (Figure S28) images show
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20 that recovered CoxFe3-xO4-DMSA-Au NPs formed aggregates probably included in an
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22 amorphous material, justifying the decreased reaction rate observed after the first cycle.19
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25 Nevertheless, CoxFe3-xO4-DMSA-Au NPs are not sintered, maintaining their single crystal
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27 nature. By EDX analysis (Figure S29) we calculated the atomic percentage of iron, cobalt and
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29
gold (79.1%, 10.1% and 10.4%, respectively; x = 0.34). This result is in agreement with the
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32 concentration ratio measured by ICP-OES and, qualitatively, also with the EELS spectrum
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34 (Figure S30). Finally, ESI images (Figure S31) confirm the homogeneous distribution of iron
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37 and cobalt in the ferrite NPs of the recovered catalyst.
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Figure 10. TEM image of the recovered catalyst after one cycle. The bar corresponds to 20 nm.
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4. CONCLUSIONS
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7 In this paper we reported an effective synthetic procedure to obtain water dispersible hybrid
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9 hetero-structured NPs, composed by a cobalt ferrite nanocore decorated by ultrasmall gold NPs.
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12 The designed protocol exploits the presence of 2,3-meso-dimercapto succinic acid acting both as
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14 coordinate ligand for water dispersible cobalt ferrite and as reducing agent for Au3+ ions. Thanks
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16 to its versatility, the procedure can be potentially applied to any type of spinel ferrite NPs,
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19 MxFe3-xO4 (M = Fe, Zn, Mn, Cu, Ni). A full characterization of each step has been provided,
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21 highlighting the factors that play a crucial role in the decoration step. Moreover, taking
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23 advantage of the ultrasmall size of Au NPs, we demonstrated that CoxFe3-xO4-DMSA-Au NPs act
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26 as efficient catalyst for the reduction of 4-NP to 4-AP showing a full conversion down to 2%
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28 molar of catalyst with an excellent knorm = 4.4·106s-1mol-1. Finally, by exploiting the
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31
magnetization of cobalt ferrite NPs, the catalyst was magnetically recovered and recycled up to 5
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33 times, maintaining a very high kobs over the cycles.
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40 ASSOCIATED CONTENT
41
42
43 Supporting Information. Synthesis of CoxFe3-xO4-OA NPs. Figure S1: TEM and statistical
44
45 distribution. Figure S2: HRTEM and diffraction pattern. Figure S3: EDX Spectrum. Ligand
46
47
48 exchange procedure (CoxFe3-xO4-DMSA NPs). Figure S4: picture of NPs before and after ligand
49
50 exchange. Figure S5: TEM images of CoxFe3-xO4-OA NPs and CoxFe3-xO4-DMSA NPs. Figure
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52
53
S6: statistical distribution. Figure S7: DLS size distribution of CoxFe3-xO4-OA NPs and CoxFe3-
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55 xO4-DMSA NPs. Figure S8: variation of the ζ-potential in function of pH and ionic strength.
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57 Figure S9: FTIR spectra. Figure S10: ICP-OES analysis. Synthesis of CoxFe3-xO4-DMSA-Au
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NPs. Figure S11: optimization process. Figure S12: STEM image of CoxFe3-xO4-DMSA-Au NPs
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6 obtained by single injection. Figure S13: statistical size distribution of Au NPs. Figure S14:
7
8 multimodal size distribution and ζ-potential value. Figure S15: STEM images of CoxFe3-xO4-
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DMSA-Au NPs. Figure S16: diffraction pattern. Figure S17: ICP-OES. Figure S18: EDX
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13 Spectrum. Magnetic properties of cobalt ferrite NPs. Figure S19: ZFC and FC magnetization of
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15 CoxFe3-xO4-DMSA NPs. Figure S20: ZFC and FC magnetization of CoxFe3-xO4-DMSA-Au NPs.
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18 Catalytic activity of CoxFe3-xO4-DMSA-Au NPs. Figure S21. Schematic representation of LH
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20 model. Figure S22: reduction efficiency after incubation with NaBH4. Figure S23: reduction
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22 efficiency after incubation with 4-NP. Table S24: kobs and knorm. Figure S25: TEM images of Au-
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24
25 DMSA NPs before and after catalytic reaction. Figure S26: UV-vis spectrum of Au-DMSA NPs.
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27 Figure S27: picture of the recovering of catalyst. Figure S28: TEM and STEM images of CoxFe3-
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29
xO4-DMSA-Au NPs after 1st cycle. Figure S29: EDX of CoxFe3-xO4-DMSA-Au NPs after 1st
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31
32 cycle. Figure S30: EELS of CoxFe3-xO4-DMSA-Au NPs after 1st cycle. Figure S31: TEM and
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34 ESI of CoxFe3-xO4-DMSA-Au NPs after 1st cycle. This material is available free of charge via the
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37 Internet at http://pubs.acs.org.
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40 AUTHOR INFORMATION
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43 Corresponding Author
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45
*E-mails: laura.polito@istm.cnr.it; anna.ferretti@istm.cnr.it
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49 Notes
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The authors declare no competing financial interest.
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54 Author Contributions
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The manuscript was written through contributions of all authors. All authors have given approval
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6 to the final version of the manuscript.
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12 ACKNOWLEDGMENT
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14 This work has been financially supported by Regione Lombardia (Italy) through the project
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16 RSPPTECH. LP thanks MIUR (Italy) for (PRIN 2010-2011: contract 2010JMAZML_003).
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21 REFERENCES
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23 (1) Song, H. Metal hybrid nanoparticles for catalytic organic and photochemical
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25 transformations. Acc. Chem. Res. 2015, 48, 491−499.
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54 Properties of Nanoparticles of Cobalt Ferrite, CoFe2O4. Chem .Mat. 2004,16,5689-5696.
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34 magnetite nanocatalysts. Appl. Catal. A-Gen. 2014, 486, 32-41.
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19 Figure 1. TEM images (scale bar = 50 nm) of a) CoxFe3-xO4-OA NPs, b) CoxFe3-xO4-DMSA NPs and c) CoxFe3-
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Figure 2. a) EELS spectrum of CoxFe3-xO4-OA NPs where the two edges starting at 708eV and 779eV,
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18 Figure 3. a) UV-Vis spectra of the CoxFe3-xO4-DMSA NPs and CoxFe3-xO4-DMSA-Au NPs obtained by a single
19 injection or by a slow dropping (41.5µL/min); b) STEM Image of CoxFe3-xO4-DMSA-Au NPs obtained by slow
20 dropping; c) STEM Image of CoxFe3-xO4-DMSA-Au NPs obtained by single injection. The scale bars
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Hysteresis loops of the cobalt ferrite samples before and after gold decoration. Hollow circles: CoxFe3-xO4-
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Figure 5. UV-vis spectra of 4-nitrophenol, sodium 4-nitrophenolate and sodium 4-aminophenolate
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23 Figure 6. a) The reduction efficiency of 4-NP by: ■ No catalyst; ● CoxFe3-xO4-DMSA NPs; ∆ 10% Au-DMSA
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