Article

pubs.acs.org/Langmuir

Gaining Control over Radiolytic Synthesis of Uniform Sub-3-

nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the
Electron Microscope
Patricia Abellan,*,†,‡ Lucas R. Parent,‡,§ Naila Al Hasan,∥ Chiwoo Park,⊥ Ilke Arslan,‡ Ayman M. Karim,#
James E. Evans,▽ and Nigel D. Browning‡
†
SuperSTEM Laboratory, SciTech Daresbury Campus, Keckwick Lane, Daresbury WA4 4AD, United Kingdom
‡
Fundamental and Computational Sciences Directorate, ∥Institute for Integrated Catalysis, and ▽Environmental Molecular Science
LaboratoryPacific Northwest National Laboratory, Post Office Box 999, Richland, Washington 99352, United States
§
Department of Chemistry & Biochemistry, University of California, San Diego, La Jolla, California 92093, United States
⊥
Department of Industrial and Manufacturing Engineering, Florida State University, Tallahassee, Florida 32306, United States
#
Department of Chemical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, United States
*
S Supporting Information

ABSTRACT: Synthesizing nanomaterials of uniform shape

and size is of critical importance to access and manipulate the
novel structure−property relationships arising at the nanoscale,
such as catalytic activity. In this work, we synthesize Pd
nanoparticles with well-controlled size in the sub-3 nm range
using scanning transmission electron microscopy (STEM) in
combination with an in situ liquid stage. We use an aromatic
hydrocarbon (toluene) as a solvent that is very resistant to
high-energy electron irradiation, which creates a net reducing
environment without the need for additives to scavenge
oxidizing radicals. The primary reducing species is molecular
hydrogen, which is a widely used reductant in the synthesis of
supported metal catalysts. We propose a mechanism of particle
formation based on the effect of tri-n-octylphosphine (TOP)
on size stabilization, relatively low production of radicals, and autocatalytic reduction of Pd(II) compounds. We combine in situ
STEM results with insights from in situ small-angle X-ray scattering (SAXS) from alcohol-based synthesis, having similar
reduction potential, in a customized microfluidic device as well as ex situ bulk experiments. This has allowed us to develop a
fundamental growth model for the synthesis of size-stabilized Pd nanoparticles and demonstrate the utility of correlating different
in situ and ex situ characterization techniques to understand, and ultimately control, metal nanostructure synthesis.

■ INTRODUCTION
The chemical and physical properties of metallic nanomaterials
can differ significantly from those of the bulk. These differences
arise from the relatively large number of surface atoms per
particle volume and from quantum confinement effects on the
nanoscale,1−3 and they can be tuned during synthesis.4 For
example, the catalytic efficiency of metallic nanoparticles and
clusters is known to be strongly particle-size-dependent.3,5,6
True control of particle size during synthesis is, therefore,
crucial to achieving optimized performance and to precisely
investigate structure−property relationships. For the specific
case of Pd, nanoparticles are widely used as catalysts and
electrocatalysts,7,8 where high efficiency in various fuel cell
types has been demonstrated. Pd is an especially effective
catalyst, for instance, of ethanol oxidation in alkaline media9,10
since it is not easily poisoned by carbon monoxide and, hence,
is a key material for applications such as hydrogen storage11,12
and sensing.13,14 Typically, the redox synthesis of particles with
well-controlled size involves the introduction of a protective
stabilizer during particle formation: surfactants, polymers,
dendrimers, and ligands are common additives used.3,15,16
Additionally, factors such as nature and concentration of
reducing agent and precursors, nucleation sites, and processing
temperature also determine the nucleation and growth kinetics
of metallic nanocrystals of uniform size and shape.15,17−19
Methods that exploit radiation chemistry have been
previously applied to the synthesis of metallic nanomateri-
als,6,20−24 including Pd nanostructures.25 Radiolytic synthesis
has also been successful in preparing metal-supported clusters
for catalytic applications.26−28 These synthesis routes use the
Received: November 15, 2015
Revised: January 7, 2016
Published: January 7, 2016

© 2016 American Chemical Society 1468 DOI: 10.1021/acs.langmuir.5b04200

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chemical effects of the absorption of high-energy radiation,
typically 60Co γ-rays or 2−20 MeV electrons,29,30 by precursor-
containing liquids to form nanostructures by reproducing a
selective reducing/oxidizing environment. Conditions to
generate free radicals of strong reducing potential can be
found and exploited for different applications.31,32 Some
strengths of radiation chemical synthesis are that the nuclei
formed are homogeneously distributed in the whole volume,
growth rate can be easily controlled, and synthesis can be
performed at room temperature.6,33
New characterization methods have been developed to
investigate colloidal synthesis and gather real-time information
at the solid−liquid interface.34−38 Among them, in situ liquid
cells used in combination with (scanning) transmission electron
microscopy [(S)TEM] uniquely allow for direct imaging of the
formation of nanoparticles with millisecond temporal reso-
lution and subnanometer spatial resolution.39−44 Control of the
experimental parameters and reproducibility of the results
requires an understanding of the effects of high-energy
electrons on the solution.45−49 Thus far, most experiments in
the fluid stage involve the use of water as a solvent. In water,
the radiation chemical yields are relatively large where highly
reactive oxidizing and reducing radicals and species are created
in about equal amounts.50 Thus, reproducing net reducing
conditions for particle growth involves the addition of
substances that convert primary radicals into free reducing
radicals (use of OH• scavengers, for instance).20,50 Since the
electron beam in the STEM is used as both irradiation source
and imaging probe to resolve dynamic processes, larger incident
electron doses may be required to achieve high-magnification
imaging in the case of small (<3 nm) nanoparticles. An ideal
environment that can be understood and thus tuned in situ in
the STEM would, therefore, consists of net reducing (or net
oxidizing) conditions, where minimum (ideally none) additives
are present, and where the yields of radical production are the
smallest possible for a given incident electron dose.
Aromatic hydrocarbons are known to be very resistant to
high-energy electron irradiation,30 with toluene being able to
create a net reducing environment, as discussed below.
Furthermore, the use of organic solvents instead of water
allows for tuning the polarity of the medium, giving access to a
broader range of synthesis conditions. Here, we report a study
aimed at finding more suitable Pd nanoparticle synthesis
environments that accomplish all the conditions above for
nanostructure control. We demonstrate the ability to control
the nucleation kinetics as well as the final size of Pd
nanoparticles, ∼2.2 nm diameter, during in situ STEM
irradiation, which is matched in bulk solution synthesis using
hexanol reduction of the same precursors. Synthesis is
performed starting from a precursor solution of palladium
acetate [Pd(OAc)2] dissolved in toluene, to which tri-n-
octylphosphine (TOP) is added as a capping agent to promote
growth stabilization.
■ EXPERIMENTAL SECTION
Scanning Transmission Electron Microscopy and Fluid
Stage. In situ STEM data sets were acquired on an 80−300 kV
FEI probe Cs-corrected Titan electron microscope equipped with an
electron gun monochromator and a Gatan Quantum ERS
spectrometer. All the experiments were performed with 300 kV
electrons. Liquid experiments in the STEM were performed on a
Hummingbird Scientific fluid stage. Silicon nitride (SiNx) windows, 10
nm thick and supported on silicon frames (Norcada, Inc.), were used
to maximize image contrast while keeping the liquid thickness
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relatively constant. Platinum spacers of 70 nm thickness were built
on one of the chips by using focused ion beam (FIB) lithography in a
dual-beam FIB/SEM (FEI Quanta). Prior to sample loading, the
silicon nitride chips were submitted to plasma cleaning for 1 min in
argon atmosphere at 150 mTorr pressure. Loading of the sample in the
fluid stage was carried out inside an MBraun glovebox filled with
purified argon where the solution was allowed to flow into the cell at 5
μL/min for 15 min. Prior to solution flow, argon was allowed to flow
directly from the environment for 10 min to ensure no residual oxygen
was present in the lines. The electron beam current values reported
have been measured by use of the screen dose meter of the
microscope, previously calibrated to give the value at the sample plane
by use of the calibration curve shown in Figure S1. Calibration of the
screen dose meter current reading of the microscope was done by use
of an analytical holder equipped with a Faraday cup near the specimen
location at the tip of the holder (Gatan, Inc.).47 An electron current of
5.7 pA and pixel dwell time of 3 μs were used for all STEM data sets,
giving rise to values of the electron dose rate of 31 and 116 e−/Å2 per
frame for 450K× and 910K× magnification, respectively. Formation
kinetics were not accurately detected for magnifications below 450K×.
A direct conversion of electron dose rates into radiation chemistry
units yields 3.1 × 107 Gy/s (450K×) and 11.5 × 107 Gy/s (910K×),
where the stopping power for 300 kV electrons in toluene is 2.352
MeV·cm2/g51 and total frame time was 3.78 s. In situ data sets 1−4 are
included as Movies S1, S2. S3, and S4, respectively. The liquid
thickness was not measured in situ. Thin liquid layer thicknesses of
100−150 nm were considered for our volume calculation in Figure 4
(see Supporting Information for further details and the effect of
thickness uncertainty in the calculations).
Precursor Solution Preparation and Nanoparticle Chemical
Synthesis. Toluene (99.8%) and recrystallized palladium(II) acetate
(99.98%) were purchased from Sigma−Aldrich (St. Louis, MO).
Palladium acetate was dissolved in toluene in septum-sealed
scintillation vials to maintain an airtight environment and degassed
with ultra-high-purity helium (99.999% purity from Oxarc) prior to
addition of the capping agent, TOP. The concentration of Pd in
toluene was 5 mM for in situ STEM experiments as well as ex situ bulk
synthesis and 50 mM for in situ small-angle X-ray scattering (SAXS)
experiments. The precursor to capping agent ratio was 1:1.5 Pd/TOP.
Storage and addition of TOP (Aldrich, 90%) was carried out in an
MBraun glovebox supplied with nitrogen. Hexanol (anhydrous,
≥99%) was also purchased from Sigma−Aldrich (St. Louis, MO)
and sparged with ultra-high-purity helium prior to solution
preparation.
Small-Angle X-ray Scattering. SAXS studies of TOP-capped Pd
nanoparticle bulk synthesis were carried out at the Argonne National
Laboratory (ANL) Advanced Photon Source (APS) with the pinhole
setup at beamlines 12-ID-C and 12-ID-B with incident X-ray energies
of 18 and 12 keV, respectively. In situ SAXS data was also collected in
a microfluidic reactor with similar results. The reacted solution from
the microfluidic reactor (at 50 mM) was diluted with toluene to 5 mM
and drop-cast on a lacey carbon film supported on a copper
transmission electron microscopy (TEM) grid (Ted Pella, Inc.) to
investigate the reaction products by STEM. From the time evolution
of particles from SAXS, a linear fit was used to obtain the nucleation
rate (arbitrary units/s) as the slope of the number of particles versus
time at the early reaction times. The slope was scaled by a factor
estimated by taking into account the initial concentration of solution,
final average nanoparticle size, and final number of nanoparticles
(where full conversion of the precursor after an extended time period
is assumed). A step-by-step estimation of the initial nucleation rate
from SAXS for similar reactions and details on microreactor fabrication
and operation, SAXS data acquisition and analysis, and materials
preparation can be found elsewhere.38
Multitarget Particle Tracking Analysis. The multitarget particle
tracking approach has been previously applied to analysis of video
frames of silver nanoparticles grown via in situ liquid STEM44,52 and
has provided insights into the attack mechanisms that occur during
degradation of electrolyte solutions in Li ion batteries.53 First, an
image segmentation algorithm was applied to successive images in
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order to extract a set of image pixel locations for nanoparticles,54 and
an object tracking algorithm was applied55 to associate the pixel
locations over multiple time frames.56 Further details can be found in
refs 52,55, and 56.
■ RESULTS
First we consider the radiation chemistry of the solvent,
toluene. It is indeed solvent radiolysis that predominantly
dictates the species and yields involved in the chemical
processes leading to metal nanostructure synthesis in the
STEM fluid stage. Aromatic hydrocarbons such as toluene are
very resistant to radiation damage because the excitation energy
is not localized in a particular bond but shared by all π-electrons
in the molecule.30 Additionally, the radiation process is
dominated by electron−ion recombination,30,57,58 limiting the
overall production of free radicals in these liquid media. An
introduction to the concept of geminate recombination and
some relevant numbers for toluene and other solvents to
illustrate this fact are given in Supporting Information. Overall,
the yield of ions escaping geminate recombination in toluene
(yield of free ions) is very low (Gfi = 0.01 μmol·J−1).59 This
means that the amount of major ionic species produced by
radiolysis of liquid toluene will be much smaller than that of
liquid water or other polar liquids such as alcohols.
Previous work has shown that the major products in
radiolysis of toluene are hydrogen and dimeric materials mainly
consisting of bibenzyl, bitolyls, and benzyltoluenes.60−63 The
rupture of C−H bonds on the methyl group is the dominant
process, leading to the formation of bibenzyl.63 The overall
reaction for toluene giving rise to molecular hydrogen and
bibenzyl (see Supporting Information for a discussion on the
production of major products in radiolysis of toluene and their
interaction with Pd2+ ions) would be
2C6H5CH3 ⇝ H 2 + (C6H5CH 2)2
Such neutral dimerized products [(C6H5CH2)2] are inert
toward the reduction of palladium. Thus, we consider
dihydrogen (H2) as the main primary species involved in the
reduction process leading to Pd0 particle formation in our
experiments. H2 is a widely used reductant in the synthesis of
supported metal catalysts.64 It is characterized by reduction
potential of E0[H2/H+] = 0 V, while for the case of Pd2+,
E0[Pd/Pd2+] = 0.915 V versus standard hydrogen electrode
(SHE).65 These values will vary when measured in a different
solvent rather than in water,66,67 however, a relatively large
potential difference should remain in toluene.
Figure 1a is a series of cropped dark-field (DF) STEM
images showing successive and concomitant in situ nucleation,
growth, and size stabilization of individual Pd nanoparticles
induced by the electron beam. The time interval between
frames is 3.78 s, and the electron dose rate is 116 e−/Å2 per
frame (see Movie S1 for complete data set showing growth of
the entire population). After nucleation, the individual
nanoparticles rapidly stabilize at around 2.2 nm diameter with
a spherical geometry. Particles indicated by arrows in frames 3
and 7 are first detected with diameters of 1.6 and 1.5 nm,
respectively, and both stabilize to around 2.2 nm by the
subsequent frame. Figure 1a shows that each successive movie
frame contains newly nucleated particles that grow and stabilize
in size to about 2.2 nm even upon further electron beam
irradiation (see also the complete STEM data sets in Movies
S1, S2, S3, and S4). Multiple individual nucleation events take
place simultaneously and continuously within the irradiated
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Figure 1. (a) Cropped sequence from a multiframe movie of the
formation and size stabilization of several Pd particles from solution.
The first frame corresponds to the first scan after initial exposure to
the electron beam. The time lapse between frames is 3.78 s.
Magnification used is M = 910000×, pixel dwell time is 3 μs, beam
current is 5.7 pA, and image size is 1024 × 1024 pixels, which
correspond to an electron dose rate of 116 e−/Å2 per frame. The
multitarget particle tracking approach was applied to determine: (b)
number of particles detected in each frame (red circles) and total
number of particles formed over time (black squares), which accounts
for detection fluctuations via a multiway data association method, and
(c) particle size evolution over time for individual particles.
volume (STEM imaging area), with formation of Pd particles
being characterized by slow nucleation rate and fast growth
rate.
For quantitative evaluation of particle nucleation kinetics, we
have applied multitarget particle tracking statistical analysis55 to
our raw STEM data sets to determine the number of particles
in each movie frame (see Experimental Section for details of the
analysis). The number of particles detected in each separate
frame per unit time is plotted as solid red circles in Figure 1b
(same data set as for Figure 1a). These are particles formed and
continuously observed after formation. To more accurately
account for all formation events, a second measurement was
performed (solid black squares in Figure 1b), which also
accounts for particles that appear and quickly disappear, some
of which might be image artifacts. Both measurements make
use of a multiway data association method56 for the analysis,
originally developed for the case of multitarget tracking of
interacting objects. This methodology has been previously
applied to systems displaying coalescence of individual particles
into larger ones or splitting of particles into different
subparts.52,53,56 The multitracking algorithm used is capable
of detecting particles that appear and shortly disappear and can
discard them to prevent the analysis results from being
corrupted by image artifacts. For our case, where particle
motion out of the viewing area and deatchment/reatachment to
the SiNx window has been observed (see Figure S2), both
analyses are informative. Quantification of nucleation kinetics in
this work has been done only for the period of time where both
measurements overlap (≤40 s). In addition to tracking the
nucleation of particles over time, individual growth kinetics can
also be obtained from the raw STEM data sets. Figure 1c shows
the projected diameter as a function of time for some individual
particles from the data set shown in Figure 1a. All the particles
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grow and stabilize within 1−2 frames to diameters that oscillate
only slightly around the system average of 2.2 nm.
The overall nucleation and growth of the particle ensemble
was also evaluated by statistical treatment of all the individual
events. The average growth curves (average diameter over
time) for particle synthesis at an incident electron dose rate of
31 e−/Å2 per frame are shown in Figure 2a. The ensemble
Figure 2. (a) Average growth of the Pd nanoparticles ensemble
measured for a dose rate of 31 e−/Å2 per frame. (Inset) Cropped DF-
STEM image of Pd particles formed after 120 s exposure and taken in
the fluid stage. Scale bar is 20 nm. (b) Total number of particles
formed per unit area as a function of time for two different dose rates,
showing a difference in slope scaling linearly with dose rate.
particle size for this case stabilizes to ∼2.3 nm. Note we
measure only a slight difference in ensemble particle size of 0.1
nm between data sets produced with electron dose rates
differing by a factor of 4 (see Figure S3 for particle size
distributions). The inset in Figure 2a shows a DF-STEM image
of a population of Pd particles formed after 120 s of electron
beam exposure (data set 3 in the growth curve) as seen in
toluene in the fluid stage. First signs of damage of the organic
solvent are found after 50 s of exposure and can be seen in the
center and left-hand side of the image. Polymerization of the
organic solvent has been previously observed in the fluid
stage.53 Figure 2b shows the total number of individual particles
per unit area as a function of time for two different electron
dose rates. Interestingly, the nucleation rate for all data sets
remains fairly constant during the experiment, even for the
highest dose rates. A change in the rate of particle formation
nearly proportional to the electron dose rate was measured.
As a control experiment, we performed a bulk ex situ
synthesis using the same precursor solution (identical molarity
and Pd/TOP ratio) to grow Pd nanoparticles with a different
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chemical reductive agent rather than by the effect of the
electron beam. Hexanol was used as a reducing agent, being of
relatively similar reducing potential [for alcohols E(V) ∼ 0 V
versus SHE in water]68,69 to molecular H2. Figure 3 shows a
Figure 3. DF-STEM image of Pd particles grown ex situ by chemical
reduction at 100 °C of 1:1.5 Pd/TOP at 5 mM in toluene (same
concentration and Pd/TOP ratio as for the STEM experiments) in the
presence of an excess of hexanol and corresponding particle size
distribution.
postmortem STEM image and corresponding particle size
distribution of a population of Pd particles grown at 100 °C
reaction temperature (see Experimental Section for details on
chemical synthesis of the particles). The average ex situ particle
size of 2.1 nm diameter matches well with the average particle
size formed by the electron beam during in situ STEM
synthesis experiments. The size of the particles is comparable
for both chemical and radiation-induced reduction processes,
thus suggesting that the Pd/TOP ratio mainly determines
particle size for both cases; that is, TOP is responsible for the
arrested growth mechanism during radiation-induced synthesis.
These ex situ results also suggest that additional factors, such as
formation of polymeric molecules from the breakdown of
organic dimeric species or of TOP itself, are most likely not
acting as cluster stabilizers.
In Figure 4 we have plotted together, using a logarithmic
scale, the number of particles formed per unit volume versus
time from the in situ STEM experiments and an estimation of
the nucleation rate based on time evolution of the particles
from in situ SAXS experiments with hexanol in a customized
microfluidic device38 (see Figure S4 for linear fits to number of
particles per unit volume versus time and Experimental Section
for details on measurements and calculations). The nucleation
rate of hexanol-based synthesis increases with reaction
temperature, from 80 to 100 °C. As already mentioned, the
nucleation rate by STEM irradiation increases with dose rate.
Notably, the nucleation kinetics in the case of hexanol-based
synthesis is 1−2 orders of magnitude slower than in the case of
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Figure 4. Plot curves of number of particles per unit volume versus
time, measured for radiolytic synthesis in STEM for two different
electron dose values (squares and triangles) and estimated for
chemical synthesis with hexanol at two different reaction temperatures
from in situ SAXS (dashed lines). A fluid thickness of 125 nm has been
used for volume estimation in STEM (see Supporting Information).
Results of a linear fit to the SAXS data (25 mM Pd concentration) for
T = 100 and 80 °C are shown. Experimental data can be found in
Figure S4. A logarithmic scale has been used to highlight the order of
production kinetics of the different syntheses.
the radiation-induced synthesis in the STEM, even at 100 °C.
We present next a discussion on the formation mechanisms of
particles, including nucleation and growth kinetics and size
stabilization mechanisms.
Typically, at high irradiation dose rates, radiation-induced
synthesis of metallic clusters occurs by direct reduction
followed by coalescence.70 All reducing species are produced
and scavenged within a short time, and a sudden generation of
a high concentration of isolated atoms is expected, resulting in a
large number of smaller nuclei and a decreasing nucleation rate
over time.70 Instead, our observations show a continuous
increase in the density of particles with no sudden decay in the
nucleation rate after the first nucleation event. Continuous
nucleation is also found for particles following slower formation
kinetics by hexanol (see Figure S4 for experimental data
resulting in nucleation rates plotted in Figure 4). This synthesis
also yielded a homogeneous particle size distribution, as shown
in a previous work.71 Nucleation typically needs to occur within
a very short period of time for control of the final particle size
to be possible (LaMer model).71 On the contrary, the linear
trend of nucleation of Pd particles over time reported here does
not follow the LaMer model for formation of uniform particles.
Continuous nucleation in the STEM could be explained by
the simultaneous occurrence of two conditions: (1) formation
of a small number of initial stable nuclei and (2) a robust size
stabilization mechanism. Indeed, if a small number of particles
is initially formed in the absence of a size stabilizer, growth
would continue over time, giving rise to fewer larger
particles.20,44,70 Instead, growth stops at about 2.2 nm size,
and newly produced Pd atoms are thus unable to incorporate
into the already formed particles. Conditions for nucleation of
stable nuclei and growth will then be met in multiple
subsequent occasions.
Formation of a small number of initial nuclei upon electron
beam irradiation implies a slower production rate of reducing
radicals as compared to the rate of Pd ions−Pd0 and Pd0−Pd0
association mechanisms. This could simply be a consequence of
a relatively low production rate of reducing agent by the
incident electron beam. A similar effect is expected if palladium
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association kinetics were accelerated, for instance by the
catalytic effect of specific locations, such as surfaces. Reduction
kinetics is thus key to understand the amount of initial nuclei
formed.
Reduction kinetics of palladium(II) acetate [Pd(OAc)2] by
H2 have been previously investigated.72 The overall chemical
equation can be written as follows:
Pd(OAc)2 + H 2 = Pd0 + 2HOAc
This is, in fact, a multistep reaction [see Supporting
Information for a discussion on the kinetics of reduction of
Pd(OAc) 2 and a description of possible autocatalytic
mechanisms]. In previous work, the kinetics of reduction of
Pd(OAc)2 by H2 in solution and on the surface of a carbon
support were compared.72 Faster reduction of Pd(II) species
was observed on the support surface. Additionally, reduction of
the Pd(II) to Pd0 could occur without intermediate formation
of Pd(I) compounds, as opposed to reduction in bulk solution.
In both cases, an autocatalytic mechanism, mainly driven by
Pd(0), was proposed. Differences in reaction kinetics due to the
presence of the stabilizer, TOP, as well as due to the different
support material, SiNx, are expected. However, it is very likely
that a similar autocatalytic reduction mechanism by the already
formed Pd0 at the nuclei surface takes place. Also, the SiNx
support may be partly responsible for the faster overall
reduction kinetics found by in situ STEM, as compared to
bulk hexanol-based reduction (see Figure 4). It can be
discussed that once the Pd metal starts to dimerize and form
small aggregates, the autocatalytic reduction pathway may
activate, promoting very fast growth of a few aggregates (see
Figures 1c and 2a) and rapidly consuming the precursors at the
surface of the particle.
The yield of H2 upon radiolysis of toluene has been
determined by use of γ-radiolysis [linear energy transfer (LET)
about 0.2 eV/nm] and 1.8 MeV electron irradiation, giving in
both cases a value of G(H2) = 0.14 molecule/100 eV,73,74
which is much lower than production yields of more reactive
species (of stronger reduction potential) from radiolysis of
water. We estimate that about 8 × 104 primary electrons have
been delivered to the irradiated area for each Pd0 incorporated
in a particle (see details in Supporting Information). Note that
an experimental value of about 6 × 103 primary electrons was
found for production of one Au0 in water.49
Finally, there is one more possibility that could lead to low
production of Pd atoms: namely, rapid depletion of precursors
inside the irradiated volume, being continuously compensated
by fast diffusion from the bulk solution. An increase of
nucleation kinetics proportional to the increase in dose rate has
been observed (Figures 2b and 4), indicative of a formation
process limited by the rate of production of neutral species
within the irradiated area, rather than by the arrival of species
from the bulk solution. Formation of particles limited by the
reaction of radiolytic species and metal ions has been previously
observed in the liquid cell for growth of metallic particles from
water with no stabilizer.44,49,75 Consistent with previous
observations where fewer faceted bidimensional platelike
crystals were grown,49 no decay of formation rate of particles
is observed after the total amount of reduced Pd incorporated
into particles becomes larger than what was initially available in
the precursor solution. We have estimated the time when
depletion of precursors occurs. Consumption of all palladium in
solution within the irradiated area for the lowest dose rate of 31
e−/Å2 per frame occurs upon formation of approximately 36
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particles (see Supporting Information for calculation details).
When it is taken into account that growth occurs on both
membranes, solution depletion is estimated to occur after about
30 s of irradiation. Slow nucleation, rather than a burst of
nucleation, is observed from the first formation event after just
<4 s exposure, where 83−95% of precursors are still available in
the irradiated area. Additionally, the same gradual nucleation
rate continues for at least a few tens of seconds beyond 30 s.
This supports our conclusion that slow nucleation is limited by
the reduction rate of metallic cations rather than by diffusion of
species. Furthermore, continuous nucleation has also been
observed in the case of synthesis by hexanol,38 presenting much
slower kinetics of formation.
Altogether, we propose the following scenario (Figure 5) for
formation of supported Pd particles in toluene by radiolysis.
Figure 5. (a) Pd salt precursor reduction pathway by H2 (multistep
process). Reduction of Pd(II) species directly to Pd0 could occur, most
likely promoted at the SiNx membranes. Reduction can follow a two-
step process from Pd(II) to Pd(I) and from Pd(I) to Pd0. An
autocatalytic reduction mechanism by Pd0 is also expected on the
nucleus surface. (b) Schematics of different stages of nanoparticle
formation shown along a representational in situ STEM growth curve.
Continuous nucleation at the SiNx membranes can be due to low
production of H2 and an autocatalytic reduction mechanism leading to
few initial nuclei formed, followed by the effect of TOP on particle size
stabilization.
The incident electrons effectively ionize the solvent,6,30,76
which is the most abundant molecule in the irradiated volume
(for diluted precursor solutions up to 5 mM over a broad range
of pH values).76 Pd(II) complexes [Pd(OAc)2], solvated
divalent Pd ions, Pd2+, and TOP are minimally ionized through
knock-on damage and, therefore, almost exclusively react with
species generated from toluene, predominantly H2. In the case
of TOP, being an electron donor ligand, no reaction with H2 is
expected. Reduction of Pd(II) species in the presence of TOP
could proceed via multiple pathways. Reaction of Pd(II) species
with H2 produces neutral Pd atoms (see Figure 5a). The effect
of the SiNx support in the STEM could promote the reduction
of Pd2+ metal ions to the neutral Pd0 state,72 speeding up
formation kinetics compared to synthesis outside the liquid cell
(Figure 4). TOP could act as a reducing agent as well (this
possibility is not included in Figure 5a). Finally, Pd0 can also
produce, through an autocatalytic process at the particle
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surface,72 Pd metal ions with unstable intermediate oxidation
state, Pd+, which are a powerful reductant themselves.30
From our growth curves of individual particles (Figure 1c),
two distinct stages may be defined, where growth proceeds
quickly at first, followed by a second stage where growth is
interrupted and particle size is almost unchanged. Polar head
groups of the TOP capping agent may bind to the nucleus
surface, with Pd nuclei initially showing only partial surface
coverage by the capping ligand, and full coverage at the time
growth is arrested (Figure 5b). This mechanism is consistent
with previous time-resolved X-ray absorption fine structure
(EXAFS) analysis showing that the TOP/Pd ratio in solution
increases as more atoms are incorporated into the nano-
particles.38 It is worth noting that no oxygen is expected to
participate in the reactions above. We should expect different
species and yields for radiolysis of toluene in the presence of air
or moisture.77,78 For this reason, and because TOP is air-
sensitive, all experiments have been performed in an inert
environment (see details in Experimental Section). Additional
results and further discussion on the stability of the solution
when exposed to air and the reaction mechanisms can be found
in Supporting Information (see Figures S5 and S6 for
agglomeration of nanoparticles due to the presence of moisture
in the solution).
As previously noted for growth of gold in water,49 the
constant formation rate of particles, even for the highest dose
rate (Figure 1c) and after consumption of more Pd than
initially present, requires continuous mobility of Pd2+ into the
reaction zone. Typically, in the fluid stage, the formation of
particles in the bulk solution and subsequent precipitation on a
SiNx surface is not observed. Instead, formation of particles is
systematically favored directly at the SiNx support surface. In
other words, the reaction between cations and radiolytic species
mainly occur at/near the window surfaces. A hemispherical
diffusion profile, in analogy to peculiar electrochemistry with
ultramicroelectrodes (UME) and small currents applied, may
be expected on both SiNx windows. A steady state for cation
diffusion could be achieved over a very small reaction area
(near the membranes as compared to the bulk liquid),
preventing cation precursor depletion near the windows.
The presence of membranes is known to have a strong
influence on formation of particles in the STEM. However,
their effects are not well understood. Among the effects of
membranes in radiolytic synthesis outside the microscope,
adsorption has been observed to facilitate the redox process and
to slow down aggregation by strongly inhibiting diffusion.28
Most generally, differences in radiolytic yields, reduction and
association kinetics, as well as possible electrostatic effects, can
occur in the STEM. For the case of preformed supported
particles, electrostatic effects produced by the electron beam
can even produce changes in particles’ mobility proportional to
the applied electron dose rates.79
The fact that the amount of Pd(II) reduced to Pd0 to be
incorporated into particles (i.e., nucleation rate) increases with
increasing dose rate is interesting and is an advantage of the e−
radiolysis synthesis method, since it makes the synthesis
process more efficient and allows a means to control reaction
kinetics in situ. Also, kinetic rates are directly measured instead
of using indirect fitting procedures. However, the time
resolution of STEM scans did not allow us to detect the first
seed nuclei formed or fully resolve the individual growth rates,
which could range from t1/2 or faster to t1/3, depending on
whether the first growth stage is fully contained within one
DOI: 10.1021/acs.langmuir.5b04200
Langmuir 2016, 32, 1468−1477
Langmuir
movie frame or two, respectively. Slower growth kinetics would
allow us to access important information on the initial stages.
The kinetics of reduction is known to influence strongly the
intrinsic structure of the nanoparticles formed, for example,
through the creation of defects or twinning events,20,75 which
leads to very different properties of the final particles.6 The in
situ STEM nucleation rate is several orders of magnitude larger
than that by wet chemistry with an alcohol (see Figure 4).
Slowing down the reduction kinetics of in situ STEM
experiments to match those measured outside the microscope
may allow us to study formation of particles with the relevant
structure and final properties.
Further methods to reduce dose and thus slow down
reaction kinetics, and to increase acquisition times, are needed.
Suitable solvents could be selected on the basis of a tradeoff
between image contrast and the amount, and type, of radicals
produced per incident electron. Technologies that enable more
efficient use of the transmitted electrons, such as direct electron
detectors or new image processing and computational methods
to retain image information at much lower doses, would also
enable faster acquisition times. Methods for reducing radiolytic
species formation would include use of solvents that minimize
the production of radiolytic species (this work), choice of initial
pH,49 low-dose imaging techniques, thinner SiNx membrane
thickness, or finding ways to control the liquid thickness on
truly two-dimensional materials like graphene.
■
CONCLUSION
We have demonstrated control over Pd nanoparticle size (<3
nm size) during real-time imaging in the fluid stage and have
used the results from our observations to develop a model for
size-controlled Pd nucleation and growth in the presence of a
capping agent (TOP). Quantification of particle formation has
been achieved with and without taking into account single/few
frames events by incorporating a multiway data association
method into the multitarget tracking analysis. Comparison of
these two measurements is important for shedding light on
kinetics of small nanometric-size particles undergoing lateral
motion out of the viewing area, intermittent attachment/
detachment to the SiNx membranes, and other sources of local
contrast change. As opposed to radiolytic synthesis outside the
microscope, where fine control of particle size requires
increasing the production of radicals, the challenge in the
STEM, where incident doses are inherently higher by orders of
magnitude, is to drastically reduce such production. An
aromatic hydrocarbon (toluene) has been used as an efficient
solvent to reduce the production of radiolytic species by the
electron beam drastically as compared to more polar liquids.
For the specific case of toluene, Pd2+ ions are subjected to a net
reducing environment defined mainly by a single reducing
species, dihydrogen. Direct observation of the formation of
nanometric supported Pd particles by molecular hydrogen is of
special interest, since this is a common reductant for supported
metal catalysts by different synthesis methods. We have
discussed formation mechanisms of particles based on the
relatively low radiolytic production of H2, an autocatalytic
reduction mechanism at the particle surface, and the effect of
the surfactant TOP on size stabilization of particles. We
reproduced size-stabilized Pd nanoparticles via ex situ synthesis
with hexanol, which has a similar reducing potential as H2, and
achieved similar final size of the particles. Using insights from in
situ experiments, supported by ex situ results, we propose a
fundamental growth process for the synthesis of sub-3 nm Pd
1474
Article
particles in the presence of a polar capping agent. Finally, we
correlate fluid-stage observations in the STEM with in situ
SAXS and confirmed that similar general trends in the
nanoparticles formation kineticsfast growth and slow
nucleation kinetics of Pd particles from tolueneare observed
not only for different dosages in the electron microscope but
also for different experimental conditions in a microfluidic
reactor. We show that the in situ STEM nucleation rate can be
controlled by tuning experimental liquid STEM parameters.
Under the conditions explored in this work, the in situ STEM
nucleation rate is several orders of magnitude larger than that
measured for synthesis by wet chemistry with alcohol. We
highlight the importance of controlling the kinetics of reaction
with the electron beam, since it determines the intrinsic
structure of the nanoparticles and thus their properties.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.lang-
muir.5b04200.
Additional text and equations and eight figures,
describing geminate recombination in radiolysis of
toluene, reaction mechanisms during radiolysis of
toluene, effect of moisture on Pd nanoparticles, and
calculations on number of incident electrons per Pd atom
incorporated into stable particles and total amount of
Pd2+ions initially available in the irradiation volumes
(PDF)
Movie S1 (data set 1) (AVI)
Movie S2 (data set 2) (AVI)
Movie S3 (data set 3) (AVI)
Movie S4 (data set 4) (AVI)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail pabellan@superstem.org.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The work involving the development of in situ stages and
solutions preparation was supported by the Chemical Imaging
Initiative, under the Laboratory-Directed Research and
Development Program at Pacific Northwest National Labo-
ratory (PNNL). PNNL is a multiprogram national laboratory
operated by Battelle for the U.S. Department of Energy (DOE)
under Contract DE-AC05-76RL01830. Use of beamlines (12-
ID-B and 12-ID-C) at the Advanced Photon Source is
supported by the U.S. DOE, Office of Science, and Office of
Basic Energy Sciences, under Contract DE-AC02-06CH11357.
A portion of the research was performed by use of the
Environmental Molecular Sciences Laboratory (EMSL), a
national scientific user facility sponsored by the DOE’s Office
of Biological and Environmental Research and located at
PNNL. C.P. was supported by the National Science
Foundation, Division of Civil, Mechanical, and Manufacturing
Innovation, under Contract NSFCMMI-1334012, by Florida
State University Committee on Faculty Research Support
Award 032968, and by the Ralph E. Powe Junior Faculty
Enhancement Award. SuperSTEM is the U.K. National Facility
for Aberration-Corrected STEM, supported by the Engineering
DOI: 10.1021/acs.langmuir.5b04200
Langmuir 2016, 32, 1468−1477
Langmuir
and Physical Research Council (EPSRC). P.A. thanks
Emmanuel Maisonhaute (Sorbonne Universities, UPMC) and
Ivan T. Lucas (Sorbonne Universities, UPMC) for helpful
discussions.
■
ABBREVIATIONS
STEM, scanning transmission electron microscopy; TEM,
transmission electron microscopy; SAXS, small-angle X-ray
scattering; FIB, focused ion beam; SEM, scanning electron
microscope; APS, advanced photon source; BF, bright field;
Pd(OAc)2, palladium acetate; TOP, tri-n-octylphosphine; SHE,
standard hydrogen electrode
■
REFERENCES
(1) Bourdon, J., Ed. Growth and Properties of Metal Clusters:
Applications to Catalysis and the Photographic Process: Proceedings of
the 32nd International Meeting of the Societe de Chimie Physique,
Villeurbanne, 24−28 September 1979; Elsevier: Amsterdam, 1980.
(2) Roduner, E. Size matters: why nanomaterials are different. Chem.
Soc. Rev. 2006, 35 (7), 583−592.
(3) Klabunde, K. J.; Richards, R. M. Nanoscale Materials in Chemistry;
2nd ed.; Wiley−Interscience: New York, 2009.
(4) Murray, C. B.; Norris, D. J.; Bawendi, M. G. Synthesis and
characterization of nearly monodisperse CdE (E = sulfur, selenium,
tellurium) semiconductor nanocrystallites. J. Am. Chem. Soc. 1993, 115
(19), 8706−8715.
(5) Somorjai, G. A.; Park, J. Y. Molecular factors of catalytic
selectivity. Angew. Chem., Int. Ed. 2008, 47 (48), 9212−9228.
(6) Belloni, J. Nucleation, growth and properties of nanoclusters
studied by radiation chemistry - Application to catalysis. Catal. Today
2006, 113 (3−4), 141−156.
(7) Pérez-Lorenzo, M. Palladium Nanoparticles as Efficient Catalysts
for Suzuki Cross-Coupling Reactions. J. Phys. Chem. Lett. 2012, 3 (2),
167−174.
(8) Cookson, J. The preparation of palladium nanoparticles. Platinum
Met. Rev. 2012, 56 (2), 83−98.
(9) Shen, P. K.; Xu, C. Alcohol oxidation on nanocrystalline oxide
Pd/C promoted electrocatalysts. Electrochem. Commun. 2006, 8 (1),
184−188.
(10) Liu, J.; Ye, J.; Xu, C.; Jiang, S. P.; Tong, Y. Kinetics of ethanol
electrooxidation at Pd electrodeposited on Ti. Electrochem. Commun.
2007, 9 (9), 2334−2339.
(11) Kishore, S.; Nelson, J. A.; Adair, J. H.; Eklund, P. C. Hydrogen
storage in spherical and platelet palladium nanoparticles. J. Alloys
Compd. 2005, 389 (1−2), 234−242.
(12) Yamauchi, M.; Ikeda, R.; Kitagawa, H.; Takata, M. Nanosize
Effects on Hydrogen Storage in Palladium. J. Phys. Chem. C 2008, 112
(9), 3294−3299.
(13) Mubeen, S.; Zhang, T.; Yoo, B.; Deshusses, M. A.; Myung, N. V.
Palladium Nanoparticles Decorated Single-Walled Carbon Nanotube
Hydrogen Sensor. J. Phys. Chem. C 2007, 111 (17), 6321−6327.
(14) Wu, G.-h.; Wu, Y.-f.; Liu, X.-w.; Rong, M.-c.; Chen, X.-m.; Chen,
X. An electrochemical ascorbic acid sensor based on palladium
nanoparticles supported on graphene oxide. Anal. Chim. Acta 2012,
745 (0), 33−37.
(15) Richards, R.; Bönnemann, H. Synthetic Approaches to Metallic
Nanomaterials. In Nanofabrication Towards Biomedical Applications;
Wiley−VCH: Weinheim, Germany, 2005; pp 3−32.
(16) Kim, S.-W.; Park, J.; Jang, Y.; Chung, Y.; Hwang, S.; Hyeon, T.;
Kim, Y. W. Synthesis of Monodisperse Palladium Nanoparticles. Nano
Lett. 2003, 3 (9), 1289−1291.
(17) Duff, D. G.; Baiker, A.; Edwards, P. P. A New Hydrosol of Gold
Clusters 0.1. Formation and Particle-Size Variation. Langmuir 1993, 9
(9), 2301−2309.
(18) Papirer, E.; Horny, P.; Balard, H.; Anthore, R.; Petipas, C.;
Martinet, A. The preparation of a ferrofluid by decomposition of
1475
Article
dicobalt octacarbonyl: II. Nucleation and growth of particles. J. Colloid
Interface Sci. 1983, 94 (1), 220−228.
(19) Xia, Y.; Yang, P.; Sun, Y.; Wu, Y.; Mayers, B.; Gates, B.; Yin, Y.;
Kim, F.; Yan, H. One-Dimensional Nanostructures: Synthesis,
Characterization, and Applications. Adv. Mater. 2003, 15 (5), 353−
389.
(20) Belloni, J.; Mostafavi, M.; Remita, H.; Marignier, J. L.; Delcourt,
M. O. Radiation-induced synthesis of mono- and multi-metallic
clusters and nanocolloids. New J. Chem. 1998, 22 (11), 1239−1255.
(21) Surendran, G.; Ramos, L.; Pansu, B.; Prouzet, E.; Beaunier, P.;
Audonnet, F.; Remita, H. Synthesis of Porous Platinum Nanoballs in
Soft Templates. Chem. Mater. 2007, 19 (21), 5045−5048.
(22) Krishnaswamy, R.; Remita, H.; Impéror-Clerc, M.; Even, C.;
Davidson, P.; Pansu, B. Synthesis of Single-Crystalline Platinum
Nanorods within a Soft Crystalline Surfactant−PtII Complex.
ChemPhysChem 2006, 7 (7), 1510−1513.
(23) Yamamoto, T. A.; Nakagawa, T.; Seino, S.; Nitani, H. Bimetallic
nanoparticles of PtM (M = Au, Cu, Ni) supported on iron oxide:
Radiolytic synthesis and CO oxidation catalysis. Appl. Catal., A 2010,
387 (1−2), 195−202.
(24) Yamamoto, T. A.; Kageyama, S.; Seino, S.; Nitani, H.;
Nakagawa, T.; Horioka, R.; Honda, Y.; Ueno, K.; Daimon, H.
Methanol oxidation catalysis and substructure of PtRu/C bimetallic
nanoparticles synthesized by a radiolytic process. Appl. Catal., A 2011,
396 (1−2), 68−75.
(25) Redjala, T.; Apostolecu, G.; Beaunier, P.; Mostafavi, M.;
Etcheberry, A.; Uzio, D.; Thomazeau, C.; Remita, H. Palladium
nanostructures synthesized by radiolysis or by photoreduction. New J.
Chem. 2008, 32 (8), 1403−1408.
(26) Belloni, J.; Delcourt, M.; Leclere, C. Radiation induced
preparation of metal catalysts: iridium aggregates. Nouv. J. Chim.
1982, 6 (1), 507−509.
(27) Bruneaux, J.; Cachet, H.; Froment, M.; Amblard, J.; Belloni, J.;
Mostafavi, M. Improvement of charge transfer kinetics at transparent
SnO 2 counterelectrodes by means of a radiolytic grafting of metallic
nanoaggregates. Electrochim. Acta 1987, 32 (10), 1533−1536.
(28) Platzer, O.; Amblard, J.; Marignier, J.; Belloni, J. Nanosecond
pulse radiolysis study of metal aggregation in polymeric membranes. J.
Phys. Chem. 1992, 96 (5), 2334−2340.
(29) Buxton, G. V.; Mulazzani, Q. G.; Ross, A. B. Critical Review of
Rate Constants for Reactions of Transients from Metal Ions and Metal
Complexes in Aqueous Solution. J. Phys. Chem. Ref. Data 1995, 24 (3),
1055−1349.
(30) Buxton, G. V. An overview of the radiation chemistry of liquids.
In Radiation Chemistry: From Basics to Applications in Material and Life
Sciences; Spotheim-Maurizot, M.; Mostafavi, M.; Douki, T.; Belloni, J.,
Eds.; EDP Sciences: Les Ulis, France, 2008; pp 3−16.
(31) Radiation Chemistry: From Basics to Applications in Material and
Life Sciences; Spotheim-Maurizot, M.; Mostafavi, M.; Douki, T.;
Belloni, J., Eds.; EDP Sciences: Les Ulis, France, 2008; p 307.
(32) Mozumder, A. Fundamentals of Radiation Chemistry; Academic
Press: San Diego, CA, 1999.
(33) Choi, S.-H.; Zhang, Y.-P.; Gopalan, A.; Lee, K.-P.; Kang, H.-D.
Preparation of catalytically efficient precious metallic colloids by γ-
irradiation and characterization. Colloids Surf., A 2005, 256 (2), 165−
170.
(34) Somorjai, G. A.; Beaumont, S. K.; Alayoglu, S. Determination of
molecular surface structure, composition, and dynamics under reaction
conditions at high pressures and at the solid-liquid interface. Angew.
Chem., Int. Ed. 2011, 50 (43), 10116−29.
(35) Blasco, T. Insights into reaction mechanisms in heterogeneous
catalysis revealed by in situ NMR spectroscopy. Chem. Soc. Rev. 2010,
39 (12), 4685−702.
(36) Ellis, P. J.; Fairlamb, I. J.; Hackett, S. F.; Wilson, K.; Lee, A. F.
Evidence for the surface-catalyzed Suzuki-Miyaura reaction over
palladium nanoparticles: an operando XAS study. Angew. Chem., Int.
Ed. 2010, 49 (10), 1820−4.
DOI: 10.1021/acs.langmuir.5b04200
Langmuir 2016, 32, 1468−1477
Langmuir
(37) Lee, A. F.; Ellis, P. J.; Fairlamb, I. J.; Wilson, K. Surface catalysed
Suzuki-Miyaura cross-coupling by Pd nanoparticles: an operando XAS
study. Dalton Trans 2010, 39 (43), 10473−82.
(38) Karim, A. M.; Al Hasan, N.; Ivanov, S.; Siefert, S.; Kelly, R. T.;
Hallfors, N. G.; Benavidez, A. D.; Kovarik, L.; Jenkins, A.; Winans, R.
E.; Datye, A. K. Synthesis of 1nm Pd Nanoparticles in a Microfluidic
Reactor: Insights from In Situ X-ray Absorption Fine Structure
Spectroscopy and Small-Angle X-ray Scattering. J. Phys. Chem. C 2015,
119, 13257.
(39) Williamson, M. J.; Tromp, R. M.; Vereecken, P. M.; Hull, R.;
Ross, F. M. Dynamic microscopy of nanoscale cluster growth at the
solid-liquid interface. Nat. Mater. 2003, 2 (8), 532−536.
(40) Evans, J. E.; Jungjohann, K. L.; Browning, N. D.; Arslan, I.
Controlled Growth of Nanoparticles from Solution with In Situ Liquid
Transmission Electron Microscopy. Nano Lett. 2011, 11 (7), 2809−
2813.
(41) de Jonge, N.; Ross, F. M. Electron microscopy of specimens in
liquid. Nat. Nanotechnol. 2011, 6 (11), 695−704.
(42) Liao, H. G.; Cui, L. K.; Whitelam, S.; Zheng, H. M. Real-Time
Imaging of Pt3Fe Nanorod Growth in Solution. Science 2012, 336
(6084), 1011−1014.
(43) Parent, L. R.; Robinson, D. B.; Woehl, T. J.; Ristenpart, W. D.;
Evans, J. E.; Browning, N. D.; Arslan, I. Direct in Situ Observation of
Nanoparticle Synthesis in a Liquid Crystal Surfactant Template. ACS
Nano 2012, 6 (4), 3589−3596.
(44) Woehl, T. J.; Evans, J. E.; Arslan, L.; Ristenpart, W. D.;
Browning, N. D. Direct in Situ Determination of the Mechanisms
Controlling Nanoparticle Nucleation and Growth. ACS Nano 2012, 6
(10), 8599−8610.
(45) Woehl, T. J.; Jungjohann, K. L.; Evans, J. E.; Arslan, I.;
Ristenpart, W. D.; Browning, N. D. Experimental procedures to
mitigate electron beam induced artifacts during in situ fluid imaging of
nanomaterials. Ultramicroscopy 2013, 127, 53−63.
(46) Grogan, J. M.; Schneider, N. M.; Ross, F. M.; Bau, H. H. Bubble
and Pattern Formation in Liquid Induced by an Electron Beam. Nano
Lett. 2014, 14 (1), 359−364.
(47) Abellan, P.; Woehl, T. J.; Parent, L. R.; Browning, N. D.; Evans,
J. E.; Arslan, I. Factors influencing quantitative liquid (scanning)
transmission electron microscopy. Chem. Commun. 2014, 50 (38),
4873−4880.
(48) Schneider, N. M.; Norton, M. M.; Mendel, B. J.; Grogan, J. M.;
Ross, F. M.; Bau, H. H. Electron−Water Interactions and Implications
for Liquid Cell Electron Microscopy. J. Phys. Chem. C 2014, 118 (38),
22373−22382.
(49) Park, J. H.; Schneider, N. M.; Grogan, J. M.; Reuter, M. C.; Bau,
H. H.; Kodambaka, S.; Ross, F. M. Control of Electron Beam-Induced
Au Nanocrystal Growth Kinetics through Solution Chemistry. Nano
Lett. 2015, 15 (8), 5314−5320.
(50) Farhataziz; Rodgers, M. A. J. Radiation Chemistry: Principles and
Applications; VCH Publishers: New York, 1987; p 641.
(51) Berger, M. J.; Coursey, J. S.; Zucker, M. A.; Chang, J. Stopping-
power and range tables for electrons, protons, and helium ions; NISTIR
4999; NIST Physical Measurement Laboratory, 1998; http://www.
nist.gov/pml/data/star/.
(52) Woehl, T. J.; Park, C.; Evans, J. E.; Arslan, I.; Ristenpart, W. D.;
Browning, N. D. Direct observation of aggregative nanoparticle
growth: kinetic modeling of the size distribution and growth rate.
Nano Lett. 2014, 14 (1), 373−8.
(53) Abellan, P.; Mehdi, B. L.; Parent, L. R.; Gu, M.; Park, C.; Xu,
W.; Zhang, Y.; Arslan, I.; Zhang, J.-G.; Wang, C.-M.; Evans, J. E.;
Browning, N. D. Probing the Degradation Mechanisms in Electrolyte
Solutions for Li-Ion Batteries by in Situ Transmission Electron
Microscopy. Nano Lett. 2014, 14 (3), 1293−1299.
(54) Park, C.; Huang, J. H. Z.; Ji, J. X.; Ding, Y. Segmentation,
Inference, and Classification of Partially Overlapping Nanoparticles.
IEEE Trans. Pattern Anal. Mach. Intell. 2013, 35 (3), 669−681.
(55) Park, C. Estimating Multiple Pathways of Object Growth Using
Non-longitudinal Image Data. Technometrics 2014, 56 (2), 186−199.
1476
Article
(56) Park, C.; Woehl, T. J.; Evans, J. E.; Browning, N. D. Minimum
Cost Multi-way Data Association for Optimizing Multitarget Tracking
of Interacting Objects. IEEE Trans. Pattern Anal. Mach. Intell. 2015, 37
(3), 611−624.
(57) Katsumura, Y.; Tabata, Y.; Tagawa, S. The formation process of
the excited state of cycloalkane liquid using picosecond pulse
radiolysis. Radiat. Phys. Chem. 1982, 19 (4), 267−276.
(58) Jonah, C. D. Decay of geminate ions in hexanes. Radiat. Phys.
Chem. 1983, 21 (1), 53−56.
(59) Allen, A. O. Yields of free ions formed in liquids by radiation;
National Standard Reference Data System, 1976; http://www.nist.
gov/data/nsrds/NSRDS-NBS57.pdf.
(60) Hoigné, J.; Gäumann, T. Strahlungschemie der Kohlenwasser-
stoffe. 4. Mitteilung. Toluol. Helv. Chim. Acta 1961, 44 (7), 2141−
2150.
(61) Gale, L. H.; Gordon, B. E.; Steinberg, G.; Wagner, C. D.
Radiolysis of Toluene: Mechanism of Formation of Benzyl Radicals. J.
Phys. Chem. 1962, 66 (8), 1538−1539.
(62) Hoigné, J.; Burns, W. G.; Marsh, W. R.; Gäumann, T.
Strahlungschemie von Kolhenwasserstoffen 10. Mitteilung Let-Effekte
in Toluol. Helv. Chim. Acta 1964, 47 (1), 247−259.
(63) Sagert, N. H.; Quinn, M. J.; Sanipelli, G. G.; Kremers, W.;
Buchannon, W. D.; Westmore, J. B. Gamma-radiolysis of toluene and
deuterated toluenesII. Liquid products. Int. J. Radiat. Appl. Instrum.
Part C 1991, 38 (5), 449−455.
(64) Toebes, M. L.; van Dillen, J. A.; de Jong, K. P. Synthesis of
supported palladium catalysts. J. Mol. Catal. A: Chem. 2001, 173 (1),
75−98.
(65) Bard, A. J.; Faulkner, L. R. Electrochemical Methods:
Fundamentals and Applications; Wiley: New York, 1980; Vol. 2.
(66) Elving, P. J.; Spritzer, M. S. Polarographic reduction of hydrogen
ion in non-aqueous solvents. Talanta 1965, 12 (12), 1243−1258.
(67) Izutsu, K. Electrochemistry in Nonaqueous Solutions, 2nd ed.; John
Wiley & Sons, 2009; DOI: 10.1002/9783527629152.
(68) Hapiot, P.; Pinson, J.; Francesch, C.; Mhamdi, F.; Rolando, C.;
Schneider, S. One-electron redox potentials for the oxidation of
coniferyl alcohol and analogues. J. Electroanal. Chem. 1992, 328 (1),
327−331.
(69) Iwasita, T. Electrocatalysis of methanol oxidation. Electrochim.
Acta 2002, 47 (22), 3663−3674.
(70) Belloni, J.; Mostafavi, M. Radiation chemistry of nanocolloids
and clusters. Stud. Phys. Theor. Chem. 2001, 87, 411−452.
(71) LaMer, V. K.; Dinegar, R. H. Theory, Production and
Mechanism of Formation of Monodispersed Hydrosols. J. Am.
Chem. Soc. 1950, 72 (11), 4847−4854.
(72) Berenblyum, A.; Al-Wadhaf, H. A.; Katsman, E.; Flid, V. Kinetics
and mechanism of palladium (II) acetate reduction by hydrogen on
the surface of a carbon support. Kinet. Catal. 2011, 52 (2), 296−304.
(73) LaVerne, J. A.; Baidak, A. Track effects in the radiolysis of
aromatic liquids. Radiat. Phys. Chem. 2012, 81 (9), 1287−1290.
(74) Hentz, R. R.; Burton, M. Studies in Photochemistry and
Radiation Chemistry of Toluene, Mesitylene and Ethylbenzene1, 2, 3.
J. Am. Chem. Soc. 1951, 73 (2), 532−536.
(75) Alloyeau, D.; Dachraoui, W.; Javed, Y.; Belkahla, H.; Wang, G.;
Lecoq, H.; Ammar, S.; Ersen, O.; Wisnet, A.; Gazeau, F.; Ricolleau, C.
Unravelling Kinetic and Thermodynamic Effects on the Growth of
Gold Nanoplates by Liquid Transmission Electron Microscopy. Nano
Lett. 2015, 15 (4), 2574−2581.
(76) Fricke, H. The Reduction of Oxygen to Hydrogen Peroxide by
the Irradiation of Its Aqueous Solution with X-Rays. J. Chem. Phys.
1934, 2 (9), 556−557.
(77) Christensen, H.; Sehested, K.; Hart, E. Formation of benzyl
radicals by pulse radiolysis of toluene in aqueous solutions. J. Phys.
Chem. 1973, 77 (8), 983−987.
(78) Yamamoto, Y.; Takamuku, S.; Sakurai, H. Gas-phase radiolysis
of toluene. J. Phys. Chem. 1970, 74 (18), 3325−3332.
(79) Woehl, T. J.; Prozorov, T. The Mechanisms for Nanoparticle
Surface Diffusion and Chain Self-Assembly Determined from Real-
DOI: 10.1021/acs.langmuir.5b04200
Langmuir 2016, 32, 1468−1477
Langmuir Article

Time Nanoscale Kinetics in Liquid. J. Phys. Chem. C 2015, 119 (36),

21261−21269.

1477 DOI: 10.1021/acs.langmuir.5b04200

Langmuir 2016, 32, 1468−1477