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http://pubs.acs.org/journal/acsodf

Converting Light Energy to Chemical Energy: A New Catalytic

Approach for Sustainable Environmental Remediation
Michelle A. Nguyen, Elsayed M. Zahran, Azaan S. Wilbon, Alexander V. Besmer, Vincent J. Cendan,
William A. Ranson, Randy L. Lawrence, Joshua L. Cohn, Leonidas G. Bachas, and Marc R. Knecht*,

Department of Chemistry, University of Miami, 1301 Memorial Drive, Coral Gables, Florida 33146, United States

Department of Physics, University of Miami, 1320 Campo Sano Drive, Coral Gables, Florida 33146, United States
*
S Supporting Information

ABSTRACT: We report a synthetic approach to form cubic

Cu2O/Pd composite structures and demonstrate their use as
photocatalytic materials for tandem catalysis. Pd nanoparticles
were deposited onto Cu2O cubes, and their tandem catalytic
reactivity was studied via the reductive dehalogenation of
polychlorinated biphenyls. The Pd content of the materials was
gradually increased to examine its inuence on particle
morphology and catalytic performance. Materials were
prepared at dierent Pd amounts and demonstrated a range
of tandem catalytic reactivity. H2 was generated via photo-
catalytic proton reduction initiated by Cu2O, followed by Pd-
catalyzed dehalogenation using in situ generated H2. The
results indicate that material morphology and composition and substrate steric eects play important roles in controlling the
overall reaction rate. Additionally, analysis of the postreacted materials revealed that a small number of the cubes had become
hollow during the photodechlorination reaction. Such ndings oer important insights regarding photocatalytic active sites and
mechanisms, providing a pathway toward converting light-based energy to chemical energy for sustainable catalytic reactions not
typically driven via light.

INTRODUCTION
Given the current global energy state, a push for rapid access to
energy conversion eciency.10,11 These charge transfer
processes can be greatly inuenced by the presence of a
sustainable energy, such as solar cells and renewable fuels, has noble metal cocatalyst12 coupled to the semiconductor, which
emerged.1,2 Accordingly, an expansion in research in the area of can readily accept photoinduced electrons to eciently transfer
photocatalysis has occurred over the past decade.3 Although them to surface adsorbed acceptor molecules such as to H+ to
signicant eort has been exerted to design and fabricate highly produce H2.1315 Additionally, these metal nanoparticle
active photocatalysts to replace conventional catalytic materi- cocatalysts frequently act as an electron reservoir and
als,4,5 little progress has been made toward reducing the overall consequently promote charge separation within the semi-
energy, materials, and resources necessary to create and conductor-metal assembly.16 Solar H2 production from photo-
maintain these light-harvesting systems. As such, existing catalytic water splitting is one of the most notable applications
catalytic technologies must evolve toward adopting sustainable of photoinduced electron transfer, along with being a promising
synthetic practices that minimize environmental and economic route to achieving renewable energy.17 Advancing toward
impacts. To this end, the ability to easily synthesize and sustainable chemical processes, photocatalytically generated H2
characterize functional nanomaterials with controlled size, could be employed in other catalytic reactions, such as
shape, composition, and overall structural morphology will hydrogenation or hydrodehalogenation, which could also
allow us to achieve catalytic technologies with optimized occur at the metal nanoparticle surface. Use of such a light-
reactivity.68 promoted tandem catalytic system has been demonstrated
While photocatalysis is appealing, it is traditionally limited to recently.9,18,19 For instance, Hirai and co-workers have reported
redox chemistries. Thus, the application of photobased the N-monoalkylation of primary amines in alcohol solvents by
approaches to non-photo-responsive catalytic reactions remains tandem photocatalytic and catalytic reactions on TiO2 loaded
exceedingly rare.9 One approach to address this limitation is to with Pd particles (Pd/TiO2).19 In separate work, we reported
fabricate multicomponent photocatalytic architectures with the use of Cu2O cubes with galvanically deposited Pd
multiple catalytic domains. For this approach, semiconductor
materials are of particular interest because of their photo- Received: June 13, 2016
induced charge transfer properties, where fast transfer of Accepted: June 16, 2016
charges across the semiconductor interface is critical for high Published: July 6, 2016

2016 American Chemical Society 41 DOI: 10.1021/acsomega.6b00076

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nanoparticles on the oxide surface (Cu2O/Pd) as catalysts for the nal biphenyl product, and the corresponding reaction rate
the reductive dechlorination of polychlorinated biphenyls constants were quantied. Comparison of the rate constants
(PCBs), a well-known environmental persistent organic demonstrated a general dechlorination reactivity order of para
toxicant present at many contaminated sites around the > meta ortho, with maximal catalytic rates obtained using
world.9 For this, photoactivation of the oxide component Cu2O/Pd materials with 9 wt % Pd deposited at a composite
results in H2 production, facilitated by Pd, via proton reduction. material catalyst loading of 2 mg/mL. These ndings provide
This H2 was subsequently activated on the Pd metal surface intriguing information concerning the active sites and
from which PCB dechlorination was processed in a tandem-like composite interface of photocatalytic materials, as well as
fashion. From this, it is clear that semiconductor-metal how such structure-dened properties aect the overall reaction
multicomponent materials can be tailored to facilitate light- kinetics for photoinitiated tandem systems. They also increase
promoted tandem catalysis, catering to reactions not typically the understanding of material structural eects over catalytic
driven via light. reactivity, opening pathways toward new structures with
In this contribution, we demonstrate that the Cu2O/Pd enhanced reactivity or translation of such photobased
tandem photocatalytic activity is highly sensitive to both the approaches to new catalytic processes, all of which are highly
overall composite material morphology and the substrate important for environmental remediation of halogenated
structure for nontraditional photocatalytic reactions (Scheme organic compounds such as PCBs.
1). To examine the structural eect, Cu2O cubes were

Scheme 1. Reactivity of Cu2O/Pd Composite Structures for

MATERIALS AND METHODS
Chemicals. CuSO4 and Na2CO3 were obtained from BDH
Photodriven Tandem Catalysis Chemicals; Pd(CH3COO)2 was acquired from Strem Chem-
icals. HR-GC hexanes and 200 proof ethanol were attained
from EMD Millipore and Pharmco-AAPER, respectively.
Finally, polyvinylpyrrolidone (PVP; MW 29 000 g/mol),
sodium citrate, glucose, 2-chlorobiphenyl (PCB 1), 3-
chlorobiphenyl (PCB 2), 4-chlorobiphenyl (PCB 3), and
biphenyl were purchased from Sigma-Aldrich. All chemicals
were used as received without further purication. Milli-Q
water (18 Mcm) was used for all experiments.
Synthesis of Cu2O/Pd Cubes. Cu2O cubes were prepared
according to synthetic methods established by Sui et al.20 In
detail, 3.0 g of PVP was dissolved in 180 mL of an aqueous
0.038 M CuSO4 solution with vigorous stirring in a round-
bottom ask. Upon complete dissolution of the PVP, the
solution was stirred for an additional 10 min. Next, 40 mL of an
aqueous 0.37 M sodium citrate and 0.61 M sodium carbonate
solution mixture was slowly added dropwise with continuous
stirring. This was followed by the addition of 50 mL of an
aqueous 1.4 M glucose solution, which was again slowly added
dropwise with continuous stirring. After complete glucose
incorporation, the reaction was stirred for 10 min. The ask was
then placed in a 70 C water bath for 2 h without stirring. Once
complete, the dark orange precipitate was ltered through a 0.2
m polycarbonate membrane, thoroughly washed with water
and ethanol, and dried under vacuum at 60 C for at least 12 h.
The as-synthesized Cu2O cubes were subsequently coated
with Pd nanoparticles via a galvanic exchange reaction.9 The
production of the Cu2O/Pd cubes is described using the
generated where varying amounts of Pd nanoparticles were deposited Pd mass % to dierentiate the samples. The
galvanically deposited on the oxide surface (015 wt %). The fabrication of 1 wt % Pd Cu2O/Pd materials is described
materials were extensively characterized to conrm their below; however, changes to the mass of Pd added were
morphology, size, composition, and component arrangement employed to reach the appropriate metal loading. In a round-
using scanning electron microscopy (SEM), transmission bottom ask, 11.3 mg of Pd(CH3COO)2 was dissolved by
electron microscopy (TEM), energy-dispersive X-ray spectros- slowly adding 200 proof ethanol until a total volume of 150 mL
copy (EDS), inductively coupled plasma optical emission was reached with stirring and sonication. Upon complete
spectrometry (ICP-OES), and powder X-ray diraction (XRD). dissolution of the Pd(CH3COO)2, 450 mg of the Cu2O
Light-promoted tandem catalytic activities of the materials were material was added to the solution and sonicated until the
investigated by monitoring the reductive dechlorination of Cu2O powder was well-dispersed. The solution was stirred for
PCBs. Under light irradiation, H2 was produced via proton 24 h in the dark as the galvanic exchange reaction proceeded.
reduction by the Cu2O material facilitated by the Pd The Cu2O/Pd 1 wt % cubes were then ltered, washed with
nanodomains. Subsequently, the in situ generated H2 was ethanol, dried under vacuum at 60 C, and then stored in a
used for Pd-catalyzed dehalogenation of PCBs. For this, PCB vacuum desiccator.
structures that positioned the Cl substituent at the ortho, meta, Photocatalytic Reductive Dechlorination of PCBs. For
and para positions were reductively dechlorinated to generate each photocatalytic experiment, 100 mg of the Cu2O/Pd
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Figure 1. SEM images of the Cu2O/Pd composite structures with a Pd mass percent deposited of (a) 0% (bare Cu2O cubes), (b) 1%, (c) 3%, (d)
6%, (e) 9%, and (f) 15%.

materials was added to a 60 mL borosilicate glass vial capped Detector Technologies EDS detector; TEM studies were
with a Teon-coated silicone septum closure. To this, 50 mL of completed using a JEOL JEM-1400 TEM. ICP-OES analysis
a 50/50 ethanol/water (v/v) solution of the specic PCB was performed using a Varian Vista-Pro CCD simultaneous
congener at a concentration of 25 M was added after being ICP-OES spectrophotometer. Powder XRD analysis was
bubbled with N2 for at least 30 min. This resulted in a catalyst completed on a Philips MRD XPert diractometer using Cu
loading of 2 mg/mL. Next, the headspace of the vial was purged K radiation. Finally, reaction progression analysis was
with N2 and the Cu2O/Pd materials were suspended by conducted on an Agilent 7820A GC equipped with a ame
sonication. Once the materials were fully dispersed, the reaction ionization detector and on an Agilent 5975C GC-MS. All
was vigorously stirred while being irradiated with a 450 W chromatograms, unless otherwise noted, showed only the
medium pressure Hg-vapor lamp operating at 60 mW/cm2, presence of PCB, biphenyl, and hexane.
based on the manufacturers specications, where the sample to
light source distance was 10 cm. To analyze the reaction
progression, 500 L aliquots of the reaction mixtures were
RESULTS AND DISCUSSION
Materials Synthesis and Characterization. As illustrated
taken at predetermined time intervals in at least triplicate trials. in Scheme 1, to achieve light-driven PCB degradation, the
Each aliquot was combined with 500 L of hexanes in order to photocatalytic capability of Cu2O was combined with the
extract the unreacted PCB and the biphenyl product for gas hydrodehalogenation activity of Pd to produce a composite
chromatography (GC) analysis. Separate reactions were also structure for photodriven tandem catalysis. For this, H2
conducted using the exact same procedures; however, the generation is processed via proton reduction by Cu2O
amount of Cu2O/Pd particles was adjusted to 50 and 150 mg photoexcitation facilitated by the Pd, followed by reductive
to give 1 and 3 mg/mL catalyst loadings, respectively. All dehalogenation using the in situ generated H2 at the Pd
experiments were conducted under ambient conditions and at component. As previously reported, the Cu2O/Pd materials
room temperature. have shown signicant tandem catalytic activity for the
Characterization. SEM was performed using a FEI/Philips reductive dehalogenation of PCBs.9 To understand both the
XL-30 eld emission SEM equipped with an Advanced fabrication of the composite structure and how this structure
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aects the reaction kinetics, the Pd content of the composite

material was varied between 0 and 15 wt % Pd. In this regard,
the Cu2O/Pd materials were synthesized to have a nal
deposited Pd mass of 1, 3, 6, 9, or 15%, where the percent value
listed represents the actual Pd mass % (relative to the Cu2O
mass) deposited onto the oxide surface. Prior to Pd deposition,
Cu2O cubes were generated with an edge length of 665 55
nm (Figure 1a). Figure 1 also presents SEM images of the
Cu2O/Pd materials after the galvanic deposition process. In
general, high yields of well-dened cubic composite structures
were generated for all of the samples. Figure 1b specically
presents the Cu2O/Pd 1% materials. Here, distinct cubes were
generated with an average edge length of 663 69 nm. Such
dimensions indicate that the addition of 1% Pd by mass does
not substantially alter the size of the cubes as compared to that
of the initial Cu2O structures. As the Pd mass increased to 3, 6,
9, and 15% (Figure 1cf), a shift in particle size was observed;
although it was evident that cubic materials were again
prepared, the average particle size increased to 689 32, 738
67, 752 63, and 814 91 nm, respectively. This increase in
particle size likely arises from the deposition of the Pd
materials, as conrmed by TEM analysis (discussed below). For
all particle sizing, at least 100 cubes were measured over
multiple SEM images (Supporting Information, Figure S1).
Interestingly, an ombre color eect from light to dark was
observed for the color of the materials as the Pd content
increased. To this end, a dark amber color was noted for the
Cu2O/Pd 1% sample, whereas the Cu2O/Pd 3% particles were
light brown in color. As the Pd mass increased to 6, 9, and 15%,
dark brown to black colors were observed for these materials,
respectively, indicative of the signicantly higher amounts of Pd
deposited.
To thoroughly examine the structural eects of the various
Pd amounts on the composite materials, TEM analysis was
conducted (Figure 2). Figure 2a presents the bare Cu2O cubes
prior to Pd deposition, where the left image shows the overall
cube structure and the right image displays a high-magnication
analysis of the oxide edge. Unfortunately, due to the material
thickness, imaging of the cube facet is not possible. In this
sample, it is clear that the surface of the metal oxide cube is
smooth, as anticipated. Figure 2b presents the analysis for the
Cu2O/Pd 1% structures, where it is evident that the Pd
nanoparticles were directly deposited on the cube surface. To
this end, the metallic nanomaterials were imaged on the Cu2O
surface as the light gray rough region at the oxide edge as
compared to the Pd-free materials. As Figure 2b depicts, the
size and spatial distribution of the noble metal components Figure 2. TEM images of (a) bare Cu2O cubes and (bf) Cu2O/Pd
were disperse, likely arising from the galvanic deposition materials with a deposited Pd mass of (b) 1%, (c) 3%, (d) 6%, (e) 9%,
process, and prior elemental mapping studies conrmed that and (f) 15%. The left panel displays a single cube, and the right panel
the Pd remains on the oxide surface.9 As the Pd content shows the zoomed-in area indicated in the left image.
increased in the Cu2O/Pd 3, 6, 9, and 15% (Figure 2cf)
samples, the deposited Pd layer topology of the surface became indicated that the deposited Pd mass percent depended on the
progressively rougher and ake-like, suggesting that multiple added Pd mass percent (relative to the Cu2O sample mass) in
layers of Pd materials were incorporated. the galvanic exchange reaction. The plot presented in Figure 3b
Additional characterization to conrm the composite ma- shows the linear relationship between the Pd mass percent
terial morphology was conducted (Figure 3). To quantify the added into the galvanic exchange reaction and the Pd mass
Pd content in the composite structures, EDS was employed. percent deposited on the Cu2O surface. For instance, when 153
From the EDS analysis of the Cu2O/Pd 9% materials (Figure mg of Pd(CH3COO)2 (17% Pd mass) was added in the
3a), Pd was successfully deposited, as evidenced by a strong reaction with 450 mg of Cu2O, 9.1 0.1% Pd mass was
peak at 2.8 keV corresponding to the Pd L X-ray line. As deposited, as measured by EDS. In general, diminished
anticipated, Cu was also present in the sample arising from the deposition amounts were observed as compared to the reaction
Cu2O core component. Similar analyses were conducted for the stoichiometry, most likely due to incomplete Pd2+ reduction at
Cu2O/Pd 1, 3, 6, and 15% materials. The EDS assessment the Cu2O interface as the ltrate was pale yellow in color for
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Figure 3. Cu2O/Pd characterization. (a) EDS analysis of the Cu2O/Pd 9% materials. For this example, when sucient Pd(CH3COO)2 was added to
the bare Cu2O cubes to reach 17% Pd mass added (relative to the Cu2O mass), 9% Pd mass was deposited, as measured by EDS. (b) Linear
relationship between the Pd mass percent added in the reaction and the Pd mass percent deposited. (c) XRD patterns of the Cu2O/Pd materials
compared to that of Pd-free Cu2O cubes (intensities are oset for clarity).

the higher Pd loadings. Pd wt % amounts for the Cu2O/Pd oxide surface. While the XRD measurements indicate that only
materials were also conrmed with ICP-OES and are presented Cu2O is present in the samples, EDS and ICP-OES conrmed
in Table S1 of the Supporting Information. Finally, the the presence of surface Pd for all of the samples, which was
crystallinity of the materials was studied via powder XRD visually observed by TEM. This eect is attributed to the
(Figure 3c). Diraction patterns of the as-synthesized thinness of the Pd layer on the surface of the oxide cube.24
structures were compared with the pattern for bulk Cu2O. Photocatalytic Reactivity. The photocatalytic reductive
The diraction patterns for all of the Cu2O/Pd materials are dechlorination of PCBs was examined using the Cu2O/Pd 1, 3,
consistent with the cubic phase of Cu2O, displaying reections 6, 9, and 15% particles irradiated with a Hg-vapor lamp in a
at 29.4, 36.3, 42.2, 61.4, 73.6, and 77.4 2, corresponding to photochemical cabinet. The reactivity of the materials was
the (110), (111), (200), (220), (311), and (222) lattice planes evaluated using three monochlorinated PCB congeners to
of Cu2O, respectively.21 Furthermore, no peaks arising from ascertain steric eects on the material reactivity: PCB 1, PCB 2,
Cu0 metal, CuO, or Pd were observed. Such results suggest that and PCB 3. These PCB substrates were specically selected due
Cu2O is the dominant species present in the composite to their positioning of the Cl group at the ortho, meta, and para
materials, consistent with the SEM, TEM, and EDS results. positions, respectively. Such structural features are known to
Additionally, the Pd layer on the Cu2O surface is quite thin, aect the catalytic reactivity based on steric constraints.2527
especially when considering the thickness of the oxide material, For these reactions, 100 mg of particles was mixed into 50 mL
and beyond the detection limit of the technique.2224 of the 25 M PCB solution, resulting in a 2 mg/mL catalyst
Taken together, signicant structural dierences can be loading, followed by light irradiation for 250 h. Figure 4a
noted in these materials based upon the eect of the Pd presents the dechlorination analysis of PCBs 1, 2, and 3 using
content. For this study, the major dierence in the preparation the Cu2O/Pd 1% materials. By monitoring the dechlorination
process for the dierent materials was the amount of Pd of the PCBs over time, the kinetics of the reactions were
introduced during the galvanic exchange reaction, where the determined and compared. For this system, PCB 3 (chlorine in
amount of Pd deposited on the Cu2O cubes was directly the para position) was dechlorinated the most eciently. In
proportional to the amount of Pd2+ added into the galvanic this regard, 89% of PCB 3 was dechlorinated after 250 h,
exchange reaction. This generally resulted in an increasingly resulting in a pseudo-rst-order rate constant kPCB3 of (7.7
rough and akey material surface as greater amounts of Pd were 0.7) 103 h1.28,29 Such a result was anticipated because PCB
deposited; however, all of the dierent nal composite 3 is the least sterically hindered congener, as compared to the
structures maintained a cubic morphology, where the size other substrates. When PCBs 2 and 1 were employed in the
increased proportional to the amount of Pd deposited on the reaction system using the Cu2O/Pd 1% tandem catalysts, kPCB2
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Figure 4. Overall reaction analysis for the photocatalytic reductive dechlorination of PCBs 1, 2, and 3 using the Cu2O/Pd materials at a catalyst
loading of 2 mg/mL in the reaction: (a) Cu2O/Pd 1%, (b) Cu2O/Pd 3%, (c) Cu2O/Pd 6%, (d) Cu2O/Pd 9%, and (e) Cu2O/Pd 15%. Note that
lines are added to guide the eye.

and kPCB1 values of (2.3 0.5) 103 and (2.4 0.7) 103
h1 were noted, respectively (Figure 5 and Supporting
Information, Table S2).
Identical analyses were conducted for all of the composite
structures prepared at the selected Pd loadings (Figure 4). For
all of the particles prepared, the rate constants for PCB
photodechlorination generally maintained the para (kPCB3) >
meta (kPCB2) ortho (kPCB1) trend (Figure 5). In this regard,
when the Cu2O/Pd 3% sample catalyzed the reaction, rate
constants of (3.4 0.5) 103, (2.7 0.1) 103, and (6.3
0.3) 103 h1 were observed for the PCB 1, 2, and 3
substrates, respectively. Note that this is the only sample where
kPCB2 < kPCB1. The k values determined for the Cu2O/Pd 6%
catalyzed reaction were (2.5 0.2) 103 (PCB 1), (4.0
0.2) 103 (PCB 2), and (7.7 0.3) 103 h1 (PCB 3),
which were slightly higher than those noted for the Cu2O/Pd
3% system. Interestingly, the material with 9 wt % Pd content
(Cu2O/Pd 9%; Figure 4d) was the most ecient dechlorina- Figure 5. Comparison of the pseudo-rst-order rate constants for PCB
photodechlorination for each of the Cu2O/Pd materials at a catalyst
tion system. Complete dechlorination of PCB 3 was practically
loading of 2 mg/mL.
achieved in 75 h. At this time point, 98% of the substrate was
dechlorinated, giving rise to a kPCB3 value of (50.8 2.9)
103 h1. Almost complete dechlorination (95%) of PCB 2 was
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Figure 6. Catalyst loading analysis using the Cu2O/Pd 9% materials for the photocatalytic reductive dechlorination of PCB 3: (a) overall reaction
analysis using the indicated catalyst loadings and (b) comparison of the pseudo-rst-order rate constants for each of the indicated catalyst loadings.

reached after 250 h of irradiation, with a corresponding kPCB2 observed from the Cu2O/Pd 9% sample. Such results were
value of (11.0 0.7) 103 h1. For the PCB 1 substrate, quite interesting as this material did not possess the greatest
diminished reactivity was noted, as anticipated, where 39% of amount of surface-deposited Pd. To elucidate the structure/
this reagent was dechlorinated in 250 h, with a kPCB1 value of function relationships of the composite material, a set of
(1.9 0.1) 103 h1. When using the material with the control experiments was carried out. To probe the photo-
highest Pd loading studied (Cu2O/Pd 15%; Figure 4e), reduced catalytic eect of the Cu2O materials, a solution of PCB 3 was
reactivity was observed as compared to the Cu2O/Pd 9% bubbled with H2 for 5 h in the presence of Cu2O/Pd 9%
sample. In this regard, when the Cu2O/Pd 15% sample particles at a catalyst loading of 2 mg/mL while in the dark
catalyzed the reaction, rate constants of (2.4 0.2) 103, (6.3 (Supporting Information, Figure S2a). After 3 h, complete
0.3) 103, and (36.5 1.3) 103 h1 were observed for dechlorination of PCB 3 was observed with only a modest
the PCB 1, 2, and 3 congeners, respectively. These lower k amount of biphenyl being detected. It is likely that biphenyl was
values, as compared to Cu2O/Pd 9%, may be due to the the dominant product generated, as indicated by GC analysis;
extensive Pd coverage of the oxide core, therefore obstructing however, due to the catalytic setup, aerosolization of the
light absorption. Nevertheless, these results indicate that the biphenyl occurred, resulting in diminished amounts detected.
reactivity of the Cu2O/Pd materials for PCB photodechlorina- To conrm this aerosolization eect, a solution of biphenyl was
tion is maximized for 9 wt % Pd on the Cu2O core. bubbled with H2 for 5 h in the absence of a photocatalyst while
When considering all of the Cu2O/Pd materials studied, a in the dark (Supporting Information, Figure S2b). Within 2.5 h,
trend was evident where the rate of reductive dehalogenation complete aerosolization of biphenyl was observed. Taken
was correlated to the location of the Cl substituent in the PCB together, these results suggest that the production of H2 is the
molecule; catalytic removal of chlorine is typically favored in rate-determining step for the tandem catalytic process. In this
the order of para > meta ortho positions.2527 In general, regard, the high degree of Pd coverage for this sample is
while all of the synthesized structures were photocatalytically anticipated to facilitate H2 generation to greater degrees than
reactive for the reductive dechlorination of all of the PCB those materials with lesser amounts of Pd, as observed herein,
congeners studied, the most signicant dechlorination was due to diminished charge recombination eects; however, when
observed for PCB 3, regardless of which Cu2O/Pd sample was more Pd is deposited on the surface, as in the Cu2O/Pd 15%
used as a catalyst. From this, it is evident that substrate steric sample, lower reactivity is observed due to diminished light
eects play an extremely important role in the material absorptivity by the Cu2O core. In addition to activating the
reactivity. In particular, the rate constants for PCB 1 were the reductive dehalogenation step of the tandem catalytic process,
lowest among all of the Cu2O/Pd materials, ranging over a the Pd metal surface likely increases the overall surface area of
small window of (1.93.4) 103 h1. This suggests that the the composite structure, providing additional adsorption sites
amount of Pd deposited on the Cu2O has little eect on the for H+ ions. Pd could then reduce adsorbed H+ ions through
dechlorination of PCB 1, most likely due to its steric hindrance. the electrons transferred from the Cu2O conduction band to
Furthermore, dechlorination of PCBs 2 and 3 was observed to form H2.30 Previous BET surface analysis has conrmed that
be enhanced as the mass of Pd increased in the catalytic surface-deposited Pd increases the overall surface area of the
materials. This likely arises from the optimized inorganic composite material.9 Therefore, it is possible for H2 generation
morphology that displays increased Pd materials for reductive to occur at both the Cu2O and Pd sites. Altogether, these
dechlorination, as well as the accessibility of the Cl substituent results provide important insights into the catalytic functions of
in the substrate structure. Taken together, these catalytic results the individual components of the composite structure and their
suggest that the Pd content, composite structures, and substrate overall roles in the tandem catalytic process.
steric eects work synergistically to inuence the overall To conrm that the observed reactivity arose from the
reactivity. particles and not light-based degradation of PCBs, a series of
On the basis of the changes in particle structure, such additional control studies was conducted. For this, solutions of
information can be correlated to the observed reactivity to PCBs 1, 2, and 3 were irradiated for 250 h in the absence of the
determine structure/function relationships. In general, the photocatalyst (Supporting Information, Figure S3). In general,
greatest reactivity for the photodechlorination reaction was while all of the PCB congeners demonstrated varying degrees
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Figure 7. SEM and TEM images of the Cu2O/Pd 9% structures after the photocatalytic reductive dechlorination of PCB 3 using a catalyst loading of
2 mg/mL. (a, b) SEM and (c) TEM images. Panel (b) shows a zoomed-in image of the red box in panel (a).

of photobased degradation, biphenyl formation was negligible. tion process and that the reaction rates are highly sensitive to
For instance, PCB 1 was quickly converted into other oxidative, the composite structure and catalyst loading. To probe whether
and nonreductive, dechlorination products, such as hydrox- the photocatalytic reductive dechlorination reaction aects the
ybiphenyl, as detected via GC-MS, with minor generation of material structure, SEM and TEM analyses were conducted on
biphenyl. Furthermore, in agreement with previous studies,28,29 the Cu 2 O/Pd 9% materials after being used for the
it was observed that PCB photodegradation was favored in the dechlorination of PCB 3 at a catalyst loading of 2 mg/mL, as
order of Cl substitution at the ortho > meta > para positions shown in Figure 7. Additional SEM and TEM images of the
under light irradiation in the absence of a photocatalyst. Such a materials presented for the postreaction analysis can be found
trend is in direct opposition to the current results, where in the Supporting Information, Figure S4. Imaging of the
photocatalytic reductive dehalogenation of PCBs favored a Cl Cu2O/Pd 9% cubes postdechlorination showed that while the
substitution order of para > meta ortho positions, with majority of the structures remained intact, some of the particles
biphenyl as the only product formed. Taken together, this became hollow (29%). In this regard, Figure 7a shows a large
suggests that other photodriven chemical processes that do not area SEM image of the materials where fully intact materials are
follow reductive dechlorination pathways are occurring in the present, although hollow structures are also evident. Figure 7b
absence of the catalyst to generate such products as shows a zoomed-in SEM image of the cubic materials in the red
hydroxylated PCBs. It should be noted that hydroxylated box of Figure 7a. In this image, it is apparent that signicant
PCBs have enhanced toxicity compared to that of the parent internal structural changes have occurred for this set of
substrate;3133 thus, reductive pathways of degradation, as materials. TEM analysis of these materials further exposes the
provided by the Cu2O/Pd material, are preferred. dramatic structural changes to the particles that become hollow
While the above control reactions conrmed the Cu2O/Pd during the reaction (Figure 7c). In this image, it is clear that the
reductive dechlorination reactivity, it is essential to determine at Cu2O/Pd materials have been internally changed, whereby the
what concentration the catalyst loading aects the tandem oxide component was potentially partially etched while the Pd
photocatalytic performance. This is especially important for layer remained intact. To examine the material composition of
transitioning energy- and material-intensive processes to the postdechlorinated particles, EDS analysis was performed.
photocatalytic routes in order to maximize reactivity while These assessments indicated that the Pd content (relative to
minimizing the consumption of resources. In this regard, the Cu2O mass) of the composite structures increased from 9.1
modied photocatalytic reactions using the Cu2O/Pd 9% 0.1% Pd mass before the reaction to 9.6 0.6% Pd mass
materials were carried out where the catalyst mass employed after the reaction occurred, suggesting that the morphological
was varied to provide loadings of 1 and 3 mg/mL. Note that all changes arose predominantly from partial etching of the oxide
of the reactions discussed above have a catalyst loading of 2 component.
mg/mL. From this analysis, shown in Figure 6a, dierent To identify and understand the structural modications to
reactivities were observed for the various catalyst loadings for the particle morphology due to photocatalysis as opposed to
the dechlorination of PCB 3. Interestingly, under these photocorrosion, a set of control experiments was conducted. In
conditions, 2 mg/mL was the optimal catalyst loading for the this study, at a catalyst loading of 2 mg/mL, the Cu2O/Pd 9%
dechlorination process. As mentioned above, under these materials were photoirradiated in the reaction solvent for 250 h
conditions 98% of PCB 3 was dechlorinated in 75 h, with a in the absence of PCBs. SEM analysis showed that the majority
kPCB3 value of (50.8 2.9) 103 h1 (Figure 6b and of the cubes were still whole (71% of the sample); however,
Supporting Information, Table S3). The 1 mg/mL catalyst 29% of the materials appeared to be pitted, suggesting that
loading gave a decreased kPCB3 value of (17.6 0.7) 103 h1. photocorrosion had occurred (Supporting Information, Figure
A further diminished kPCB3 value of (9.9 0.9) 103 h1 was S5a).8,34,35 This pitted morphology was signicantly dierent
observed for the 3 mg/mL catalyst loading. These results than that observed after the photodechlorination reaction,
indicate that 2 mg/mL is the most ecient catalyst loading for which generated hollow structures, suggesting that the
the dechlorination process. At a lower catalyst loading, the hollowing eect was not due to photocorrosion. To rearm
decreased amount of catalytic materials presented led to lower this hypothesis, a second control study was completed where
reactivity, whereas for the 3 mg/mL catalyst loading, the high bare Cu2O cubes at a catalyst loading of 2 mg/mL were
material concentration resulted in inecient light absorption by photoirradiated in the solvent for 250 h. In this analysis,
the materials, causing diminished reactivity. pronounced surface reconstruction was observed (Supporting
From the above studies, it is clear that the Cu2O/Pd Information, Figure S5b), displaying jagged overgrowths on the
materials control the overall photodriven reductive dechlorina- oxide. Although no pitting was evident in the bare Cu2O
48 DOI: 10.1021/acsomega.6b00076
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sample, hollow cubes were also not observed, supporting the Pd/Fe bimetallic nanotubes with 0.9 wt % Pd was achieved in
hypothesis that photocorrosion does not drive Cu2O/Pd 25 h at a catalyst loading of 0.25 mg/mL. This high
material etching. dechlorination eciency was attributed to the high surface
These postreaction analyses provide important insights area to volume ratio of the hollow nanotubes structure. For
concerning the photocatalytic mechanism of the Cu2O/Pd these systems, the production of H2 by Fe0 in aqueous solution
composite structures. In the reaction system with PCB 3, leads to iron corrosion. As such, H2 production and iron
hollowing of the cubes is evident. This control study suggests reactivity decrease over time; therefore, Pd/Fe materials are not
that the hollow cubes are a result of photodechlorination, which sustainable as a result of surface oxidation and precipitation of
may aect the recyclability of the materials vide inf ra; pitting is iron oxides/hydroxides on the surface of the iron.39,40 While
evident from the Cu2O/Pd 9% materials and particle surface these materials are the most reactive for PCB dechlorination,
reconstruction is observed in the bare Cu2O cubes after being they are not directly comparable to the Cu2O/Pd systems due
photoirradiated in ethanol/water. Additionally, the postdech- to the signicant dierences in H2 generation (Fe oxidation vs
lorination wide-area EDS analysis shows that the Pd mass photocatalysis). While the Cu2O/Pd materials demonstrated
percent is higher after the reaction. Taken together, these lower reactivity, they represent a new avenue to materials with
postreaction analyses suggest that photodechlorination is potential long-term reactivity for in-eld photodechlorination
responsible for the hollowing of the cubes. Although using sunlight as the energy source. Further studies are
speculative, it is possible that the shell of the hollow cubes is underway to enhance the reactivity of the tandem catalysts,
composed mainly of Pd; however, additional studies are including pathways to enhance their recyclability.
required to determine this ne level of detail.
Because of the observed structural changes of the Cu2O/Pd
after the rst catalytic cycle, a reduction in the photocatalytic
CONCLUSIONS
In summary, we have generated cubic Cu2O/Pd composite
activity for subsequent catalytic cycles could be observed. As structures with tandem photocatalytic reactivity. It was
such, recyclability studies of the composite materials as catalysts demonstrated that the Pd content in the material aects the
for PCB photodechlorination were conducted using Cu2O/Pd particle surface morphology, where higher amounts of Pd result
7.5% materials with PCB 3 at a catalyst loading of 2 mg/mL. in structures with a akey topology. Additionally, the cubic
Figure S6 in the Supporting Information presents the shape of the particles was maintained regardless of the material
dechlorination analysis and the resulting rate constants for composition. Although simple, this architecture is strategic for
the recyclability studies. For this process, when the 75 h transitioning energy- and material-intensive reactions that
reaction period of the rst cycle was completed, the Cu2O/Pd require H2 as a reagent to more sustainable, photocatalytic
7.5% material was ltered, washed, and dried. Once the material methods. The as-synthesized Cu2O/Pd particles demonstrated
was completely dry, it was weighed, and the appropriate volume high tandem catalytic performance for the reductive dehaloge-
of PCB 3 was added in order to maintain a catalyst loading of 2 nation of PCBs 3 and 2, but they showed slow dechlorination
mg/mL. For the rst cycle, 88% of PCB 3 was dechlorinated rates for PCB 1. The data indicate that the overall
after 75 h, resulting in a kPCB3 value of (29.8 2.0) 103 h1. dechlorination reaction rate results from a synergistic eect of
For the second cycle, 60% of PCB 3 was dechlorinated after 75 several key factors, including the surface morphology and
h, giving a kPCB3 value of (10.6 1.2) 103 h1. As is evident, composition of the materials and the steric eects of the
diminished reactivity was noted for the second reaction cycle, substrate. Postreaction analysis showed that some of the Cu2O/
likely arising from the catalytic material degradation. It is Pd cubes had become hollow following dechlorination. The
evident that the redox potential of Cu2O intrinsically exists light-driven tandem catalytic system demonstrated herein
within its band gap energy, which might lead to self-oxidation exemplies how current photocatalyst materials for H 2
or self-reduction and depletion of copper species into the production can be applied to reactions not typically fueled by
solution.36 Additionally, Cu2O oxidation to CuO at the light. The fundamental understanding of material structural
composite material surface could be occurring resulting in eects over catalytic function and reactivity is important in the
diminished reactivity; however, partial reduction back to Cu2O design of photocatalytic systems for sustainable reactivity.
should restore the reactivity. Additional studies are required to
determine the actual basis of the reactivity changes.
Optimization of this tandem catalytic system is still in

*
ASSOCIATED CONTENT
S Supporting Information
progress; however, in comparison to other catalysts used for the The Supporting Information is available free of charge on the
dechlorination of PCBs, the Cu2O/Pd composite materials are ACS Publications website at DOI: 10.1021/acsomega.6b00076.
highly unique in that light is used as the energy source to drive Cu2O SEM images, size distribution histograms, ICP-
the reaction. For this, the most established class of materials for OES analysis, pseudo-rst-order rate constants for the
PCB dechlorination is based on Pd/Fe nanostructures. For PCB dechlorination reactions, reaction analysis for
example, Wang et al. reported the synthesis of nanoscale Pd/Fe control PCB photodegradation and dechlorination
particles for the dechlorination of PCBs.37 Within 17 h, studies, SEM and TEM images of the materials
complete dechlorination of the PCB congeners of Aroclor 1254 postreaction, and reaction analysis for recyclability
by Pd/Fe nanoparticles was observed. The initial PCB solution studies (PDF)

mixture concentration was 5 mg/L, and the catalyst loading was
50 mg/mL. Although complete dechlorination was achieved
within 17 h, a less concentrated PCB solution and a AUTHOR INFORMATION
signicantly higher catalyst loading than those employed herein Corresponding Author
were used. In an additional approach, Zahran et al. synthesized *E-mail: [email protected]. Phone: (305) 284-9351.
Pd/Fe bimetallic nanotubes that demonstrated high reactivity.38 Notes
Dechlorination of 25 M 3,34,4-tetrachlorobiphenyl using The authors declare no competing nancial interest.
49 DOI: 10.1021/acsomega.6b00076
ACS Omega 2016, 1, 4151
ACS Omega

Article

ACKNOWLEDGMENTS (19) Shiraishi, Y.; Fujiwara, K.; Sugano, Y.; Ichikawa, S.; Hirai, T. N-
Monoalkylation of Amines with Alcohols by Tandem Photocatalytic
We would like to thank the University of Miami for nancial and Catalytic Reactions on TiO2 Loaded with Pd Nanoparticles. ACS
support of this research. A.S.W. was supported by an IMSD Catal. 2013, 3, 312320.
grant (1R25GM076419). E.M.Z. acknowledges the Depart- (20) Sui, Y.; Fu, W.; Yang, H.; Zeng, Y.; Zhang, Y.; Zhao, Q.; Li, Y.;
ment of Applied Organic Chemistry, National Research Centre, Zhou, X.; Leng, Y.; Li, M.; Zou, G. Low Temperature Synthesis of
Egypt, for granting an academic leave. Cu2O Crystals: Shape Evolution and Growth Mechanism. Cryst.

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51 DOI: 10.1021/acsomega.6b00076
ACS Omega 2016, 1, 4151