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Article
18.1% single palladium atom catalysts on
mesoporous covalent organic framework for
gas phase hydrogenation of ethylene
Chun-Te Kuo, Yubing Lu,
Pezhman Arab, K. Shamara
Weeraratne, Hani El-Kaderi,
Ayman M. Karim
helkaderi@vcu.edu (H.E.-K.)
amkarim@vt.edu (A.M.K.)
Highlights
18.1 wt % palladium single atoms
are supported on mesoporous
covalent organic framework
Article
18.1% single palladium atom catalysts
on mesoporous covalent organic framework
for gas phase hydrogenation of ethylene
Chun-Te Kuo,1 Yubing Lu,1 Pezhman Arab,2 K. Shamara Weeraratne,2 Hani El-Kaderi,2,*
and Ayman M. Karim1,3,*
SUMMARY
Noble metal single-atom catalysts maximize metal utilization and
offer opportunities to design heterogeneous catalysts at the molec-
ular scale. Mesoporous covalent organic frameworks provide an
ideal support to stabilize metal single atoms with specific ligand
configuration similar to a homogeneous catalyst. In this work, a
high loading of single Pd atoms, 18.1 wt %, on mesoporous imine-
linked covalent organic framework was synthesized, characterized,
and evaluated for ethylene hydrogenation. X-ray photoelectron
spectroscopy, X-ray absorption spectroscopy, and diffuse-reflec-
tance infrared Fourier transform spectroscopy of adsorbed CO
demonstrate that the Pd is atomically dispersed with a highly homo-
geneous local coordination. The Pd single atoms are active for hy-
drogenation of ethylene to ethane at room temperature. The study
demonstrates that mesoporous COFs provide a large number of
identical metal binding sites that are good candidates for immobiliz-
ing metal single atoms and their use in gas-phase catalytic applica-
tions.
INTRODUCTION
Supported metal single atoms,1–6 dimers,7–10 and subnanometer clusters11–15 have
recently drawn significant interest because they exhibit extraordinary catalytic per-
formance due to their unique geometric structure and electronic properties
compared with nanoparticles. Hülsey et al.16 showed that Rh single atoms supported
on phosphotungstic acid have extraordinary activity for CO oxidation even at around
50 C (323 K). We recently reported that Pt single atoms and subnanometer clusters
exhibit remarkably high selectivity for hydrogenation of acetylene to ethylene in
contrast to the low selectivity on large Pt nanoparticles.17 Because of the importance
of palladium as a catalyst for various reactions such as (selective) hydrogenation,18–21
dehydrogenation,22–25 and cross-coupling reactions,26–29 several strategies for syn-
thesizing Pd with controlled nuclearity have been reported. Pei et al.30 prepared Cu-
alloyed Pd single-atom catalyst and reported high selectivity, 85%, toward ethylene 1Department of Chemical Engineering, Virginia
at 100% acetylene conversion. Yan et al.31 fabricated atomically dispersed Pd on gra- Polytechnic Institute and State University,
phene using atomic layer deposition and reported 100% selectivity to butenes at 95% Blacksburg, VA 24060, USA
2Department of Chemistry, Virginia
conversion during selective hydrogenation of 1,3-butadiene.
Commonwealth University, Richmond, VA
23284-2006, USA
Covalent organic frameworks (COFs) are crystalline porous organic solids con- 3Lead contact
structed from linking organic building blocks together by strong covalent *Correspondence: helkaderi@vcu.edu (H.E.-K.),
bonds.32–34 With the aid of reticular chemistry, COFs can be designed with a precise amkarim@vt.edu (A.M.K.)
control over their textural properties (i.e., pore size and shape, surface area) while https://doi.org/10.1016/j.xcrp.2021.100495
Cell Reports Physical Science 2, 100495, July 21, 2021 ª 2021 The Author(s). 1
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
ll
OPEN ACCESS
Article
the chemical nature of the building blocks dictates the chemical functionality of the
pores. Given their high surface areas and diverse chemical functionalities, COFs
have attracted considerable interest in heterogeneous catalysis because of their
ability to host catalytic metals in the form of both metal nanoparticles and single
atoms coordinated to the walls of the frameworks.35–40 The latter is of great interest
to metal single-atom catalytic processes because the periodic structure of COFs en-
ables high loading and rapid access of catalytic centers without compromising mass
transport rates of the reactants and products. Metal loading in COFs is typically car-
ried out by either pre- or post-synthetic modification strategies.38,41 Chelated metal
ions can be part of the building blocks prior to polymerization or metal ions can be
introduced after framework synthesis which gives more flexibility in terms of metal
loading level and metal type. For example, imine-linked COFs have been explored
as metal support scaffolds because of their Schiff-base nature, which proved to be an
effective strategy for accessing recyclable catalysts with remarkable activity in many
catalytic processes, especially Suzuki cross-coupling reactions.38,42–47 Surprisingly,
COFs use in gas-phase catalytic transformation remains very scarce.
A B C
N1s XPS spectrum for all the nitrogen atoms of the framework upon complexation
with PdCl2 (Figure 3B), indicating binding of PdCl2 to the imine groups.47
Figure 4A shows the XANES spectra at the Pd K-edge of dried PdCl2@ILCOF-1 cata-
lyst and Pd standard samples, PdCl2 and PdO. PdO has the highest white-line inten-
sity, while PdCl2@ILCOF-1 and PdCl2 are similar but with different spectral patterns.
As shown by the EXAFS results (Figures 4B and 4C; Figure S1), the PdCl2@ILCOF-1
EXAFS spectrum has peaks with some similarities to PdO and PdCl2. The EXAFS
modeling results (Figure 5; Table 1) show that Pd, on average, is bound to two Cl
and two N atoms at 2.03 and 2.31 Å, respectively (see detailed fit in Table S1 and
Figure S3). The results show that PdCl2 remains intact during the synthesis and binds
to the framework through two N atoms. This is consistent with the XPS results, which
showed similar spectra for the PdCl2@ILCOF-1 catalyst and PdCl2(phen). We can
conclude from the EXAFS and XPS results that Pd is stabilized as isolated single
atoms within the pores of ILCOF-1. We note that the Pd remained isolated and
the Pd coordination was unaffected by pretreatment in He at 120 C, as confirmed
by the almost identical XANES and EXAFS spectra (Figure S2). To determine the ho-
mogeneity of the local environment around the Pd atoms in the PdCl2@ILCOF-1
catalyst, CO adsorption was studied at 40 C by diffuse-reflectance infrared Fourier
transform spectroscopy (DRIFTS). A symmetrical and relatively narrow band at
2,130 cm1 (Figure 4D; full width at half maximum [FWHM] of 20 cm1) was
observed. No other CO bands were present between 1,800 and 2,200 cm1, where
the typical vibrational frequencies for linear, bridge, and hollow CO bound on Pd are
reported,50–54 confirming that Pd is present as isolated single atoms. The CO band
position on Pd atoms in the PdCl2@ILCOF-1 catalyst (2,130 cm1) is very close to that
reported on Cu-alloyed Pd single atoms (2,133 cm1).30 The relatively narrow
2,130 cm1 CO band in DRIFTS indicates that the local environment of the Pd single
atoms in the PdCl2@ILCOF-1 catalyst is similar.
A B
C D
DRIFTS showing that Pd remained mostly present as single atoms in the spent cata-
lyst (see Table S1; Note S1; Figures S5–S7). We note that although the Pd is present
mostly as single atoms in the spent catalyst, the DRIFTS and EXAFS results indicate
the presence of a minority Pd clusters, and possibly dimers, which contribute to the
measured reactivity.
Figure 6 shows the dependence of the turnover frequency (TOF) on the hydrogen and
ethylene partial pressures. The slopes of best linear fit to the kinetic data under
steady-state ethylene hydrogenation indicate that the reaction order in H2 was
0.59 G 0.01 and the reaction order in C2H4 was 0.01 G 0.01 (Figure 6). Kinetic studies
of ethylene hydrogenation have been reported on supported metal single atoms,63
subnanometer clusters,61,65–67 and nanoparticles.68,69 For example, the Gates group
studied ethylene hydrogenation on supported Ir65,66,70,71 and Rh60,61,67,72 single
atoms, pair sites, and small clusters, and the catalysts were found to be active at
353 K and atmospheric pressure. On MgO-supported Ir pair-site and Ir6 catalysts,
the reaction order in H2 and C2H4 were found to be 0.5 and 0, respectively. In
another study, Guzman and Gates63 characterized and tested mononuclear gold
complexes supported on MgO for ethylene hydrogenation at atmospheric pressure
and 353 K. The reaction order in H2 (Phydrogen = 4.7–60.0 kPa at Pethylene = 5.3 kPa) was
0.5 and that the reaction order in ethylene (Pethylene = 4.7–40.0 kPa at Phydrogen =
5.3 kPa) was 0.0 on mononuclear gold complex catalyst supported on MgO. More-
over, Molero et al.69 measured the kinetics of ethylene hydrogenation on Pd(111)
A B
C D
A B
EXPERIMENTAL PROCEDURES
Resource availability
Lead contact
Further information and requests for resources and data should be directed to and
will be fulfilled by the lead contact, Ayman M. Karim (amkarim@vt.edu).
Materials availability
Unless otherwise noted, reagents obtained from commercial suppliers were used
without further purification. Solvents were technical grade and were used without
further purification. See catalyst preparation section for full details of synthetic
procedures.
Catalyst preparation
ILCOF-1 was synthesized according to our previously reported procedure.48 In brief,
a Pyrex tube, with outer diameter (OD) of 12 mm and inner diameter (ID) of 10 mm,
was charged with the monomers tetrakis(p-formylphenyl)pyrene (20 mg, 32 mmol)
and 1,4-p-phenylenediamine (7.0 mg, 64 mmol). Then, the monomers were sus-
pended in a solution obtained by mixing 3.0 mL 1,4-dioxane and 0.6 mL 3.0 M acetic
acid. The mixture was sonicated for 10 min, and 6 M acetic acid (0.6 mL) was added
slowly. The tube was degassed by three freeze-pump-thaw cycles and flash-frozen at
77 K using a liquid N2 bath and then flame-sealed under vacuum. The mixture was
heated at 120 C for 3 days. The resulting mixture was filtered and washed with anhy-
drous acetone followed by tetrahydrofuran (THF) to afford ILCOF-1 as a yellow pow-
der (20 mg).
PdCl2@ILCOF-1 was synthesized using the ILCOF-1 and PdCl2 as follows. A dry
25 mL Schlenk flask with a stir bar was charged with ILCOF-1 (70 mg, 0.09 mmol) un-
der an inert atmosphere. A freshly prepared solution of bis(benzonitrile)palladium(II)
chloride (PdCl2[CNPh]2, 70 mg) in anhydrous chloroform (15 mL) was added using a
syringe. The resulting brown mixture was stirred at room temperature for 2 h under a
N2 atmosphere. The product was isolated by filtration and washed with anhydrous
chloroform via Soxhlet under N2 atmosphere overnight. The solid was dried under
vacuum at 120 C to obtain PdCl2@ILCOF-1 (97 mg, 95% yield) as a dark brown pow-
der. The palladium content of the sample was determined using inductively coupled
plasma optical emission spectroscopy (ICP-OES) analysis using a Vista MPX CCD
Simultaneous ICP-OES, and the Pd content was found to be 18.1 wt %.
Catalyst characterization
For porosity analysis of the samples, argon sorption measurements were carried out
using a Quantachrome Autosorb iQ volumetric analyzer using ultrahigh purity (UHP)
grade argon at 87 K. The samples were outgassed at 110 C under vacuum for 24 h
before collecting argon sorption isotherms. The specific surface area of the samples
was calculated from the argon adsorption branch on the basis of the Brunauer-Em-
mett-Teller (BET) model. PSD was calculated from adsorption argon isotherms by
nonlocal density functional theory (NLDFT) using a cylindrical pore (zeolite) model.
Powder XRD patterns were collected on a Panalytical X’Pert pro multipurpose
diffractometer (MPD) with a copper Ka radiation.
The XPS analysis was conducted using a Thermo Fisher Scientific ESCALAB 250 in-
strument with a monochromatized Al Ka X-ray source. For preparation of the sam-
ples for XPS, the powder was pressed into a piece of double-stick carbon tape, which
was mounted on the sample holder. For the purpose of charge compensation during
XPS analysis, a combination of a low-energy electron flood gun and an argon ion
flood gun was used. The binding energy scale of the XPS spectrum was calibrated
by setting the C1s peak at 285.0 eV. The XPS data were analyzed using Thermo
Avantage software (version 4.84).
A B
situ Praying Mantis diffuse reflection cell (Harrick Scientific Products). Prior to CO
chemisorption, the catalyst was first dried in 100 sccm N2 flow at 120 C for 12 h. After
the N2 treatment, the catalyst was cooled down to 40 C using liquid nitrogen un-
der 40 sccm N2. For the spent catalyst, the catalyst was first exposed to a flow of
0.5 kPa C2H4 and 5 kPa H2 (balance N2, 160 sccm total flowrate). A background spec-
trum was collected at 40 C under N2 and subtracted from the series of subsequent
spectra. A 1 kPa CO gas (balance N2) flowed through the sample for 20 min and then
purged with 40 sccm N2 to remove the gas phase CO on the PdCl2@ILCOF-1 cata-
lyst, while a series of CO spectra were collected continuously. Each spectrum is an
average of 32 scans with data spacing of 0.482 cm1. The CO (5%, balance N2),
H2, and C2H4 (20%, balance N2) were obtained from Airgas, and N2 was obtained
from in-house liquid N2 boil-off. N2 and H2 were purified by high-capacity moisture
and oxygen traps (Restek catalog #21997 and #20601). CO was purified with a cor-
rosive gas purifier (Metal-X Purification Medium, Nanochem).
XAS measurements at the Pd K-edge for the PdCl2@ILCOF-1 samples were per-
formed at the Stanford Synchrotron Radiation Light Source (SSRL) at beamline 9-3
using an in-house-built cell with a 4 mm ID glassy carbon tube.79 Beamline 9-3 is a
16-pole, 2 T wiggler side station with vertically collimating mirror for harmonic rejec-
tion and a cylindrically bend mirror for focusing. The photon energy was selected us-
ing a liquid nitrogen-cooled, double-crystal Si (220) f = 90 monochromator. The
samples were scanned simultaneously in transmission and fluorescence detection
modes using ion chambers (filled with pure N2) and a 100-element solid-state Ge
monolith detector (Canberra). A Pd standard foil was scanned simultaneously with
each sample for energy calibration. Step-scanning X-ray absorption spectra were
measured from 24,150 to 25,244 eV, corresponding to photoelectron wave number
k = 15.2 Å1. XANES and EXAFS data processing and analysis were performed using
Athena and Artemis programs of the Demeter data analysis package.80,81 For each
sample, four scans were collected and merged after alignment. c(k) was obtained by
subtracting smooth atomic background from the normalized absorption coefficient
using the AUTOBK code. The theoretical EXAFS signal was constructed using the
FEFF6 code82 and fitted to the data in R-space using the Artemis program. The theo-
retical EXAFS signals for Pd-N and Pd-Cl scattering paths were constructed using the
FEFF6 code using the crystal structure of Pd(OAc)2TOP2 and replacing the O atom
bound to Pd from the acetate with N and the phosphorous bound to Pd in trioctyl-
phosphine with Cl. For the Pd-Pd scattering path, we used an fcc Pd structure. The
spectra were fitted by varying the coordination number of the single scattering
paths, Pd-Pd, Pd-N, and Pd-Cl, the effective scattering lengths, the bond length dis-
order of each path, and the correction to the threshold energy, DE0 (DE0 was the
same for Pd-N and Pd-Cl because these paths were calculated using the same
model). Because of the strong correlation between the parameters of the Pd-N
and Pd-Cl scattering paths, especially coordination numbers and bond disorders,
we used one common parameter for the bond length disorder of both paths. This
allowed us to obtain smaller uncertainties in the model fit parameters for comparison
purposes between samples. S02 (the passive electron reduction factor) was obtained
by first analyzing the spectrum for a Pd foil, and the best fit value (0.79) was fixed dur-
ing the fitting. The k range used for Fourier transform of the c(k) was 3–12.3 Å1, and
the r range for fitting was 1.2–2.3 Å for fitting Pd-N and Pd-Cl scattering paths only
and 1.2–2.9 Å when Pd-Pd needed to be included in the fit. The best parameters fit
using a k weight of 2 in Artemis are reported, but the results were similar to those
using k weights of 1, 2, and 3.
The conversion and TOF (rate of reaction per Pd atom per second) of ethylene hydro-
genation were determined from differential conversion and calculated as shown
below. We note that no products other than C2H4 and C2H6 were detected by the
Micro GC and that the carbon balance (outlet/inlet) was close to 100% under all
conditions.
moles of C2 H6 ðoutletÞ
Conversion =
moles of C2 H4 ðinletÞ
rate of C2 H6 formation moleC2 H6 g1
cat s
1
TOF s1 = 1
moles of surface Pd molePd gcat
Catalytic hydrogenation of ethylene was carried out with an ethylene (C2H4) partial
pressure of 0.5 kPa and hydrogen (H2) partial pressure of 5 kPa at 20 C. Kinetics ex-
periments were performed by varying the C2H4 and H2 partial pressures in the
ranges 0.5–2.5 kPa and 1–5 kPa, respectively. The PdCl2@ILCOF-1 catalyst was
found to be very stable, with less than 5% change in activity over a 6 h period (the
typical time for the kinetic measurement). The only product detected was ethane,
and there was no measurable conversion of C2H4 and H2 in the absence of the
catalyst.
SUPPLEMENTAL INFORMATION
Supplemental information can be found online at https://doi.org/10.1016/j.xcrp.
2021.100495.
ACKNOWLEDGMENTS
This research was sponsored primarily by the American Chemical Society Petroleum
Research Fund (PRF) and was accomplished under award number 55575-ND5. Use
of the SSRL (beamline 9-3, user proposal 4938) was supported by the U.S. Depart-
ment of Energy, Office of Basic Energy Sciences, under contract DE-AC02-
76SF00515.
AUTHOR CONTRIBUTIONS
C.-T.K. conducted the ethylene hydrogenation kinetics, DRIFTS measurements (and
helped with XAFS), performed the data analysis, and wrote the first draft of the
manuscript. Y.L. performed the XAFS and some of the DRIFTS experiments. P.A.
and K.S.W. synthesized the catalyst and performed the surface area, XRD, and
XPS measurements. A.M.K. and H.E.-K. conceived the idea and directed the project.
C.-T.K., Y.L., H.E.-K., and A.M.K. cowrote the paper. All authors discussed the results
and commented on the paper.
DECLARATION OF INTERESTS
The authors declare no competing interests.
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Supplemental information
He at
Pretreatment He at 30 °C H2 at 30 °C
110 °C
NPd-Pd - - 0.8±0.2
3 2
σ2 Pd-Cl × 10 (Å ) 3±2 4±1 4±1
3 2
σ2 Pd-Pd × 10 (Å ) - - 8±2
a b b b
∆E0 Pd-N/Cl (eV) 12 12 12
Reduced χ2 57 73 36
(b)
(c)
2
Figure S1. Pd K-edge k -weighted EXAFS data in k-space for (a) PdCl2@ILCOF-1 dried, (b) PdCl2 (c)
PdO.
(a)
(b)
(c)
Figure S2. Pd K-edge X-ray absorption spectroscopy of PdCl2@ILCOF-1 catalysts (fresh and dried).
2
XANES (a), and EXAFS magnitude (b) and imaginary (c) part of the of the Fourier transformed k -
-1
weighted χ(k) data, Δk=3-12.0 Å .
(a)
(b)
Figure S3. EXAFS fit to PdCl2@ILCOF-1 dried. Contribution of different scattering paths. (N path =Pd-N
and Cl path = Pt-Cl). (a) r-space magnitude part. (b) r-space imaginary part.
Figure S4. stability test of the PdCl2@ILCOF-1. Dependence of TOF on C2H4 partial pressure was
measured at a constant H2 partial pressure of 5 kPa. The stability test was performed at the initial
condition after ~6 h measurement.
Note S1 related to state of the catalyst in H2 and after reaction
In order to understand the catalyst structure after reaction condition, DRIFTS of CO adsorption after in-situ
ethylene hydrogenation, 0.5 kPa C2H4 and 5 kPa H2 in N2 balance at 20 °C, was conducted and is shown
-1
in the orange spectrum in Figure S5. The linearly bound CO band red-shifted from 2130 to 2122 cm , while
-1
a smaller portion did not shift (see shoulder band at 2130 cm ). It is plausible that the red-shift is due to a
change in the electronic property of Pd after exposure to H2 and ethylene (e.g. presence of H2 and/or
1-6 −1
ethylene on Pd and or the support). Additionally, a CO band at 1920 cm which can be assigned to bridge
7-12
adsorbed CO on Pd clusters that formed during the exposure to H2 flow. However, we did not observe
-1
a linear CO band in the 2000-2100 cm range. Our DRIFTS results suggest that under reaction conditions
a small percentage of Pd single atoms agglomerate into clusters, likely smaller than 1 nm. This is consistent
with the EXAFS results showing that Pd was still mostly present as single atoms (EXAFS after H2 treatment,
Table S1, Figure S5 and S6), where the Pd-N and Pd-Cl coordination numbers were still close to those
before reaction. Additionally, reduction of the PdCl2@ILCOF-1 catalyst at 120 °C resulted in almost
-1
complete reduction of the Pd and formation of nanoparticles as indicated by the metallic linear (2067 cm )
-1
and bridge (1919 cm ) CO adsorption peaks in DRIFTS (green spectrum in Figure S5). From the
-1
comparison between the two spectra in Figure S5, we could see that the small peak at 1922 cm only
represents a very small proportion of the Pd, and the large majority of the Pd is still present as single atoms
-1
(CO peak at 2122 cm ) after ethylene hydrogenation.
Figure S5. DRIFTS spectra of CO adsorption on the PdCl2@ILCOF-1 catalyst (1) at -40 °C after in-situ
ethylene hydrogenation reaction (0.5 kPa C2H4 and 5 kPa H2 in N2 balance) at 20 °C (orange) and (2) at
25 °C after H2 treatment at 120 °C (green).
(a)
(b)
(c)
Figure S6. Pd K-edge X-ray absorption spectroscopy of PdCl2@ILCOF-1 catalysts (dried and H2 flow at
2
30 °C). XANES (a), and EXAFS magnitude (b) and imaginary (c) part of the of the Fourier transformed k -
-1
weighted χ(k) data, Δk=3-12.0 Å .
(a)
(b)
2
Figure S7. Pd L3-edge EXAFS spectra and fit of the Fourier transformed k -weighted χ(k) data (∆k= 3-
-1
12.0 Å ) for the PdCl2@ILCOF-1catalyst after H2 flow at 30 °C. (a) EXAFS magnitude and (b)imaginary
2 -1
part of the of the Fourier transformed k -weighted χ(k) data, Δk=3-12.0 Å
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