Single-Atom-Based Vanadium Oxide Catalysts Supported on Metal-Organic Frameworks: Selective Alcohol Oxidation and Structure-Activity Relationship

Article abstract of DOI:10.1021/jacs.8b05107

We report the syntheses, structures, and oxidation catalytic activities of a single-atom-based vanadium oxide incorporated in two highly crystalline MOFs, Hf-MOF-808 and Zr-NU-1000. These vanadium catalysts were introduced by a postsynthetic metalation, a

Full text of DOI:10.1021/jacs.8b05107

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Communication
Single-Atom Based Vanadium Oxide Catalysts supported on Metal–Organic
Frameworks: Selective Alcohol Oxidation and Structure–Activity Relationship
Ken-ichi Otake, Yuexing Cui, Cassandra T. Buru, Zhanyong Li, Joseph T. Hupp, and Omar K. Farha
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b05107 • Publication Date (Web): 27 Jun 2018
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J
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J
Ken-ichi Otake, Yuexing Cui, Cassandra T. Buru, Zhanyong Li, Joseph T. Hupp, Omar K. Far-
ha*
J K
, ,
J Department of Chemistry and Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Ev-
anston,
K
Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
Supporting Information Placeholder
ABSTRACT: We report the syntheses, structures, and oxidation
catalytic activities of a single-atom-based vanadium oxide incor-
porated in two highly crystalline MOFs, Hf-MOF-808 and Zr-
NU-1000. These vanadium catalysts were introduced by a
postsynthetic metalation, and the resulting materials (Hf-MOF-
8
08-V and Zr-NU-1000-V) were thoroughly characterized
through a combination of analytic and spectroscopic techniques
including single-crystal X-ray crystallography. Their catalytic
properties were investigated using the oxidation of 4-
methoxybenzyl alcohol under an oxygen atmosphere as a model
reaction. Crystallographic and variable-temperature spectroscopic
studies revealed that the incorporated vanadium in Hf-MOF-808-
V changes position with heat, which led to improved catalytic
activity.
Owing to their high catalytic performance in various redox-
1
–6
mediated reactions and availability, vanadium oxide catalysts
have found extensive applications in chemical and environmental
industries, including the mass production of sulfuric acid and
phthalic anhydride and the remediation of environmental pollu-
2,5–7
tion.
Most vanadium catalysts used industrially are deposited
on the surface of a porous solid support, such as silica, alumina,
titania, zirconia, and zeolites, primarily to increase the surface
area and stability, essential to creating a superior catalyst. These
catalyst supports were initially assumed to be inert in terms of
reactivity. However, subsequent studies revealed that the perfor-
mance of these and many other supported catalysts are often high-
ly dependent on the identity of the support. These observations,
termed ‘support effects’, typically thought to derive from support-
induced, catalytically relevant changes in the geometric and/or
characterization of deposited species somewhat difficult. Fur-
thermore, multiple forms of active sites may be present.
4
4
Figure 1. Structures of pristine (a) Hf-MOF-808 and (b) Zr-NU-
1
000 with the corresponding structures of their inorganic nodes
and organic linkers.
OH) (OH) (H O) (BTC) ] ;
Hf-MOF-808 ([Hf (µ -O) (µ -
6 3 4 3
H BTC
=
benzene-1,3,5-
([Zr (µ -O) (µ -
4
6
2
6
2 ∞
3
tricarboxylylic
acid
and
Zr-NU-1000
6
3
4
3
8
–11
electronic structures of the active species.
However, the origin
OH) (OH) (H O) (TBAPy) ] ; H TBAPy = 1,3,6,8-(p-benzoic-
4
4
2
4
2 ∞
4
and detailed mechanism of such effects often are unclear, primari-
ly due to the difficulty in determining the “true” active-species
structure under operando conditions. To better understand “sup-
port effects” and move toward the goal of “catalyst formation by
design”, comprehending structure–activity relationships in heter-
ogeneous catalysis is essential.
catalyst supports, such as high-area metal oxides, lack uniform
surfaces and pore structures, making unambiguous structural
acid)pyrene).
As an alternative to conventional catalyst supports, metal–
organic frameworks (MOFs) – infinite coordination networks
composed of metal ions or clusters connected by organic linkers
1
2–18
Unfortunately, conventional
19–24
and possessing well-defined structures
– have emerged as
prominent candidates. MOFs offer uniform porosity and a high
25,26
degree of freedom for structural tuning.
Furthermore, unam-
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biguous structural determination of the installed catalytic species
Hf-MOF-808-V and Zr-NU-1000-V were obtained via solu-
tion-phase metalation, SIM, of pre-existing Hf-MOF-808 and Zr-
NU-1000. (See Supporting Information for detailed procedures
and characterization, Figures 2, S1–S7.). Briefly, vanadyl acety-
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through crystallographic techniques is viable due to the periodici-
ty of MOF structures. These advantages can lead to an atomically
precise understanding the compositions of catalyst active sites,
and their attachment to supports, thereby elucidating structure–
activity relationships. From this perspective, our group as well as
others have investigated newly installed catalytic species in
MOFs, which can be introduced using postsynthetic modification
methods such as solvothermal deposition in MOFs (SIM) and
lacetonate (V(O)(acac) ), was dissolved in a methanol solution
2
containing each MOF. Striking color changes (from white to yel-
low for Hf-MOF-808-V and from yellow to dark yellow for Zr-
NU-1000-V) were observed during the SIM process, indicating
the successful incorporation of vanadium species. Consistent with
the color changes, ligand-to-metal charge-transfer (LMCT) peaks
centered at around 4.0 eV appeared in the diffuse reflectance UV
spectra (Figure S3). Inductively coupled plasma optical emission
spectroscopy (ICP-OES) measurements indicated vanadium load-
ings of 1.1 ± 0.2 and 1.0 ± 0.2 per node for Hf-MOF-808-V and
Zr-NU-1000-V, respectively. To verify the porosity of Hf-MOF-
2
7–38
atomic layer deposition in MOFs (AIM).
Here we report the syntheses, structures, and catalytic proper-
ties of single-metal-atom vanadium species incorporated in two
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highly crystalline MOFs, Hf-MOF-808
and Zr-NU-1000.
Both feature M -type oxide cluster nodes (M = Hf or Zr) and high
6
porosity (Figure 1). The vanadium species were deposited in the
two MOFs using the SIM method (creating V-SIM MOFs: Hf-
MOF-808-V and Zr-NU-1000-V), and the resulting MOFs were
characterized using a combination of analytical and spectroscopic
808-V and Zr-NU-1000-V, N sorption isotherm measurements at
2
77 K were conducted (Figures 1c–d, and S4). The Brunauer–
Emmett–Teller (surface) areas only decrease from 1620 to 1400
2
3
2
3
m /cm for Hf-MOF-808-V and from 1030 to 680 m /cm for Zr-
NU-1000-V, indicating that porosity is retained during V-SIM. In
addition, density function theory (DFT) calculated average pore
size distribution showed only small decreases in their pore sizes,
from 18 to 15 Å for Hf-MOF-808-V and from 30 to 27 Å for the
mesopore of Zr-NU-1000-V, suggesting partial occupation of
these pores by the vanadium species but overall retention of the
pore structures.
techniques including N sorption isotherms, infrared (IR), Raman,
2
diffuse reflectance UV, X-ray photoelectron (XPS) spectrosco-
pies, as well as single-crystal X-ray diffraction (SCXRD) anal-
yses. In these MOFs, the single-vanadium(V)-atom species were
anchored on the metal oxide nodes with different binding motifs,
specifically chelating in Hf-MOF-808-V and both bridging and
monodentate binding in Zr-NU-1000-V. Their catalytic properties
were investigated via alcohol oxidation reaction using oxygen as
the oxidant. Heat treatment was found to alter the locations of a
fraction of the vanadium ions in Hf-MOF-808-V, resulting in
significantly higher catalytic activity and an overall simplification
of siting.
In the diffuse reflectance infrared Fourier transform spectra
−1
(DRIFTS; Figure S5), a sharp peak at ~3650 cm and a broad
−1
peak at around 900 cm emerged for both Hf-MOF-808-V and
Zr-NU-1000-V, which were attributed to the V–O–H stretching
mode and the vibration modes involving the V–O–M (M = Hf or
1,42,43
Zr) bond, respectively.
In addition, a decrease in intensity of
the peak associated with terminal and bridging−OH stretches on
−1
the node at 3670 cm was observed. These features suggest
chemisorption of vanadium oxide species on the node for both Hf-
MOF-808-V and Zr-NU-1000-V; this conclusion was corroborat-
ed by Raman spectroscopy measurements (Figure S6).
To determine the oxidation states of the incorporated vanadium
species, X-ray photoelectron spectroscopy (XPS) measurements
were performed (Figure S7). The V 2p core-level spectra of Hf-
MOF-808-V (Figure S7a) and Zr-NU-1000-V (Figure S7b) fit
well with single-component binding energies of 517.0 (2p3/2) and
5
24.3 (2p1/2) eV for MOF-808-V, and 517.6 (2p3/2) and 524.6 eV
(
2p1/2) for NU-1000-V, respectively, which are similar to the en-
44
ergies of other reported V(V) compounds. These data indicated
that the V(IV) precursor was oxidized to V(V) when incorporated
on the nodes of MOFs.
To obtain further structural insight about the incorporated
vanadium species, SCXRD analyses were conducted (Figures S8–
1
1, and Table S1). The structures of vanadium species were found
to be quite different in Hf-MOF-808-V (Figure 3) versus Zr-NU-
000-V (Figures S10–11). In Hf-MOF-808-V, three types of
1
crystallographically non-equivalent single-atom vanadium sites
were observed, binding to the Hf -node in chelating mode (V1,
6
Figure 2. Powder X-ray diffraction patterns (PXRD; rt) and N2
isotherms (77 K). PXRD for (a) Hf-MOF-808 (black), Hf-MOF-
808-V (red), and Hf-MOF-808-after catalysis (rose) and (b) Zr-
NU-1000 (black), Zr-NU-1000-V (blue), and Zr-NU-1000-after
V2, and V3 in Figures 3b–e, S8). This positional disorder of va-
nadium sites might be explained by the partial hydration of vana-
dium sites; V1 and V3 would be assigned as the hydrated vanadi-
um. The crystallographically estimated loadings were 0.48 (V1),
catalysis (light blue). N adsorption (filled symbol) and desorption
2
0.54 (V2), and 0.48(V3) vanadium per Hf -node, aligning well
6
isotherms (open symbol) of (c) Hf-MOF-808 (black circle), Hf-
MOF-808-V (red square), and Hf-MOF-808-after catalysis (rose
triangle) (b) Zr-NU-1000 (black circle), Zr-NU-1000-V (blue
square), and Zr-NU-1000-after catalysis (light blue triangle). Vads
= adsorbed amount.
with the loadings determined by ICP-OES (see Supporting Infor-
mation for detailed discussion). For Zr-NU-1000-V, multiple
single-atom vanadium species were observed on the bridging
position (V1) and the monodentate positions (V2, V3) of the Zr6-
node (Figures S11d–f). In addition to vanadium, acac ligands
crystallographically were also observed coordinated on the MOF
node of Zr-NU-1000-V (Figure S11c). Their crystallographically
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estimated loadings were 0.56 (V1), 0.40 (V2), and 0.12(V3) va-
those for V1 and V3 became negligible. Thus, the catalytic mate-
rial evolves from one featuring multiple single-V-atom sites, to
one characterized by a single site.
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nadium per Zr -node, consistent with the loadings observed by
6
ICP-OES, i.e., a single atom per node, but each occupying one of
three possible sites.
Variable-temperature IR and Raman measurements clearly in-
dicated reversible changes in structure of the anchored vanadium
species, ascribable to dehydration and rehydration (Figures S14–
17, see Supporting Information for details). The combined results
indicated that a dehydrated form of V2 of Hf-MOF-808-V is the
active site for catalytic oxidation of the alcohol by Hf-MOF-808-
V. Consistent with this picture, catalyst heating under vacuum,
followed by transfer to the reaction solution under conditions that
preclude re-hydration of Hf-MOF-808-V, boosted the initial TOF
to 6.1 ± 0.1 h (open red circles in Figure 4b; TONs are 12.4 at
4h reaction time). For Zr-NU-1000-V, no clear dependence of
TOF on heating time was observed, suggesting that either the
catalytic performances of bridging (V1) and monodentate (V2 and
V3) vanadium sites are similar, or that this catalyst, in contrast to
Hf-MOF-808-V, does not evolve with time. In addition, XPS
spectra after heating and vacuum, the V2p3/2 peak of Zr-NU-1000
did not show any shift, while that of Hf-MOF-808-V showed a
slight shift of 0.2 eV toward higher binding energy (Figure S18).
Given the structural information, the V-SIM MOFs were exam-
ined as catalysts for a model reaction, the oxidation of 4-
o
methoxybenzyl alcohol (1) by O in toluene as solvent at 105 C
2
45
(
Figure 4a). The reactions were performed with suspensions of
the V-SIM MOFs (7.5 mol% of V to the substrate 1) (Figure 4,
S12; see Supporting Information for details). As shown in the
reaction time profiles monitored by GC-FID, the V-SIM MOFs
catalyzed the oxidation (Figure 4b for Hf-MOF-808-V and S12a
for Zr-NU-1000-V), while the bare MOFs displayed negligible
activity. Additionally, high selectivity (>99%) was confirmed by
GC-MS towards the formation of 4-methoxybenzaldehyde (2) was
observed without any generation of the over-oxidized product, 4-
methoxybenzoic acid. At 4h reaction time, their turnover numbers
(TONs) are estimated to be 11.3 (Hf-MOF-808-V) and 8.2 (Zr-
NU-1000-V). Turnover frequencies (TOFs) at low conversion
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(<12% Fig. 4b) were essentially identical:1.9 ± 0.1 h for Hf-
–
1
MOF-808-V and 2.1 ± 0.1 h for Zr-NU-1000-V. Interestingly,
with Hf-MOF-808-V as catalyst the rate of reaction increased
over the first hour, with the TOF averaging 3.8 ± 0.1 h between
–1
the 1st and 2nd hours. (See Figures 4b and S12a.)
Figure 4. (a) Catalytic reaction scheme of 1 to form 2 (b) Reac-
tion time profiles for the catalytic oxidation of 1 to 2. Inset is the
structure of the putative active site of the Hf-MOF-808-V catalyst.
The substrate scope was further expanded (Table S3, entries 3–
8). In all cases, Hf-MOF-808-V showed higher catalytic activities
than Zr-NU-1000-V with the selectivity towards the aldehyde
product. The origins of this distinct difference in catalytic activi-
ties between Hf-MOF-808-V and Zr-NU-1000-V could be as-
cribed to their difference in the binding motif of the vanadium
Figure 3. Crystal structures of Hf-MOF-808-V collected at 100
K. (a) 3D structure (b) the magnified figure of the node where V1
(blue), V2 (red-orange), and V3(green) sites are represented in
different colours. (c–e) the crystal structures of the node and
structure representations for clarity. In (c)–(e), the side views of
the MOF node are shown, where V1, V2, V3 sites are extracted.
oxide spiecies on the node (“chelating” on Hf-MOF-808 and
2, 46
“bridging and monodantate” on Zr-NU-1000).
To assess the catalysts’ stability, recollected Hf-MOF-808-V
and Zr-NU-1000-V were washed several times with fresh toluene
to remove residual substrates and products, and the oxidation
reaction was performed with the recycled material. No significant
decreases in product conversion or aldehyde selectivity were ob-
served (Figure S19). Importantly, ICP-OES measurements of the
reaction mixture filtrates revealed no detectable vanadium, imply-
ing that no catalyst leaching. Additionally, ICP-OES assessments
To elucidate the origin of the increase in TOF, we determined
the single-crystal X-ray structure of Hf-MOF-808-V after heating
the material overnight at 105 öC (Figure S13, Table S2). As seen
in F –F electron density maps after the heat treatment (Figure
o
c
S13b), the residual densities corresponding to V2 intensify, while
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following use as catalysts matched those the pristine compounds.
Additionally, hot filtration tests showed no leaching which further
support the heterogeneous nature of the catalysts (Figure. S20).
Furthermore, multiple post-catalysis characterization studies indi-
cated the structure and composition of Hf-MOF-808-V and Zr-
NU-1000-V were retained during and after catalysis (Figures
S21–22).
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temporal evolution of the Hf -supported, single-atom catalyst
6
from multi-site to single-site form, is manifested in kinetic
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Hupp, J. T. Chem. Soc. Rev. 2009, 38 (5), 1450–1459.
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The photographs of single crystals, crystallographic data, Diffuse-
reflectance UV and IR, Raman, XPS spectra. This material is
available free of charge via the Internet at http://pubs.acs.org.
(
25) Islamoglu, T.; Goswami, S.; Li, Z.; Howarth, A. J.; Farha, O. K.;
Hupp, J. T. Acc. Chem. Res. 2017, 50, 805–813.
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Marco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.; Stair, P. C.;
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e-mail: o-farha@northwestern.edu.
Ø¥•≥
*
(28) Li, Z.; Peters, A. W.; Bernales, V.; Ortuño, M. A.; Schweitzer, N.
.
M.; DeStefano, M. R.; Gallington, L. C.; Platero-Prats, A. E.; Chap-
man, K. W.; Cramer, C. J.; Gagliardi, L.; Hupp, J. T.; Farha, O. K. ACS
Cent. Sci. 2017, 3,31−38.
(29) Li, Z.; Peters, A. W.; Platero-Prats, A. E.; Liu, J.; Kung, C. W.;
Noh, H.; DeStefano, M. R.; Schweitzer, N. M.; Chapman, K. W.; Hupp, J.
T.; Farha, O. K. J. Am. Chem. Soc. 2017, 139 (42), 15251–15258.
The authors declare no competing financial interests.
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(
30) Peng, Y.; Huang, H.; Zhang, Y.; Kang, C.; Chen, S.; Song, L.; Liu,
D.; Zhong, C. Nat. Commun. 2018, 9, 187.
31) Ji, P.; Manna, K.; Lin, Z.; Feng, X.; Urban, A.; Song, Y.; Lin, W.
J. Am. Chem. Soc. 2017, 139, 7004-7011
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This work was supported as part of the Inorganometallic Catalyst
Design Center, an EFRC funded by the DOE, Office of Science,
Basic Energy Sciences (DE-SC0012702). This work made use of
the J.B. Cohen X-ray Diffraction Facility supported by the
MRSEC program of the National Science Foundation (DMR-
(
(
J.; Liang, J.; Zhang, Z.; Zhang, T.; Long, L.; Sun, J.; Lin, W. Angew.
Chemie - Int. Ed. 2016, 55 (16), 4962–4966.
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C.; Lin, W. Nat. Commun. 2016, 7, 12610.
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W. Chapman, J. M. Notestein, J. T. Hupp, O. K. Farha, Inorg. Chem.
1
121262) at the Materials Research Center of Northwestern
University. This work made use of Keck-II facilities of the
NUANCE Center at Northwestern University, which has received
support from the Soft and Hybrid Nanotechnology Experimental
(
(
SHyNE) Resource (NSF NNCI-1542205); the MRSEC program
NSF DMR-1121262) at the Materials Research Center; the
2
016, 55, 11954-11961
35) Feng, D.; Wang, K.; Su, J.; Liu, T. F.; Park, J.; Wei, Z.; Bosch,
(
International Institute for Nanotechnology (IIN); the Keck
Foundation; and the State of Illinois, through the IIN. We thank
Prof. Justin Notestein for access to the diffuse reflectance instru-
ment.
M.; Yakovenko, A.; Zou, X.; Zhou, H. C. Angew. Chemie - Int. Ed. 2015,
54 (1), 149–154.
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W. J. Am. Chem. Soc. 2016, 138, 12234–12242.
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38) Yuan, S.; Qin, J.-S.; Li, J.; Huang, L.; Feng, L.; Fang, Y.; Lollar,
(44) NIST X-ray Photoelectron Spectroscopy Database, Version 4.1
(National Institute of Standards and Technology, Gaithersburg, 2012);
http://srdata.nist.gov/xps/.
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P. C.; Sauer, J.; Freund, H. J. J. Catal. 2004, 226 (1), 88–100.
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needs to be provided and for the size requirements of the artwork.
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Figure 1. Structures of pristine (a) HfꢀMOFꢀ808 and (b) ZrꢀNUꢀ1000 with the corresponding structures of
their inorganic nodes and organic linkers. HfꢀMOFꢀ808 ([Hf
benzeneꢀ1,3,5ꢀtricarboxylylic acid and ZrꢀNUꢀ1000 ([Zr (ꢁ
1,3,6,8ꢀ(pꢀbenzoicꢀacid)pyrene).
6
(ꢁ
ꢀO)
3
ꢀO)
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(ꢁ
ꢀOH)
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(OH)
(H
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(H
O)
2
O)
(TBAPy)
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(BTC)
2
]∞; H3BTC =
6
3
(ꢁ
4 3
4
(OH)
4
2
4
2
]∞; H4TBAPy
=
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Figure 2. Powder X-ray diffraction patterns (PXRD; rt) and N
2
isotherms (77 K). PXRD for (a) Hf-MOF-808
(
1
black), Hf-MOF-808-V (red), and Hf-MOF-808-after catalysis (rose) and (b) Zr-NU-1000 (black), Zr-NU-
000-V (blue), and Zr-NU-1000-after catalysis (light blue). N adsorption (filled symbol) and desorp-tion
2
isotherms (open symbol) of (c) Hf-MOF-808 (black circle), Hf-MOF-808-V (red square), and Hf-MOF-808-
after catalysis (rose triangle) (b) Zr-NU-1000 (black circle), Zr-NU-1000-V (blue square), and Zr-NU-1000-
after catalysis (light blue trian-gle). Vads = adsorbed amount.
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Figure 3. Crystal structures of Hf-MOF-808-V collected at 100 K. (a) 3D structure (b) the magnified figure of
the node where V1 (blue), V2 (red-orange), and V3(green) sites are represented in different colours. (c–e)
the crystal structures of the node and structure representations for clarity. In (c)–(e), the side views of the
MOF node are shown, where V1, V2, V3 sites are extracted
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Figure 4. (a) Catalytic reaction scheme of 1 to form 2 (b) Reac-tion time profiles for the catalytic oxidation
of 1 to 2. Inset is the structure of the putative active site of the Hf-MOF-808-V catalyst.
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