Dense Alkyne Arrays of a Zr(IV) Metal-Organic Framework Absorb Co(CO) for Functionalization

Article abstract of DOI:10.1021/acs.inorgchem.0c00328

Finely dispersed Co(0) and CoO species were efficiently loaded into a stable metal-organic framework to impart catalytic activities to the porous solid. The metalation of the MOF host is facilitated by the dense arrays of accessible alkyne units that boost the alkyne-Co(CO) interaction. The tetrakis(4-carboxylphenylethynyl)pyrene linker, with eight symmetrically backfolded alkyne side arms, features strong fluorescence and a dendritic Sierpinski shape. The resultant Zr(IV)-MOF features NU-901 topology (scu net, with rhombus channels) and breathing properties (e.g., the contracted (porous) phase reverts to the as-made phase upon contact with DMF (dimethylformamide)). The inserted Co(CO) guests quickly react with air to form atomically dispersed CoO species (nondiffracting), and subsequent thermal treatment at 600 °C of the CoO-loaded solid generates an electrocatalyst for the oxygen evolution reaction (OER).

Full text of DOI:10.1021/acs.inorgchem.0c00328

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Article
Dense Alkyne Arrays of a Zr(IV) Metal−Organic Framework Absorb
Co (CO) for Functionalization
2
8
Yingxue Diao, Jieying Hu, Shengxian Cheng, Feixiang Ma, Mu-Qing Li, Xiangzi Hu, Yang Yang Li,
Jun He,* and Zhengtao Xu*
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sı Supporting Information
ABSTRACT: Finely dispersed Co(0) and CoO species were
efficiently loaded into a stable metal−organic framework to impart
catalytic activities to the porous solid. The metalation of the MOF
host is facilitated by the dense arrays of accessible alkyne units that
boost the alkyne-Co (CO) interaction. The tetrakis(4-carboxyl-
2
8
phenylethynyl)pyrene linker, with eight symmetrically backfolded
alkyne side arms, features strong fluorescence and a dendritic
Sierpinski shape. The resultant Zr(IV)-MOF features NU-901
topology (scu net, with rhombus channels) and breathing
properties (e.g., the contracted (porous) phase reverts to the as-made phase upon contact with DMF (dimethylformamide)).
The inserted Co (CO) guests quickly react with air to form atomically dispersed CoO species (nondiffracting), and subsequent
2
8
thermal treatment at 600 °C of the CoO-loaded solid generates an electrocatalyst for the oxygen evolution reaction (OER).
he metalation of metal−organic framework (MOF)
dense and symmetrical array of alkyne functions (H L1; Figure
4
T
materials closely impacts the topical areas of heavy
1A). The geometric design of H L1 follows our long-standing
4
1
−6
7−17
18−20
38−43
metal removal,
heterogeneous catalysis, 2 sensors,
interest
in the self-similar feature of Sierpinski molecules,
1−26
44−50
and fundamental studies of crystal structures
because of
with their distinct, symmetrically backfolded side arms
contrasting the starburst shape of traditional dendrimers. The
1,2,3-positions of the contiguous alkyne units in this Sierpinski
molecule facilitate metal uptake, not only because of their
dense, chelation-prone array but also because of the spatial
accessibility of the flanking alkyne units. For these are freer
than the (middle) backbone alkyne unit, i.e., freer to move
about, and also to accommodate the geometric changes
entailed in bonding to metal centers. To solubilize the large,
pyrene-based conjugate backbone, tert-butyl groups are
the versatile functions that can arise from the metal guests. To
facilitate metal uptake, MOF hosts are often equipped with
secondary donor groups, in addition to the primary groups for
network construction. To prevent the secondary groups from
competing against the primary linking units (and disrupting
the formation of the host net), the difference in chemical
9
hardness is important. An early work utilized a pyridinyl (soft)
linker equipped with phenol (hard) groups: the pyridinyls and
Cd(II) ions first form the open net; the hydroxyl units then
bind Ti(IV) guests for catalysis. More distinct hard-and-soft
design has also been extensively implemented in the form of
appended to the side arms. The H L1 molecule thus designed
4
and synthesized reacts with Zr(IV) ions to form a porous 3D
net that effectively takes up cobalt guests, which, even after
carbonizing at 600 °C, remain finely dispersed and afford
distinct catalytic activity for oxygen evolution reactions.
The orange, polycrystalline powder of ZrL1 was solvother-
mally prepared from H L1, ZrOCl ·8H O, N,N-diethylforma-
4
,22,27−29
the carboxyl−sulfur combination.
In this context, the alkyne function presents a curious case.
On the one hand, alkyne units, as chemically soft groups, are
known to form π-complexes (e.g., via η -alkyne bonds) with
2
30−34
soft metal centers such as Ag(I) and Au(I);
alkyne groups
4
2
2
are also reacted with Co (CO) , Fe (CO) , and other metal
2
8
3
12
mide (DEF, the solvent), and benzoic acid (the modulator).
Powder X-ray diffraction (PXRD) reveals an orthorhombic
symmetry (a = 42.10, b = 24.02, and c = 19.19 Å; pattern b,
carbonyls to form complexes in solution chemistry inves-
3
5,36
tigations.
On the other hand, alkyne groups have been
largely left out as secondary donors for metal uptake in the
design of MOF materials. Such scarcity is surprising, as alkyne
groups generally withstand the solvothermal conditions of
MOF synthesis: cases are known where the alkyne units are
built into side chains branching off the MOF backbone and are
Received: February 1, 2020
37
therefore poised to act as secondary donors.
To exploit alkyne−metal interactions for functionalizing
porous materials, here we report a designer linker featuring a
©
XXXX American Chemical Society
https://dx.doi.org/10.1021/acs.inorgchem.0c00328
A
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Article
1−55
5
structures reported by Farha, Stock, and Zhou,
which
feature the scu topology based on tetratopic carboxyl linkers
and eight-connected Zr O clusters (with four equatorial edges
6
8
−
of the Zr octahedron sealed off by H O/OH species; Figure
6
2
1
B). The identically oriented Zr O octahedra are arranged in
6 8
a centered rectangular lattice to generate rhombus-shaped
channels (Figure 1). The side-arm alkyne units are likely
disordered in the channel region, but their well-defined vicinal
positions within the linker favor intramolecular pathways for
reactions among the alkyne units (e.g., at 600 °C; see below).
The scu net of the orthorhombic ZrL1, with its rhombus
channels, compares instructively with the hexagonal NU-1000
and cubic NU-1100, with both built on tetratopic carboxyl
linkers and Zr O nodes (Figures S5 and S6). The NU-1000
6
8
structure also features a (4,8)-connected net but consists of
trigonal and hexagonal channels (i.e., the csq net). Compared
with the rhombus channel of NU-901, the trigonal channel of
NU-1000 is only half its size while the hexagonal ones are 3
times as large in cross-section. The targeted formation of the
54,56,57
scu and csq nets in Zr-based MOFs has been reported.
The adoption of the scu net by ZrL1 is likely driven by the
steric effect from the rigid and bulky side arms of L1. For
example, the smaller trigonal channel of the NU-1000-type
structure (the csq net) may not accommodate the side arm
volumes of L1. On the other hand, the NU-1100 structure
features a (4,12)-connected ftw net, with the Zr O clusters
6
8
2
,58
being 12-connected in the ideal form.
The NU-1100
structures can exhibit twinning and disorder regarding linker
59
orientations and are generally solved in highly symmetric,
cubic space groups, contrasting the orthorhombic ZrL1
(
Figure S8).
Elemental analysis found C (66.88%), H (4.88%), and N
0.40%) for activated ZrL1, which fits the formula
(
Zr O (OH) (H O) (C H O )3.0(L1)1.25 [calculated C
6
4
8
2
4
7
5
2
(
66.63%), H (4.85%)]. The benzoate (C H O )/L1 ratio
7 5 2
1
Figure 1. (A) Molecule H L1 (featuring eight secondary alkyne
was also verified by the H NMR of the activated sample
extracted into acetone-d (using K PO , DCl/D O; Figure S4).
Benzoate ions bonded to the residual open sites of the Zr
4
groups). (B−D) Structure of ZrL1: the eight-connected Zr cluster
6
6
3
4
2
(
(
panel B) and views of the network along the b (panel C) and c axes
panel D). H atoms were omitted for clarity. Red spheres, O; gray, C;
6
51
clusters were also observed in the NU-901 prototype. The
:1.25 cluster/linker ratio indicates that out of the eight
blue, Zr-based polyhedron.
1
connecting sites of the Zr cluster in the scu net of ZrL1, only
6
Figure 2; details of the refinement are included in the SI). The
PXRD of as-made ZrL1 can be modeled after the NU-901-type
five were taken by the L1 linker (with the other three being
−
sealed off by the benzoate or H O/OH species). The
2
significant linker deficiency (i.e., 3/8 = 37.5%) of ZrL1 can be
attributed to the steric repulsion from the bulky side arms of
L1.
The thermogravimetric analysis (TGA; Figure S14a) of a
powder of H L1 suggests that the departure of the t-butyl and
4
carboxyl units (accounting for 30.8% of weight loss) lasts up to
5
00 °C, with a weight fraction of 51.4% remaining at 900 °C.
Similarly, TGA of the activated ZrL1 sample (Figure S14b)
reveals a distinct step of weight loss (of ca. 33%) of up to 517
°
C, corresponding to the departure of the water, benzoate, t-
butyl, and carboxyl components, with the residue at 900 °C
(
40.7%) far exceeding the ZrO weight.
2
Both flexibility and resilience were observed for the ZrL1
framework. The PXRD of the activated ZrL1 (i.e., a guestless
sample obtained by solvent exchange with acetone and then
evacuation) exhibits broadened peaks shifted to higher angles
Figure 2. PXRD patterns (Cu Kα, λ = 1.5418 Å) for ZrL1: (a)
calculated from the crystal structure model following PCN-606
topology; (b) measured from an as-made sample, covered by a DMF
droplet during scanning; (c) from a fresh activated sample; (d) from
an activated sample after being stored in air for 40 days; and (e) from
(
pattern c, Figure 2), indicating lattice contraction and the
partial loss of long-range order. The contracted phase,
however, maintains significant gas uptake, exhibiting a typical
2
(d) moistened by DMF.
type-I isotherm with a Langmuir surface area of 486 m /g in
B
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CO sorption at 195 K (Figures 3 and S15). The gas sorption
2
behaviors reveal the ultramicroporosity of activated ZrL1,
Figure 4. IR spectra for samples of (a) activated ZrL1, (b) ZrL1-
Co (CO) , and (c) ZrL1-CoO.
2
6
ZrL1-CoO to be 1:1.49. With the above ZrL1 formula, a L1/
Co ratio of 1:7.2 can be deduced, corresponding to about half
Figure 3. CO (195 K) adsorption and desorption isotherms for an
activated ZrL1 sample (red graphs), ZrL1-CoO sample (blue graphs),
and ZrL1-CoO-600 sample (green graphs).
2
(
7.2/16 = 45%) of the eight alkyne side arms of each L1 linker
being engaged as the [Co (CO) (RCCR)] complex. The
2
6
efficient uptake of Co (CO) as enabled by the alkyne side
2
8
which allows the selective penetration by CO (and not by N )
arms is also highlighted by the poor Co (CO) uptake (e.g.,
2
2
2 8
because of its smaller kinetic diameter, quadruple moment, and
mostly limited to the external surfaces) of a MOF wherein the
60
72
stronger thermal motion at 195 K (relative to 77 K for N2).
alkyne units were built into the linker backbone instead.
Notably, activated ZrL1 is quite persistent (e.g., even after
exposure to the moist air of Hong Kong for 40 days, its
diffraction profile remains unchanged (Figure 2d)). The air
stability may be partially ascribed to the bulky hydrophobic
side arms that prevent water from eroding the metal node.
Interestingly, upon contact with the DMF solvent, the
contracted phase (i.e., activated ZrL1) reverts to the open
phase of the as-made sample, as revealed by PXRD (pattern e,
Figure 2; cf. pattern b). The swift recovery of the pristine phase
is likely associated with the linker deficiency (i.e., 37.5%),
Comparison with other related MOFs (e.g., the isoreticular
PCN-606 and NU-901 ) with regard to metalation and
catalysis, however, still warrants attention.
53
73
The ZrL1-CoO solid continues to feature a type-I isotherm
in CO sorption (195 K, Figures 3 and S16), with a smaller
2
2
−1
Langmuir surface (340 m g ) than for activated ZrL1 (486
2
−1
m g ), which is consistent with partial pore occupation by
the CoO guests. ZrL1-CoO also exhibits greater hysteresis
indicative of ultramicropore blocking by the CoO guests.
PXRD of ZrL1-Co (CO) and ZrL1-CoO indicates that the
2
6
leading to lower-connected Zr nodes (i.e., five-connected) and
host frameworks remain upstanding (Figure S13), although an
unusually strong background (likely due to the CoO
6
6
1
consequently more flexibility for framework dynamics.
Framework dynamics of Zr-MOF solids often arise from the
7
4
fluorescence ) largely obscures the diffraction signals.
Notably, no diffraction peaks from CoO or other phases
were observed, indicating the finely dispersed (and thus
nondiffracting) nature of the CoO species within the MOF
matrix; the fine distribution of CoO is also supported by SEM
and TEM images (Figures S19−S22) of the ground samples of
ZrL1-CoO, which reveal no large aggregated particles (e.g., of
CoO) aside from the MOF matrix. The diffuse reflectance
spectra (Figure S18) reveals the optical band gaps for the
ZrL1, ZrL1-Co (CO) , and ZrL1-CoO solids to be about 2.19,
6
1,62
21,39,63,64
supple topology,
linker flexibility,
and partial
6
5
hydrolysis of the carboxylate donors (e.g., switching from
the bidentate bridging mode to the monodentate or
uncoordinated mode). Further study is needed on how these
factors contribute to the dynamic, breathing properties of
ZrL1.
Unlike the strenuous (e.g., by vacuum deposition) grafting
66−68
of metal carbonyl guests into other MOF matrixes,
the
alkyne-functionalized ZrL1 solid (activated, orange-red) read-
2
6
ily binds Co (CO) from a THF solution to form the dark-
1.72, and 1.25 eV, respectively.
CoO is known to be a good electrocatalyst for the oxygen
evolution reaction (OER) when strongly coupled with various
2
8
brown ZrL1-Co (CO) solid. The characteristic, strong IR
2
6
−
1
peaks at 2089, 2054, and 2028 cm (Figure 4b) of the CO
stretches point to the known μ -alkyne dicobalt hexacarbonyl
carbon substrates including graphene and amorphous
2
69−71
75−77
complexes [Co (CO) (RCCR)].
Compared with the
carbon.
To enhance charge transport for electrocatalysis
2
6
yellow-fluorescing ZrL1 (emission peak at 585 nm for the
activated, contracted phase and 572 nm for the open phase;
Figure S10), ZrL1-Co (CO) is nonemissive.
applications, the ZrL1-CoO sample was heated to 600 °C for 3
h to carbonize the organic linkers (e.g., by cyclizing the alkyne
units). The resulting black sample, ZrL1-CoO-600, remains
2
6
2
−1
The ZrL1-Co (CO) solid (brown) can be heated in air
e.g., at 75 °C for 3 h) to remove the CO ligands (IR evidence;
porous (surface area, 352 m g ; Figures 3 and S17), and the
lack of distinct peaks in its PXRD pattern (Figure S23)
indicates an amorphous structure with the Co species
remaining highly dispersed (i.e., they do not aggregate into
crystalline particles in the thermal treatment). In a 0.1 M KOH
solution, the ZrL1-CoO-600 electrode gave a η10 of 544 mV
and a small TS of 80 mV/dec (Figure S24), which are
significantly enhanced over the control sample (i.e., without
2
6
(
Figure 4c). The resultant solid was denoted ZrL1-CoO
because XPS reveals the Co 2p peak at 779.7 eV with distinct
satellite features at ∼786 eV indicative of the CoO species
(Figure S11). Semiquantitative elemental analysis by EDX
measurements (Figure S12) also indicate substantial cobalt
content, with Zr/Co atomic ratios of 1:1.5 and 1:1.4 for ZrL1-
Co (CO) and ZrL1-CoO, respectively. Further elemental
2
Co components) of ZrL1-600 (η > 577 mV at 1.0 mV/cm , TS
2
6
analysis by ICP-OES quantifies the Zr/Co atomic ratio in
= 284 mV/dec). ZrL1-CoO-600 as an OER catalyst was thus
C
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found to compare well with some of the cobalt-enabled MOF
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AUTHOR INFORMATION
Corresponding Authors
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Jun He − School of Chemical Engineering and Light Industry,
Guangdong University of Technology, Guangzhou 510006,
Guangdong, P. R. China; orcid.org/0000-0001-7062-4001;
Phone: 86 138 2211 8686; Email: junhe@gdut.edu.cn
Zhengtao Xu − Department of Chemistry, City University of
Hong Kong, Kowloon, Hong Kong, P. R. China; orcid.org/
(7) Gui, B.; Yee, K.-K.; Wong, Y.-L.; Yiu, S.-M.; Zeller, M.; Wang,
C.; Xu, Z. Tackling poison and leach: catalysis by dangling thiol-
palladium functions within a porous metal-organic solid. Chem.
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T.; He, J.; Xu, Z. Room-temperature acetylene hydration by a Hg(II)-
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000-0002-7408-4951; Phone: 852 34424679;
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9) Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. A Homochiral Porous
Authors
Metal-Organic Framework for Highly Enantioselective Heteroge-
Yingxue Diao − Department of Materials Science and
Engineering and Department of Chemistry, City University of
Hong Kong, Kowloon, Hong Kong, P. R. China
neous Asymmetric Catalysis. J. Am. Chem. Soc. 2005, 127, 8940−
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(
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Jieying Hu − Department of Materials Science and Engineering,
City University of Hong Kong, Kowloon, Hong Kong, P. R.
China; School of Chemical Engineering and Light Industry,
Guangdong University of Technology, Guangzhou 510006,
Guangdong, P. R. China
Shengxian Cheng − Department of Chemistry, City University
of Hong Kong, Kowloon, Hong Kong, P. R. China
Feixiang Ma − Department of Mechanical Engineering, City
University of Hong Kong, Kowloon, Hong Kong, P. R. China;
orcid.org/0000-0002-2449-9139
Mu-Qing Li − Department of Chemistry, City University of
Hong Kong, Kowloon, Hong Kong, P. R. China
Xiangzi Hu − Department of Chemistry, City University of Hong
Kong, Kowloon, Hong Kong, P. R. China
Yang Yang Li − Department of Materials Science and
Engineering, City University of Hong Kong, Kowloon, Hong
Kong, P. R. China; orcid.org/0000-0003-4153-9558
Functionalized UiO-67-Type Porous Single Crystal: Filling in the
Synthetic Gap. Inorg. Chem. 2019, 58, 1462−1468.
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Z.; Lu, T.-B. Anchoring CoII Ions into a Thiol-Laced Metal-Organic
Framework for Efficient Visible-Light-Driven Conversion of CO2 into
CO. ChemSusChem 2019, 12, 2166−2170.
(12) Mon, M.; Rivero-Crespo, M. A.; Ferrando-Soria, J.; Vidal-
Moya, A.; Boronat, M.; Leyva-Perez, A.; Corma, A.; Hernandez-
Garrido, J. C.; Lopez-Haro, M.; Calvino, J. J.; Ragazzon, G.; Credi, A.;
Armentano, D.; Pardo, E. Synthesis of Densely Packaged, Ultrasmall
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Recovery and Catalysis in a Highly Flexible Methionine-Decorated
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(14) Baek, J.; Rungtaweevoranit, B.; Pei, X.; Park, M.; Fakra, S. C.;
Liu, Y.-S.; Matheu, R.; Alshmimri, S. A.; Alshehri, S.; Trickett, C. A.;
Somorjai, G. A.; Yaghi, O. M. Bioinspired Metal-Organic Framework
Catalysts for Selective Methane Oxidation to Methanol. J. Am. Chem.
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Complete contact information is available at:
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Notes
(15) Sun, C.; Skorupskii, G.; Dou, J.-H.; Wright, A. M.; Dinca, M.
The authors declare no competing financial interest.
Reversible Metalation and Catalysis with a Scorpionate-like Metallo-
ligand in a Metal-Organic Framework. J. Am. Chem. Soc. 2018, 140,
17394−17398.
ACKNOWLEDGMENTS
■
(16) Feng, X.; Song, Y.; Li, Z.; Kaufmann, M.; Pi, Y.; Chen, J.; Xu,
The work was supported by a GRF grant from the Research
Grants Council of HKSAR (CityU 11306018) and an SRG
grant from City University of Hong Kong (project 7004820).
Z.; Zhong, L.; Wang, C.; Lin, W. Metal-Organic Framework Stabilizes
a Low-Coordinate Iridium Complex for Catalytic Methane
Borylation. J. Am. Chem. Soc. 2019, 141, 11196−11203.
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