Article

Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX pubs.acs.org/IC

Solvent-Free Photoreduction of CO2 to CO Catalyzed by Fe-MOFs

with Superior Selectivity
Xiao-Yao Dao, Jin-Han Guo, Yuan-Ping Wei, Fan Guo, Yi Liu, and Wei-Yin Sun*
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical
Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures,
Nanjing University, Nanjing 210023, China
*
S Supporting Information

ABSTRACT: It is deemed as a desired approach to utilize

solar energy for the conversion of CO2 into valuable products,
and the majority of the MOFs-based photocatalytic reductions
of CO2 have focused on formic acid (HCOOH) production
Downloaded by UNIV OF MELBOURNE at 16:20:47:869 on June 11, 2019

with an organic solvent as the reaction medium. Herein, we

report a solvent-free reaction route for the photoreduction of
from https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00824.

CO2 catalyzed by Fe-MOFs, namely, NH2-MIL-53(Fe)

[(Fe(OH)(NH 2−BDC)]•G, NH2-MIL-88B(Fe) [Fe3O-
(H2O)3(NH2−BDC)3]Cl•G, and NH2-MIL-101(Fe) [Fe3O-
(H2O)3(NH2−BDC)3]Cl•G (NH2−BDC = 2-aminotereph-
thalic acid; G = guest and/or solvent molecules). Compared
with the orthodox reaction route, the present out-of-the-way photocatalytic reduction of CO2 with superior selectivity to CO
occurs at the gas−solid interface. The reaction procedure is environmentally friendly and provides a possibility to address the
CO2 emission problem. Importantly, NH2-MIL-101(Fe) shows the highest photocatalytic activity among these Fe-MOFs due to
its efficient charge separation and electron transfer.

■ INTRODUCTION
Carbon dioxide (CO2), a product of fuel combustion, is one of
the main greenhouse gases and is rapidly increasing in the
atmosphere, which may cause catastrophic consequences such
as ice melting at the north and south poles, rising sea level, and
increasing global temperature.1−4 Thus, CO2 capture and
conversion technologies are considered as the most potential
and effective strategies to deal with the problem.5−8 Among
the varied technologies, artificial photosynthesis is an up-and-
coming method to obtain solar-to-chemical energy conversion
with new chemical bonds formation.9−12 Importantly, the
photocatalytic reduction of CO2 can not only reduce the CO2
emission but also solve the energy problems. To date,
traditional photocatalysts, such as inorganic catalysts and
molecular complexes, have been developed for photocatalytic
reduction of CO2. However, these materials endure some
inevitable defects even though they have respective prepon-
derances. Although most of inorganic catalysts exhibit high
stability during the reaction, these materials are relatively inert
in chemical reactivity and photogenerated charge carriers.13 As
for the molecular complexes, the active sites can have high
activity; however, the catalysts are usually difficult to recollect
and recycle for reuse.14 Hence, it is essential to develop new
effective materials combining the advantages of both inorganic
and molecular complexes to overcome their drawbacks.
Metal−organic frameworks (MOFs) have been demonstra-
ted to be a promising class of hybrid materials constructed
from metal centers and polydentate organic linkers with
tunable functionality.15,16 Due to their inherently large surface
areas, controllable pores, and confined catalytic active sites,
MOFs materials possess unparalleled advantages as well as
application scope.17−20 Interestingly, photoredox catalysis has
shown great opportunities for CO2 transformation.12,21−23 In
2011 it was reported that for the photoreduction of CO2 in
MOF, the photoreduction of CO2 to CO was realized by
incorporating molecular catalyst ReI(CO)3(5,5′-dcbpy)Cl into
the framework of UiO-67 using acetonitrile (MeCN) as the
solvent and triethanolamine (TEOA) as the sacrificial agent.24
Subsequently, Li and co-workers presented the photocatalytic
reduction of CO2 to HCOO− under visible light irradiation by
using amino-functionalized MOFs, including NH2-MIL-
125(Ti), NH2−UiO-66(Zr), and Fe-based MOFs of amino-
functionalized NH2-MIL-53(Fe), NH2-MIL-88B(Fe), and
NH2-MIL-101(Fe).25−27 What is more, Jiang et al. employed
a mesoporous Zr-porphyrin MOF (PCN-222) for effective
integration of CO2 capture and CO2 reduction to HCOO−
under visible-light irradiation.28 Recently, Wang and co-
workers developed a Co-containing ZIF-9 and coupled it
with different materials such as Ru complex, CdS, and C3N4 for
reduction of CO2 into CO with organic solvent as the reaction
medium, and all of these photoreduction reactions give H2 as a
byproduct.29−31 In spite of these excellent works, the reaction
medium is organic solvent; furthermore, the photocatalytic
Received: March 21, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.inorgchem.9b00824

Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Scheme 1. Schematic Illustration for the Photocatalytic CO2 Reduction in Solvent-Free System at the CO2/Fe-MOF Interfacea

a
(a) CO2 steel cylinder, (b) mass flow controller, (c) vacuum pump, (d) circulating pump, (e) photoreactor, (f) heating plate, (g) automatic gas
sampler, (h) gas chromatograph, (i) pressure meter, and (j) light source.

Figure 1. SEM images and XRD patterns of NH2-MIL-53(Fe) (A, a), NH2-MIL-88B(Fe) (B, b), and NH2-MIL-101(Fe) (C, c).

CO2 reduction still remains at a relatively low efficiency, and
the explorations were mainly concentrated on the HCOOH
production. To improve the photocatalytic efficiency and
enhance the selectivity of the products, great effects have been
adopted, including the predesign of bridging ligand and
modification of photocatalysts. However, it is still a challenge
to update the reaction route of the photocatalysis, which is
significant and attractively promising for enhancing CO2
conversion.
Herein, we employ a solvent-free route to photoredox
catalytic CO2 conversion (Scheme 1). In this strategy, three
classical Fe-based MOFs of NH2-MIL-53(Fe) [(Fe(OH)-
(NH2−BDC)]•G, NH2-MIL-88B(Fe) [Fe3O(H2O)3(NH2−
BDC)3]Cl•G, and NH2-MIL-101(Fe) [Fe3O(H2O)3(NH2−
BDC)3]Cl•G (NH2−BDC = 2-aminoterephthalic acid; G =
B DOI: 10.1021/acs.inorgchem.9b00824
guest and/or solvent molecules) were employed as photo-
catalysts for photocatalytic reduction of CO2. Amino func-
tional group was introduced into the framework to improve
light absorption and enhance the affinity toward CO2. In this
reaction system, MOF was uniformly dispersed into a glass
fiber film with assistance of TEOA as a sacrificial electron
donor for the photocatalytic CO2 conversion. Simultaneously,
gas was circulated in the pipeline by a pump to increase the
touch area between the catalyst and reaction gas. Hence, the
solvent-free route generates a gas−solid interface at CO2 and
MOF. Compared with a conventional gas−liquid−solid
reaction route, the solvent-free, gas−solid interfacial route
has advantages, such as being environmentally friendly and
creating a large contact area, which benefits in situ CO2
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 2. XPS spectra of NH2-MIL-53(Fe) (a), NH2-MIL-88B(Fe) (b), and NH2-MIL-101(Fe) (c): survey (a), and Fe 2p (b) spectra.
adsorption as well as providing a possibility for addressing the
reduction of the CO2 emission problem.
■ EXPERIMENTAL SECTION
Syntheses of Fe-MOFs: NH2-MIL-53(Fe), NH2-MIL-88B(Fe),
and NH2-MIL-101(Fe). NH2-MIL-53(Fe), NH2-MIL-88B(Fe), and
NH2-MIL-101(Fe) were synthesized according to the literature with
some modifications.27,32 NH2-MIL-101(Fe) was prepared by reaction
of NH2−BDC (0.1 mmol) with FeCl3·6H2O (0.2 mmol) in DMF (10
mL) at 110 °C for 24 h. NH2-MIL-88B(Fe) was prepared similarly to
NH2-MIL-101(Fe) except for addition of methanol (2 mL) to DMF
(8 mL). As for NH2-MIL-53(Fe), NH2−BDC and FeCl3·6H2O (1:1,
0.5 mmol) were dissolved in deionized (DI) water (10 mL) and
stirred for 30 min, and then the mixture was transferred to a Teflon-
lined autoclave for the hydrothermal treatment at 150 °C for 24 h.
After being cooled to room temperature, the resultant precipitates
were separated by centrifugation and washed thoroughly with DMF
and ethanol. The obtained solids were dried in a vacuum oven at 80
°C for 12 h for further characterization and investigation.
■
RESULTS AND DISCUSSION
Characterization of Catalysts. Fe-MOFs of NH2-MIL-
53(Fe), NH2-MIL-88B(Fe), and NH2-MIL-101(Fe) were
synthesized through hydro-solvothermal reactions and charac-
terized by varied methods. The morphologies of these as-
synthesized Fe-MOFs crystals were observed via scanning
electron microscopy (SEM). As illustrated in Figure 1(A−C),
NH2-MIL-53(Fe) exhibits favorable dispersibility but irregular
shapes with micronano sizes and NH2-MIL-88B(Fe) presents a
spindle-shaped morphology with an average size of 1 μm in
length and 400 nm in diameter, while NH2-MIL-101(Fe)
embodies uniform feature and representative octahedral
morphology with an average edge length of around 1 μm.
The crystalline structures of these as-prepared products were
confirmed by powder X-ray diffraction (PXRD). The PXRD
patterns of these Fe-based MOFs are shown in Figure 1(a−c),
and the as-obtained samples display well-defined diffraction
peaks that matched well with the simulated ones,32,33
manifesting the pure phase of the synthesized Fe-MOFs.
Furthermore, scanning electron microscopy analysis associated
with energy dispersive X-ray spectroscopy (EDX) indicates the
existence of Fe, C, O, and N in Fe-MOFs (Figure S1). To
further ensure the chemical composition and demonstrate the
presence of amino functional groups in the Fe-MOFs, Fourier
C DOI: 10.1021/acs.inorgchem.9b00824
Article
transform infrared (FT-IR) spectra were recorded (Figure S2).
Characteristic bands of NH2−BDC at 3510 and 3390 cm−1
were assigned to the asymmetric and symmetric stretching
vibrations of the N−H bond, and blue-shifts were observed for
the characteristic peaks of the amino group in the Fe-MOFs. In
addition, the peaks around 1251 cm−1 correspond to the C−N
stretching vibrations.34 Furthermore, shifts were also found for
the asymmetric and symmetric stretching vibration bands of
the coordinated carboxylate groups in Fe-MOFs compared
with the ones in NH2−BDC.35 These results prove that the
expected amino-functionalized Fe-MOFs have been success-
fully achieved. In addition to the EDX analysis, X-ray
photoelectron spectroscopy (XPS) was further employed to
examine the composition of the Fe-based MOFs (Figure 2a). It
can be seen that the results of XPS match well with those of
EDX. The high resolution spectra of Fe 2p (Figure 2b) show
two distinct peaks corresponding to the Fe 2p1/2 and Fe
2p3/2,36−38 and the separation of 13.7 eV between them
ensures the presence of Fe(III).
In order to elucidate the semiconductor behavior of Fe-
MOFs, the optical response of NH2-MIL-53(Fe), NH2-MIL-
88B(Fe), and NH2-MIL-101(Fe) was examined by UV−vis
diffuse-reflectance spectroscopy (DRS). As shown in Figure 3,
all samples have absorption in the visible region suggesting the
feasibility of photocatalytic ability. Mott−Schottky measure-
ments were further conducted. As displayed in Figure S3, the
positive slopes of the samples imply that these MOFs possess
an n-type semiconductor character.39 The flat-band potentials
of NH2-MIL-53(Fe), NH2-MIL-88B(Fe), and NH2-MIL-
101(Fe) are determined to be −1.1, −0.73, and −0.78 V vs
NHE, respectively (Figure S3), which are corresponding to the
conduction band (CB) for n-type semiconductors. Given the
more negative CB potentials of these MOFs than the redox
potential of CO2 to CO (−0.53 V vs NHE), these Fe-MOFs
may have potential for the photocatalytic reduction of CO2.
Catalytic Performance. The photoreduction of CO2
catalyzed by Fe-MOFs was investigated in a solvent-free
reaction system with dispersed catalyst in filter film by
employing TEOA as a sacrificial electron donor. Figure 4a
and 4b show the yield of photoreduction of CO2 within 5 h
under visible light irradiation (400−780 nm). The nonlinear
CO production curves in Figure 4a are attributed to the high
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
Figure 3. Diffuse-reflectance UV/vis spectra of NH2-MIL-53(Fe),
NH2-MIL-88B(Fe), and NH2-MIL-101(Fe).
boiling point of TEOA, resulting in little CO generation at the
initial stage due to the slow volatilization of TEOA as observed
in the reported gas−solid photocatalytic reaction system.40,41 It
is noteworthy that no H2 and CH4 evolution was detected
during the photocatalytic reaction (Figure S4). In addition, no
liquid product such as HCOOH was observed as ensured by
1
H NMR spectral measurements (Figure S5), which is ascribed
to the solvent-free reaction system.40−44 The results indicate
that all the Fe-MOFs possess a superior selectivity for
conversion of CO2 to CO. Under the uniform reaction
conditions, NH2-MIL-101(Fe) shows the best catalytic
performance for photocatalytic reduction of CO2 to CO
among the three Fe-MOFs, with a CO formation rate of 87.6
μmol g−1, which is about 5.6 times higher than that of NH2-
MIL-53(Fe) (15.7 μmol g−1). To understand the behavior of
photocatalytic reaction, a range of control experiments were
carried out (Table S1). In the absence of catalyst, light, CO2,
or TEOA, the target product is undetectable. Obviously, all of
these in one can make the photocatalysis effective. Stability is
one of the main factor in evaluation the performance of a
photocatalyst. As shown in Figure 5a, NH2-MIL-101(Fe) was
consecutively utilized as the deoxygenative CO2 conversion
catalyst for four cycles. After multiple cycles, no overt
Figure 4. Photocatalytic CO production (a) and photocatalytic CO production rates (b) of NH2-MIL-53(Fe), NH2-MIL-88B(Fe), and NH2-MIL-
101(Fe).
D DOI: 10.1021/acs.inorgchem.9b00824
Article
inhibition activity was expressed in the replicated tests,
implying that the catalyst is stable during the photocatalytic
reactions. A slight decrease in photocatalytic activity may be
partly caused by loss of photocatalyst during each evacuation.
Subsequently, the used catalysis was collected by centrifugation
and filtration, and the PXRD patterns of the fresh and reused
NH2-MIL-101(Fe) samples match well (Figure 5b), further
emphasizing the considerable durability of the photocatalyst.
The employed Fe-MOFs consist of Fe(III) and NH2−BDC
linkers but different framework structures (Figure S6).45 NH2-
MIL-53(Fe) contains μ2−OH and corner-sharing Fe(III)
octahedra without weak coordinated water molecules, and
there are μ3-O-bridged Fe3O clusters in both NH2-MIL-
88B(Fe) and NH2-MIL-101(Fe) with terminal coordinated
H2O molecules, which can be removed upon activation to
generate coordination unsaturated metal sites that can act as
catalytic active sites.46−50 In addition, the results of CO2
adsorption of Fe-MOFs show that the CO2 uptakes are 8.6,
9.2, and 61.6 cm3/g for NH2-MIL-53(Fe), NH2-MIL-88B(Fe),
and NH2-MIL-101(Fe), respectively (Figure S7). It is
noteworthy that NH2-MIL-101(Fe) and NH2-MIL-88B(Fe)
exhibit better photocatalytic capability than NH2-MIL-53(Fe),
even though NH2-MIL-88B(Fe) has poor CO2 adsorption. It
implies that the coordination unsaturated metal sites in NH2-
MIL-101(Fe) and NH2-MIL-88B(Fe) are dominant in
determining the catalytic activity.
The μ−O-Fe clusters in the amino-functionalized Fe-MOFs
can be directly excited by visible light,51,52 and the semi-
conductor behaviors of the Fe-MOFs have been identified by
UV−vis DRS and Mott−Schottky measurements (vide ante).
Thus, the band gap can be estimated by intercept of the
tangents of (Ahυ)2 vs photon energy, where A is a constant and
hυ is the incident photon energy (Figure 6a).40 The band gap
values of the Fe-MOFs are determined to be about 1.98, 1.72,
and 1.77 eV for NH2-MIL-53(Fe), NH2-MIL-88B(Fe), and
NH2-MIL-101(Fe), respectively. It can be seen that NH2-MIL-
88B(Fe) and NH2-MIL-101(Fe) with similar metal clusters
have a close band gap as well as the flat-band potentials (Figure
S3). To further understand the photocatalytic reactions,
photoluminescence (PL) spectra for NH2-MIL-53(Fe), NH2-
MIL-88B(Fe), and NH2-MIL-101(Fe) were measured upon
excitation at 350 nm (Figure 6b). It is notable that NH2−BDC
ligand shows a robust emission at 485 nm,52,53 while the Fe-
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article

Figure 5. (a) Recycling performance and (b) XRD patterns of NH2-MIL-101(Fe) before and after photocatalysis.

Figure 6. (a) Plots of (Ahv)2 vs photon energy, (b) PL emission spectra (λex= 350 nm), (c) photocurrent responses, and (d) EIS Nyquist plots for
NH2-MIL-53(Fe), NH2-MIL-88B(Fe) and NH2-MIL-101(Fe).

MOFs display remarkably decreased fluorescence. The evident
luminescence quenching implies the effect of ligand-to-metal
charge transfer (LMCT) upon the incorporation of the organic
groups into the framework of Fe-MOFs. To further validate
the photoresponsive properties, the photocurrent measure-
ments were also employed to reflect the efficiency of
photogenerated charge separation, in which a higher photo-
current often leads to a better photocatalytic property.54 The I-
E DOI: 10.1021/acs.inorgchem.9b00824
t curves (Figure 6c) with visible-light illumination show that
NH2-MIL-101(Fe) possesses the highest photocurrent among
the Fe-MOFs, suggesting that NH2-MIL-101(Fe) may have
higher active catalytic capacity. In addition, electrochemical
impedance spectroscopy (EIS) can be used to characterize the
carrier mobility of these samples (Figure 6d).55 Obviously, the
results demonstrate that NH2-MIL-101(Fe) exhibits the
smallest resistance, reflecting that more efficient charge transfer
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry
occurred. The conductivities of the samples were calculated
from the Nyquist plots by using equation, σ = L/(S × Ret),
where L (cm) and S (cm2) are the thickness and area of the
sample, respectively, and the electron-transfer resistance (Ret)
is equivalent to the diameter of semicircle in the Nyquist
diagram.56 The results exhibit that NH2-MIL-101(Fe) has a
higher conductivity of 4.1 × 10−6 S cm−1 than those of NH2-
MIL-53(Fe) and NH2-MIL-88B(Fe) with conductivities of 1.1
× 10−6 and 2.2 × 10−6 S cm−1, respectively. The difference of
the conductivities can be explained by their distinct framework
structures. Closely arranged four μ3-O-bridged Fe3O clusters as
a tetrahedron in NH2-MIL-101(Fe) (Figure S6c) is more
efficient for electron mobility than the triangular bipyramidal
arrangement of five Fe3O clusters in NH2-MIL-88B(Fe)
(Figure S6b), while NH2-MIL-53(Fe) with μ2−OH bridges
(Figure S6a) has poorer conductivity than NH2-MIL-88B(Fe)
and NH2-MIL-101(Fe) with μ3-O-bridged Fe3O clusters. To
sum up, NH2-MIL-101(Fe) shows brilliant photocatalytic
activity, which may be ascribed to the unique structure,
matched band gap, efficiently charge separation, as well as
electron transfer.
■
CONCLUSIONS
In summary, we employed a solvent-free route to photoredox
catalytic CO2 conversion, which is environmentally benign.
Furthermore, the solvent-free route can generate a gas−solid
interfacial reaction that can increase the touch probability
between the catalyst and the reaction gas. Thus, three classical
Fe-based MOFs of NH2-MIL-53(Fe), NH2-MIL-88B(Fe), and
NH2-MIL-101(Fe) with amino-functionalized organic linkers
were adopted as catalysts for the photocatalytic reduction of
CO2, and the results demonstrate that they exhibit photo-
catalytic activity with superior selectivity for conversion of CO2
to CO. The distinct photocatalytic activities of the Fe-MOFs
catalysts were discussed. NH2-MIL-101(Fe) performs with the
highest photocatalytic activity, which may be ascribed to the
unique structure with unsaturated coordination metal sites as
well as effective electron transfer. It is anticipated that the
solvent-free route can be applied to a variety of catalytic
reactions, particularly for gas-involved reactions.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b00824.
Additional characterization data and photocatalytic
results (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: sunwy@nju.edu.cn. Fax: +86 25 89682309.
ORCID
Wei-Yin Sun: 0000-0001-8966-9728
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We gratefully acknowledge the National Basic Research
Program of China (2017YFA0303504) and the National
Natural Science Foundation of China (21573106) for financial
F DOI: 10.1021/acs.inorgchem.9b00824
Article
support of this work. This work was also supported by a
project funded by the Priority Academic Program Develop-
ment of Jiangsu Higher Education Institutions.
■
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