Nano Research

https://doi.org/10.1007/s12274-017-1943-2

Ni-doped ZnCo2O4 atomic layers to boost the selectivity

in solar-driven reduction of CO2
Katong Liu, Xiaodong Li, Liang Liang, Ju Wu, Xingchen Jiao, Jiaqi Xu, Yongfu Sun (), and Yi Xie ()

Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, University of Science and
Technology of China, Hefei 230026, China

Received: 31 October 2017 ABSTRACT

Revised: 20 November 2017
Accepted: 29 November 2017
© Tsinghua University Press
and Springer-Verlag GmbH
Germany, part of Springer
Nature 2017
KEYWORDS
atomic layers,
Ni-doped,
zinc cobaltite,
selectivity of CO2 reduction
Regulating the selectivity of CO2 photoreduction is particularly challenging.
Herein, we propose ideal models of atomic layers with/without element doping
to investigate the effect of doping engineering to tune the selectivity of CO2
photoreduction. Prototypical ZnCo2O4 atomic layers with/without Ni-doping
were first synthesized. Density functional theory calculations reveal that introducing
Ni atoms creates several new energy levels and increases the density-of-states at
the conduction band minimum. Synchrotron radiation photoemission spectroscopy
demonstrates that the band structures are suitable for CO2 photoreduction,
while the surface photovoltage spectra demonstrate that Ni doping increases the
carrier separation efficiency. In situ diffuse reflectance Fourier transform
infrared spectra disclose that the CO2− radical is the main intermediate, while
temperature-programed desorption curves reveal that the ZnCo2O4 atomic
layers with/without Ni doping favor the respective CO and CH4 desorption.
The Ni-doped ZnCo2O4 atomic layers exhibit a 3.5-time higher CO selectivity
than the ZnCo2O4 atomic layers. This work establishes a clear correlation between
elemental doping and selectivity regulation for CO2 photoreduction, opening
new possibilities for tailoring solar-driven photocatalytic behaviors.

1 Introduction the concentration of CO2 in the atmosphere while

Carbon dioxide emissions have substantially con-
tributed to climate change and global warming, which
have destroyed marine ecosystems and negatively
impacted human health [1–4]. Thus, it is urgent to
convert CO2 into an energy-bearing carbon form via a
sustainable approach i.e., one that does not increase
simultaneously solving the energy and environmental
problems. In this regard, solar-driven reduction of
CO2 is a valuable method that has used diverse
semiconductors, including ZnO, TiO2, BiWO4, and
ZnIn2S4, as photocatalysts [3, 5–10]. To date, no effective
methods have been developed to tune the product
selectivity of CO2 photoreduction; the various carbon-

Address correspondence to Yongfu Sun, yfsun@ustc.edu.cn; Yi Xie, yxie@ustc.edu.cn

2 Nano Res.
based products are difficult to separate and hence
impede practical applications. Doping engineering has
been widely utilized to tailor the electronic structure
of semiconductors [11–14] and hence change the
behavior of CO2 reduction. Significant progress has
been made in the field of water splitting using element
doping engineering; CO2 is catalytically reduced in
H2O, and the element doping engineering is applied
to suppress the generation of H2. For instance, Sato
and colleagues reported a nitrogen-doped Ta2O5
semiconductor as an effective photocatalyst for CO2
photoreduction; it had a higher selectivity toward
HCOOH evolution during the photocatalytic conversion
with a selectivity for HCOOH > 75% [15]. However,
atomic-level insights into the role of doping engineering
for tailoring product selectivity of CO2 photoreduction
are still not clear because of abundant micro- and
nanostructures on the surface of the reported
photocatalysts [16].
Herein, we begin by building an ideal model of
atomically thin, two-dimensional layers; the atomic
thickness enables an ultrahigh fraction of low-
coordinated surface atoms to serve as highly catalytically
active sites. We deliberately doped transition metal
atoms into the atomic layers to tailor their electronic
structure and regulate the product selectivity during
CO2 photoreduction to hydrocarbon fuels. Taking the
nontoxic semiconductor of cubic-ZnCo2O4 (its crystal
structure is shown in Fig. S1(a) in the Electronic
Supplementary Material (ESM)) as an example,
2.5-nm-thick ZnCo2O4 atomic layers with/without
Ni-doping were successfully fabricated. Density
functional theory (DFT) calculations disclosed that Ni
doping confined in the ZnCo2O4 atomic layers increased
the density of states (DOS) at the conduction band
minimum (CBM) with respect to the perfect ZnCo2O4
atomic layers, thus favoring the transport and
separation process of the photoexcited charge carrier.
Moreover, the band structures for the Ni-doped
ZnCo2O4 atomic layers and the ZnCo2O4 atomic
layers were measured using synchrotron radiation
photoemission spectroscopy (SRPES) and ultraviolet
visible absorption spectroscopy (UV–vis). The results
implied that both the ZnCo2O4 atomic layers with/
without Ni-doping possessed appropriate band
structures for CO2 reduction to CO and CH4. Surface
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photovoltage spectra (SPV) showed that the carrier
separation efficiency of the Ni-doped ZnCo2O4 atomic
layers was higher than that of the ZnCo2O4 atomic
layers. Hence, in situ diffuse reflectance infrared Fourier
transform spectroscopy (DRIFTS) was performed to
detect the intermediates during the reduction process,
where the CO2− radical was the main intermediate
during the CO2 photoreduction for both samples. In
addition, temperature-programed desorption (TPD)
measurements were used to investigate the product
desorption processes; CO preferentially desorbed from
the Ni-doped ZnCo2O4 atomic layers, and CH4 was
prone to desorb from the ZnCo2O4 atomic layers. The
real-time product monitoring system demonstrated
that the Ni-doped ZnCo2O4 atomic layers contained
higher proportions of CO in the products, suggesting
that the Ni-doped ZnCo2O4 atomic layers boosted
the selectivity for solar-driven reduction of CO2. Based
on the characterizations and photoreduction perfor-
mances, the as-synthesized ZnCo2O4 atomic layers
with Ni-doping successfully changed the selectivity
toward CO and CH4 evolution. This work provides
valuable insights into the role of element doping
engineering for selectively regulating CO2 photore-
duction, showing great promise for designing catalysts
with highly selective performances.
2 Experimental section
2.1 Synthesis of ZnCo2O4 atomic layers
In a typical procedure [17, 18], 300 mg of Co(NO3)2·6H2O,
150 mg of Zn(NO3)2·6H2O, and 100 mg of KNO3 were
added (in that order) to a 5-mL transparent solution
containing 100 mg of hexadecyl trimethyl ammonium
bromide (CTAB) dissolved in deionized water under
constant magnetic stirring. The as-prepared solution
was transferred to a 40-mL autoclave after 10 min of
stirring, and 30 mL of ethylene glycol was added to
the autoclave followed by another 10 min of stirring.
The system was maintained at 140 °C for 36 h. After
naturally cooling to room temperature, the obtained
precipitate was washed several times with water and
ethanol to obtain the amaranthine product, and then
dried using vacuum freeze-drying equipment for
further characterization.
Nano Res.
2.2 Synthesis of Ni-doped ZnCo2O4 atomic layers
In a typical procedure, 300 mg of Co(NO3)2·6H2O,
150 mg of Zn(NO3)2·6H2O, and 30 mg of Ni(NO3)2·6H2O
were added (in that order) to a 5-mL transparent
solution containing 100 mg of CTAB dissolved in
deionized water under constant magnetic stirring.
The as-prepared solution was transferred to a 40-mL
autoclave after 10 min of stirring, and 30 mL of
ethylene glycol was added to the autoclave followed
by another 10 min of stirring. The system was
maintained at 140 °C for 36 h. After naturally cooling
to room temperature, the obtained precipitate was
washed several times with water and ethanol to obtain
the violet product, which was then dried using vacuum
freeze-drying before further characterization.
2.3 Characterization
Field-emission scanning electron microscopy images
were obtained using an FEI Sirion-200 scanning electron
microscope. Transmission electron microscopy (TEM)
images and high-resolution TEM images were obtained
using a JEOL-2010 transmission electron microscope
with an acceleration voltage of 200 kV. X-ray diffraction
(XRD) patterns were recorded using a Philips X’Pert
Pro Super diffractometer with Cu Kα radiation (λ =
1.54178 Å). Atomic force microscopy (AFM) was
performed using a Veeco DI Nano-scope MultiMode V
system. X-ray photoelectron spectra (XPS) were
acquired on an ESCALAB MKII using Mg Kα (hν =
1,253.6 eV) as the excitation source. The binding
energies obtained in the XPS spectral analysis were
corrected for specimen charging by referencing C 1s
to 284.8 eV. Inductively coupled plasma atomic
emission spectrometry (ICP-AES) was performed
using an Atomscan Advantage (Thermo Jarrell Ash
Corporation (USA)). Room-temperature UV–vis diffuse
reflectance spectroscopy (DRS) and UV–vis absorption
spectra were recorded on a Perkin Elmer Lambda
950 UV-vis-near infrared spectrophotometer. Fourier
transform infrared (FT-IR) spectra were acquired on a
Nicolet FT-IR spectrometer (Thermo Fisher Scientific)
using KBr tablets, scanning from 4,000 to 400 cm−1 at
room temperature. In situ DRIFTS was performed
using the Nicolet FT-IR spectrometer with a gas
path system and a reaction chamber (HVC-DRM-5).
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A surface area and porosity analyzer (Micromeritics
ASAP 2020 M PLUS HD88) was used to measure the
Brunauer–Emmett–Teller (BET) isothermal adsorption,
Barrett–Joyner–Halenda pore-size distribution, and
CO2 isothermal adsorption. A chemisorption analyzer
(Micromeritics Autochem 2920) was used to conduct
CO and CH4 TPD measurements. The synchrotron
radiation photoemission spectroscopy spectra were
measured using a photon energy of 40 eV at the
Catalysis and Surface Science Endstation (BL11U) at
the University of Science and Technology of China. The
work function (Φ) was calculated from Φ = hν − Ecutoff
(hν is the incident photon energy of 40 eV), while a
bias of −5 V was used to gain the secondary electron
cutoff (Ecutoff).
2.4 Surface photovoltage measurements
SPV spectra were obtained using a lock-in amplifier.
The measurement systems include a lock-in amplifier
(SR830, Stanford Research Systems, Inc.), mono-
chromatic light, light chopper (SR540, Stanford Research
Systems, Inc.), and electroconductive chamber. Mono-
chromatic light was generated from a 500-W xenon
lamp (CHF-XM-500 W, global xenon lamp power)
using a monochromator (Omni-3007, No.16047, Zolix
Instruments Co.).
2.5 Photocatalytic CO2 reduction measurements
Photocatalytic CO2 reduction measurements were
conducted using a Lab SolarIII AG system (Perfectlight
Limited, Beijing). The temperature of the reaction cell
was maintained at 25 ± 0.2 °C by recirculating cooling
water during irradiation. In the typical CO2 photo-
catalytic reduction process, 20 mg of the as-synthesized
photocatalyst (ZnCo2O4 atomic layers with/without
Ni doping) was homogeneously dispersed onto a
quartz plate in the reaction cell containing 2 mL of
deionized water. A PLS-SXE300/300UV xenon lamp
(Trusttech Co., Ltd. Beijing) with a standard AM 1.5
filter provided light irradiation with an output light
density of about 100 mW·cm−2. The instrument was
initially vacuum-treated three times and then pumped
using high-purity CO2 (99.99%) to reach atmospheric
pressure. During light irradiation, the gas products
were qualitatively analyzed using a Techcomp GC7900
gas chromatograph (flame ionization detector, TDX-01
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4 Nano Res.

column) by identifying the chromatographic peaks. A 3 Results and discussion

sampling interval of 1 h was set using an automatic
sampler with a single cycle time of 21 h.
2.6 Density functional theory calculations
The first-principles calculations were performed using
the Vienna ab initio simulation package [19]. The
interaction between the ions and valence electrons
was described using projector augmented wave
potentials, and the exchange-correlation between
electrons was treated using the generalized gradient
approximation in the Perdew–Burke–Ernzerhof form
[20]. The screened hybrid functional proposed by
Heyd, Scuseria, and Ernzerhof [21] was adopted to
obtain accurate densities for the electronic states; the
plane wave cutoff energy was 480 eV, and a 3 × 3 × 1
forsheet k-point mesh was used. Ionic relaxations
were carried out under the conventional energy
(10−4 eV) and force (0.01 eV·Å−1) convergence criteria.
The single-layer along the [100] projection was used
to mimic the as-prepared 2.5-nm-thick atomic layers,
in which a 1.5-nm-thick vacuum layer was added to
avoid interactions between adjacent layers.
3.1 Characterizations of Ni-doped ZnCo2O4 atomic
layers
ZnCo2O4 atomic layers and Ni-doped ZnCo2O4 atomic
layers were first successfully synthesized using a
low-temperature and straightforward solvothermal
method. For example, the full characterizations of
the Ni-doped ZnCo2O4 atomic layers were shown as
follows. The XRD patterns were readily assigned
to cubic ZnCo2O4 (JCPDS 23-1390; Figs. S1–S3 in the
ESM). Additionally, the XPS spectra in Fig. S4 in the
ESM indicate the presence of Zn2+, Co3+, and O2−;
meanwhile, the Ni 2p3/2 peak at 856.0 eV indicate that
Ni was successfully doped in the lattice; Ni2+ was
the major species in the products (Fig. 1(d)). Element
mapping was further conducted to determine the
distribution of component elements; elemental Ni
was uniformly distributed in the synthetic products,
which is consistent with the XPS results. In addition,
the measured atomic percentage of doped Ni atoms
was 4.84% using ICP-AES. The FT-IR spectrum in
Fig. S5 in the ESM indicates the absence of organic

Figure 1 Characterizations of the Ni-doped ZnCo2O4 atomic layers: (a) TEM image, (b) high-resolution TEM image, and (c) the
corresponding interplanar spacing profiles along the dashed green lines; (d) X-ray photoelectron spectroscopy of Ni 2p, (e) atomic force
microscopy image, and (f) the corresponding height profiles; (g) high-angle annular dark-field scanning transmission electron
microscopy image and the corresponding energy-dispersive X-ray spectroscopy mapping images of Ni-doped ZnCo2O4 atomic layers.

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Nano Res.
matter on the surfaces and the formation of clean
Ni-doped ZnCo2O4. Moreover, the TEM image in
Fig. 1(a) reveals that the as-obtained products possess
a sheet-like morphology. As revealed by the high-
resolution TEM image in Figs. 1(b) and 1(c), the 2.08 Å
interplanar spacing matches well with the d400 spacings,
and the corresponding dihedral angle of 90° agrees
with the calculated angle between the (040) and (004)
planes of cubic ZnCo2O4, suggesting the [100] orientation
of the synthetic two-dimensional Ni-doped ZnCo2O4
atomic layers. The AFM image and corresponding
height profiles in Figs. 1(e) and 1(f) show average
thicknesses of approximately 2.5 nm, which correspond
to the three-unit cell thickness along the [100] projection.
Consequently, it was verified that clean Ni-doped
ZnCo2O4 atomic layers were first successfully fabricated.
For comparison, non-doped ZnCo2O4 atomic layers of
the same thickness were also synthesized under the
same conditions (except for the Ni source; Figs. S1–S6
in the ESM). Therefore, two ideal models of atomic
layers with/without element doping were subsequently
built to study the role of doping engineering for
selectivity regulating solar-driven CO2 reduction.
Figure 2 (a) Surface photovoltage response and temperature-programmed desorption curves of (b) CO2, (c) CH4, and (d) CO for the
Ni-doped ZnCo2O4 atomic layers and ZnCo2O4 atomic layers.
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3.2 Suitable band structures for CO2 photoreduction
Generally, when the semiconductor photocatalyst
absorbs photons with energies higher than its band
gap, the electrons would be excited into the conduction
band, leaving holes in the valence band [22, 23]. The
photogenerated electrons would be captured by CO2
and hence reduce it to carbon-based fuels, while the
photoexcited holes would simultaneously oxidize H2O
to O2. Thus, a suitable band structure is crucial for
photocatalytic reduction of CO2. Two prerequisites
exist for the band structure to realize solar-driven
CO2 reduction: (1) The conduction band edge should
be more negative than the potential of CO2 reduction,
and (2) the valence band edge should be more positive
than the potential of water oxidation. Hence, UV–vis
DRS and SRPES were performed to investigate their
band structures. As shown in Fig. 2(a), the Ni-doping
endowed the ZnCo2O4 atomic layers with significantly
increased photoabsorption from 300 to 2,500 nm. In
addition, the inset graph showed calculated bandgaps
of 2.51 and 2.67 eV for the Ni-doped ZnCo2O4 atomic
layers and the ZnCo2O4 atomic layers, respectively.
Specifically, the extra adsorption band at 387 nm for
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the Ni-doped ZnCo2O4 atomic layers belonged to d–d
crystal-field transitions (3T1(3P)→3A2(3F) transitions)
for high-spin Ni2+ (3d8). Three absorption bands were
observed at 524, 580, and 628 nm, which could be
assigned to the d–d crystal-field transitions (1T2(3G),
1
T1(3D), 3T2(3P)→ground state 1A1(5D) transitions) for
the low-spin Co3+ (3d6) in tetrahedral coordination [24].
The absorption peak around 1,250 nm corresponded
to the transition from 3T1(3P)→ground state 1A1(5D),
3
T2(3F)→3A2(3F), and 3T2(3F)→3A2(3F) for low-spin Co3+
(3d6), according to Tanabe–Sugano theory [25], in
which the electrons in fully occupied electron levels
can be easily excited to the unoccupied levels under
irradiation, thus providing a superior light conversion
efficiency. Moreover, SRPES, which was a powerful
technique for resolving the energy band structures,
was also performed to determine the band structure
positions. The calculated work functions of the ZnCo2O4
atomic layers with/without Ni-doping are 3.04 and
3.06 eV, respectively, using the equation provided in
section 2.3 (Fig. 3(c)). Meanwhile, the ZnCo2O4 atomic
layers with/without Ni-doping showed valence band
maxima that are 2.72 and 2.78 eV below the Fermi
level, respectively (Fig. 3(d)).
Therefore, the valence band maxima relative to
the vacuum level for the ZnCo2O4 atomic layers
with/without Ni-doping are 1.26 and 1.34 eV, respec-
tively. Along with the optical band gaps, the electronic
band energies were calculated for both samples relative
to a normal hydrogen electrode, as shown in Fig. 3(b);
their valence bands could produce oxygen and their
conduction bands could satisfy both the carbon
monoxide and methane production potentials, which
further verify their photocatalytic performances to
produce carbon forms and oxygen.
3.3 Enhanced electron–hole separation efficiency
and chemisorption properties
The separation process of photoexcited electron–hole
pairs is a major concern for promoting solar-driven
CO2 reduction. Thus, an in-depth understanding of
the charge separation is necessary to achieve efficient
CO2 photoreduction [22]. In this case, SPV spectra
were measured to investigate the charge carrier

Figure 3 Electronic band structures for the Ni-doped ZnCo2O4 atomic layers and the ZnCo2O4 atomic layers. (a) UV−vis diffuse
reflectance spectra, (b) band structures and corresponding reduction potentials, (c) secondary electron cutoff (Ecutoff) measured by SRPES,
and (d) SRPES valence band spectra.

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Nano Res.
separation process of both samples [7, 8]. As illustrated
in Fig. 2(a), the Ni-doped ZnCo2O4 atomic layers exhi-
bited higher SPV responses than the ZnCo2O4 atomic
layers, suggesting that the doped Ni atoms promoted
the separation efficiency of the photoexcited carriers.
Despite the improvement, it was still not clear if the
selectivity change was caused by Ni-doping. In this
case, specific surface area measurements (BET) and CO2
isothermal adsorption were conducted. Intriguingly,
because of the similar morphologies, thicknesses, and
crystal orientations, both the Ni-doped ZnCo2O4 atomic
layers and the ZnCo2O4 atomic layers exhibited nearly
the same specific surface area (43.77 vs. 45.18 m2·g−1,
respectively) (Fig. S7(a) in the ESM). In addition, the
similar adsorption amount of CO2 at ambient tem-
perature (Fig. S7(b) in the ESM) further demonstrated
the consistent physical properties of the ZnCo2O4
atomic layers with/without Ni-doping; thus, the
different selectivity might be caused by chemical
doping by Ni atoms. Moreover, TPD analyses were
conducted to study the chemisorption process of the
involved species in the reduction process. Note that
the chemidesorption temperatures of CO2 from the
ZnCo2O4 atomic layers with/without Ni-doping were
69 and 47 °C (Fig. 2(b)), respectively, which suggests
the strong adsorption of CO2 with Ni-doped ZnCo2O4
atomic layers, thus favoring the photoreduction
process. More importantly, the chemidesorption tem-
peratures of CH4 for the Ni-doped ZnCo2O4 atomic
layers and the ZnCo2O4 atomic layers were 61 and
18 °C, respectively, while their CO chemidesorption
temperatures were 10 and 74 °C, respectively (Figs. 2(c)
and 2(d)). Thus, CO desorption was favored over CH4
desorption on the Ni-doped ZnCo2O4 atomic layers,
whereas the reverse occurred for the ZnCo2O4 atomic
layers. Ni-doped ZnCo2O4 atomic layers might possess
a higher CO production rate, while the ZnCo2O4
atomic layers exhibit a higher CH4 production rate.
In short, the doping engineering confined in atomic
layers would likely regulate product selectivity for
CO2 photoreduction.
3.4 Boosted performances of solar-driven CO2
reduction
The Ni-doped ZnCo2O4 atomic layers exhibit an
enhanced CO2 photoreduction activity relative to that
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of the ZnCo2O4 atomic layers because of the advantages
discussed above. Their photoreduction measurements
were performed for a gas-solid system, of which
the gases were a mixture of CO2 and water vapor.
As shown in Fig. 4(a), the Ni-doped ZnCo2O4 atomic
layers provided CO and CH4 yields of 31.4 and
20.2 μmol·g−1·h−1, respectively, while the ZnCo2O4
atomic layers exhibited CO and CH4 yields of 12.4
and 28.1 μmol·g−1·h−1, respectively. Conspicuously,
the selectivity of CO/CH4 for the Ni-doped ZnCo2O4
atomic layers was 352% greater than that of the
ZnCo2O4 atomic layers, which agreed with the TPD
results shown in Figs. 2(c) and 2(d). The ZnCo2O4 atomic
layers with/without Ni-doping could simultaneously
realize H2O oxidation to O2 with average O2 evolution
rates of approximately 51.6 and 59.7 μmol·g−1·h−1,
respectively, during the 20-h photocatalysis tests
(Fig. S8 in the ESM). The yields of O2 were close to
the theoretical yields of 56.1 and 62.4 μmol·g−1·h−1
derived from the CO and CH4 yields, respectively.
These results verified the crucial role of Ni-doping in
improving the photocatalytic selectivity of CO/CH4
production in CO2 photoreduction. Both samples
survived three 21-h cycles (Fig. 4(b)) and maintained
nearly the same CO2 photoreduction activities and
selectivities, indicating their superior stabilities. Based
on the above analysis, Ni-doping could account for the
3.5 times greater selectivity of CO/CH4 production
during CO2 photoreduction.
3.5 In situ DRIFTS and possible mechanism of
CO2 photoreduction
To disclose the insight of the CO2 photoreduction
process, in situ DRIFTS of both samples was
conducted to detect their intermediates during CO2
photoreduction; in situ DRIFTS is a real-time technique
for observing the surface species that exist in the
transition states. As an example, the synthetic Ni-doped
ZnCo2O4 atomic layers generated new species with
increasing illumination time (Fig. 5(a)).
The concentrations of the involved species in the
photoreduction process correspond to the response
intensity depicted by the color in the three-dimensional
(3D) color-fill surface and heat maps of Fig. 5(a). Broad
peaks were visible from 1,600 to 1,700 cm−1 (Fig. 5(b));
the peaks at 1,679 and 1,123 cm−1 could be attributed
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Figure 4 3D histogram for the photoreduction of CO2 under irradiation from a 300-W xenon lamp for the Ni-doped ZnCo2O4 atomic
layers (cylinders cubes) and ZnCo2O4 atomic layers (cylinders). (a) Reduction rates during one 21-h cycle and (b) stability of three
cycles.

Figure 5 In situ diffuse reflectance infrared Fourier transform spectroscopy of CO2 photoreduction process for the Ni-doped ZnCo2O4
atomic layers. (a) 3D color-fill surface of photocatalysis for up to 40 min and (b) the corresponding heat maps.

to the absorption band of bicarbonate (asymmetric
stretching of b-HCO3−), while the peak at 1,565 cm−1
was assigned to the symmetric OCO stretching of
CO2− radicals [26, 27], implying that an electron
could be spontaneously transferred to CO2 under
illumination, ascribed to the transition process of CO2
+ e− → CO2−. Peaks at 2,109 and 1,320 cm−1 gradually
increased as the photolysis time increased; these
peaks could be assigned to physically adsorbed CO
(COad) [28] and the H–C–H bending vibration in CH4
[29], indicating an accumulation of photoreduction
products [30]. These as-assigned peaks also existed in
the photocatalytic process of the non-doped ZnCo2O4
atomic layers, as shown in Fig. S9 in the ESM, in
which the vibration peaks of COad and intermediate
CO2− were weaker than that of the Ni-doped ZnCo2O4
atomic layers, indicating that the Ni-doped ZnCo2O4
atomic layers provided a higher CO yield. Overall,
these spectroscopic data confirmed that the surface
bound CO2− species were the most likely reaction
intermediates from CO2 photoreduction using both
Ni-doped ZnCo2O4 atomic layers and ZnCo2O4 atomic
layers. To further confirm the crucial role of Ni-doping
engineering in tailoring the electronic structure at
an atomic level, we performed DFT calculations to
investigate the variation in the DOS. Evidently, as
revealed by the calculated DOS shown in Fig. 6, the
presence of the Ni dopant endowed the ZnCo2O4
atomic layers with an increased DOS at the CBM
with respect to the perfect ZnCo2O4 atomic layers in
the slab. In addition, the spatial distribution of the
orbital wave functions at the CBM revealed that the

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Nano Res. 9

Figure 6 Density functional theory calculations. Calculated density of states of (a) Ni-doped ZnCo2O4 atomic-layer slab and (b) ZnCo2O4
atomic-layer slab. Charge density distribution calculation of (c) Ni-doped ZnCo2O4 atomic-layer slab and (d) ZnCo2O4 atomic-layer slab.

increased charge density originated from the Co and

Zn atoms with the introduction of Ni atoms (Figs. 6(b)
and 6(d)). More importantly, the introduction of Ni
atoms produced several new energy levels in the
Ni-doped ZnCo2O4 atomic layers in the slab (Fig. 6),
which could be ascribed to splitting of the Ni 3d
states [18]. In this case, the photogenerated electrons
could be easily excited via the d→d internal transition
of tetrahedrally coordinated Ni ions under solar light
irradiation, suggesting that the Ni dopants confined
in the atomic layers could be directly involved in the
photocatalytic CO2 reduction and hence significantly
improve the photocatalytic activity and selectivity.
Hence, a possible solar-driven reduction path was
proposed (Scheme 1) according to the intermediates
revealed by in situ DRIFTS [10, 31–33].
Generally, the CO2 photoreduction includes the
following crucial processes: (1) generating electron–
hole pairs with illumination on the semiconductor,
(2) separating photoexcited electron–hole pairs,
(3) adsorbing CO2, (4) transferring photogenerated
electrons to CO2, forming CO2− and allowing the
Scheme 1 Schematic illustration for the possible mechanism
of CO2 reduction with the as-synthesized ZnCo2O4 atomic layers
with/without Ni-doping under illumination.
following reduction reaction, and (5) desorbing the
reduction products. Interestingly, as verified by the
SPV spectra, Ni-doping assisted the electron–hole
pair process in the ZnCo2O4 atomic layers; thus,
more photogenerated electrons are anticipated in the
following reduction of CO2. UV–vis spectroscopy
and SRPES indicated that the band structures of both
the Ni-doped ZnCo2O4 atomic layers and the ZnCo2O4
atomic layers were suitable for CO2 reduction to CO
and CH4. Moreover, the reaction intermediates were

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detected as CO2− radicals using in situ DRIFTS,
suggesting that the photogenerated electrons would
initially reduce CO2 to CO2− radicals. The as-produced
intermediates would further react with photoexcited
electrons and H+ to transform into CO and CH4 via
different paths, as shown in Scheme 1. The TPD
results revealed that the CO desorption process was
easier using the Ni-doped ZnCo2O4 atomic layers,
while the CH4 desorption process was easier using
the ZnCo2O4 atomic layers; this implies that the
Ni-doping engineering benefitted the CO a desorption
process. The Ni atoms doped in the lattice of the
ZnCo2O4 atomic layers changed the adsorption energy
of different species for the extra adsorption structure
of Ni–O; Co–O and Zn–O (O in CO2 and CO)
(Scheme S1 in the ESM) could account for the
different chemisorption ability of the products for
Ni-doped ZnCo2O4 atomic layers and ZnCo2O4 atomic
layers.
4 Conclusions
Element doping confined to atomically thin two-
dimensional layers was first applied as a selective
tuning approach for photocatalytic CO2 reduction. As
a proof-of-concept prototype, ZnCo2O4 atomic layers
with/without Ni doping were first synthesized using
a low temperature (i.e., 140 °C) solvothermal strategy.
Energy-dispersive X-ray spectroscopy mapping
clarified the uniform distribution of doped Ni atoms
in the ZnCo2O4 atomic layers. The band structures
obtained by UV–vis spectroscopy and SRPES indicated
that both the Ni-doped ZnCo2O4 atomic layers and
the ZnCo2O4 atomic layers could photoreduce CO2 to
CO and CH4. The higher separation efficiency of the
photo-excited electron–hole pairs for the Ni-doped
ZnCo2O4 atomic layers was verified by the SPV spectra.
In situ DRIFTS spectra provided evidence for the
existence of CO2− radical as the main intermediate in
the photoreduction of CO2 for both samples. TPD
curves revealed that the Ni-doped ZnCo2O4 atomic
layers showed a lower CO desorption temperature
than the ZnCo2O4 atomic layers, indicating that the
chemisorption ability with products would account
for the preferential selectivity of CO evolution for
Ni-doped ZnCo2O4 atomic layers. Furthermore, DFT
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Nano Res.
calculations illustrated that the Ni doping led to a
higher DOS near the CBM and new doping energy
levels, beneficial for a higher separation efficiency of
photogenerated electron–hole pairs. As a result, the
Ni-doped ZnCo2O4 atomic layers possessed CO and
CH4 formation rates of 31.4 and 20.2 μmol·g−1·h−1,
respectively, while those of the ZnCo2O4 atomic
layers were 12.4 and 28.1 μmol·g−1·h−1, respectively; the
former shows a 3.5 times higher selectivity toward
CO evolution than CH4 production. Briefly, this work
developed an element-doping strategy for tuning the
product selectivity of solar-driven CO2 reduction with
atomically thin semiconductors, providing important
clues for controlling and tailoring the selectivity of
the desired products during CO2 photoreduction.
Acknowledgements
This work was financially supported by the National
Key Research and Development Program of China
(Nos. 2017YFA0303500 and 2017YFA0207301), the
National Natural Science Foundation of China (Nos.
21422107, U1632147, 21331005, U1532265, and 11621063),
Youth Innovation Promotion Association of CAS (No.
CX2340000100), Key Research Program of Frontier
Sciences of CAS (No. QYZDY-SSW-SLH011), the
Fundamental Research Funds for the Central
Universities (Nos. WK2340000063 and WK2340000073)
and Scientific Research Grant of Hefei Science Center
of CAS (No. 2016HSC-IU002).
Electronic Supplementary Material: Supplementary
material (Figs. S1–S9) is available in the online version
of this article at https://doi.org/10.1007/s12274-017-
1943-2.
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