You are on page 1of 12

catalysts

Article
NOx Removal by Selective Catalytic Reduction
with Ammonia over a Hydrotalcite-Derived NiFe
Mixed Oxide
Ruonan Wang 1 , Xu Wu 1, *, Chunlei Zou 1 , Xiaojian Li 1 and Yali Du 2, *
1 College of chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China;
wangruonan0490@link.tyut.edu.cn (R.W.); zouchunlei0492@link.tyut.edu.cn (C.Z.);
mlixiaojian@163.com (X.L.)
2 College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong 030619, China
* Correspondence: wuxu@tyut.edu.cn (X.W.); dyl0037@163.com (Y.D.);
Tel.: +86-035-1601-8528 (X.W.); +86-13513635848 (Y.D.)

Received: 24 July 2018; Accepted: 6 September 2018; Published: 8 September 2018 

Abstract: A series of NiFe mixed oxide catalysts were prepared via calcining hydrotalcite-like
precursors for the selective catalytic reduction of nitrogen oxides (NOx ) with NH3 (NH3 -SCR).
Multiple characterizations revealed that catalytic performance was highly dependent on the phase
composition, which was vulnerable to the calcination temperature. The MOx phase (M = Ni or Fe)
formed at a lower calcination temperature would induce more favorable contents of Fe2+ and Ni3+
and as a result contribute to the better redox capacity and low-temperature activity. In comparison,
NiFe2 O4 phase emerged at a higher calcination temperature, which was expected to generate more
Fe species on the surface and lead to a stable structure, better high-temperature activity, preferable
SO2 resistance, and catalytic stability. The optimum NiFe-500 catalyst incorporated the above virtues
and afforded excellent denitration (DeNOx ) activity (over 85% NOx conversion with nearly 98% N2
selectivity in the region of 210–360 ◦ C), superior SO2 resistance, and catalytic stability.

Keywords: NiFe-LDH; mixed oxide; NiFe2 O4 spinel; NOx ; NH3 -SCR

1. Introduction
Emission of nitrogen oxides (NOx ) is a main contributing factor to the induction of regional air
pollution and ecosystem acidification [1]. During the past few decades, stringent regulations on NOx
emissions have been issued worldwide and various measures have been devoted to diminish NOx ,
among which the removal of NOx from stationary sources by selective catalytic reduction of NOx with
NH3 (NH3 -SCR) has been attracting significant attention due to the low cost and high efficiency [2–4].
The most adopted SCR catalysts in practical applications are V-based catalysts, while the toxicity of
active vanadium species, together with high N2 O formation at high temperatures, restricts their further
application [5]. Therefore, for the current situation, developing environmentally friendly substitutive
catalysts with excellent efficiency, strong stability, and high SO2 resistance in NH3 -SCR is imperative.
Recently, great efforts have been made to exploit novel NH3 -SCR catalysts, and some transition
metal oxide catalysts have received wide attention [6–8]. Notably, iron-based catalysts have been
considered as a potential candidate for the NH3 -SCR application due to their high reactivity,
cost-effectiveness, superior SO2 durability, and non-toxicity. However, pure iron catalysts are subject
to to the limitations of a low acid amount [9] and inferior N2 selectivity beyond 330 ◦ C [10,11].
Up to now, a lot of reports have found that introducing other active ingredients (e.g., titanium
oxides [12], manganese oxides [13], or tungsten oxides [2]) is an effective way to promote the denitration
(DeNOx ) performance of iron-based catalysts. Especially, nickel species possess abundant surface

Catalysts 2018, 8, 384; doi:10.3390/catal8090384 www.mdpi.com/journal/catalysts


Catalysts 2018, 8, x FOR PEER REVIEW 2 of 12

Up to now, a lot of reports have found that introducing other active ingredients (e.g., titanium
Catalysts 2018, 8, 384 2 of 12
oxides [12], manganese oxides [13], or tungsten oxides [2]) is an effective way to promote the
denitration (DeNOx) performance of iron-based catalysts. Especially, nickel species possess abundant
surface
acidity acidity sites
sites [14] and[14] and a favorable
a favorable ability toability to increase
increase the N2 selectivity
the N2 selectivity of NH3of -SCRNHreactions
3-SCR reactions
[15,16],
[15,16],
which was which was expected
expected to be introduced
to be introduced into theinto the iron-based
iron-based catalytic
catalytic systemsystem [17]. Furthermore,
[17]. Furthermore, nickel
nickel oxides are considered as valuable materials to induce a synergistic effect
oxides are considered as valuable materials to induce a synergistic effect with other active species, with other active
species,
such as such
NiMnO as NiMnO [18,19]
x [18,19]x and andx NiTiO
NiTiO x [20],are
[20], which which
veryare very sensitive
sensitive to the synthesis
to the synthesis process.process.
ItItwas
wasreported
reportedthatthatlayered
layereddouble
doublehydroxide
hydroxide(LDHs)(LDHs)materials
materialsare
areexcellent
excellentprecursors
precursorsfor forthethe
preparation of metal oxide catalysts with the desired chemical and phase composition
preparation of metal oxide catalysts with the desired chemical and phase composition [21]. Thermal [21]. Thermal
decomposition
decompositionof ofhydrotalcite-like
hydrotalcite-like materials
materialscouldcouldproduce
producelayered
layereddouble
doubleoxides
oxides(LDOs)
(LDOs)possessing
possessing
aarelatively high surface area, which could promote the catalytic
relatively high surface area, which could promote the catalytic performance. performance.
Herein,
Herein,aaseries
seriesofofeconomical
economical and
and eco-friendly
eco-friendly NiFe
NiFemixed
mixedoxides catalysts
oxides werewere
catalysts prepared
preparedvia
calcining
via calcininga hydrotalcite-like
a hydrotalcite-like compound
compound at atvarious
varioustemperatures.
temperatures.The TheNH NH 3-SCR
3 -SCR activity,
activity, SO
SO 2
2
resistance, and stability were evaluated for the different NiFe mixed oxides catalysts.
resistance, and stability were evaluated for the different NiFe mixed oxides catalysts. The correlations The correlations
among
among phase
phase composition,
composition, structure,
structure, andand catalytic
catalytic performance
performance were were systematically
systematically explored
explored by by
XRD
XRD (X-ray
(X-ray diffraction),
diffraction), FT-IR
FT-IR (Fourier
(Fourier Transform
Transform Infrared),
Infrared), TG (thermogravimetric analysis),
TG (thermogravimetric analysis), N N22
physisorption,
physisorption, NH NH33-TPD
-TPD (NH(NH33-Temperature
-Temperature Programmed
Programmed Desorption),
Desorption), H H22-TPR
-TPR (H (H22-Temperature
-Temperature
Programmed
Programmed Reduction),
Reduction), and and XPS
XPS (X-ray
(X-ray Photoelectron
Photoelectron Spectroscopy).
Spectroscopy). It It was
was proved
proved that that the
the DeNO
DeNOxx
performance
performance was highly dependent on the phase composition of NiFe mixed oxides catalysts,which
was highly dependent on the phase composition of NiFe mixed oxides catalysts, which
was
was available
available viavia adjusting
adjusting thethe calcination
calcination temperature
temperature of of NiFe-LDH.
NiFe-LDH.This This work
work may may serve
serve asas anan
important
important reference
reference forforLDH
LDHprecursors
precursorstoto be be tailored
tailored for for potential
potential applications
applications in adjusting
in adjusting the
the phase
phase component
component and catalytic
and catalytic performance.
performance.

2.
2.Results
Resultsand
andDiscussion
Discussion

NH
NH33-SCR
-SCRreactions
reactionsover
overNiFe
NiFemixed
mixedoxides
oxidescatalysts
catalystsatatvarious
variouscalcination
calcinationtemperatures
temperatures(400
(400°C,
◦ C,

500 °C, and 600 °C) were performed during 150–450 °C and the results are given in Figure 1A. It is
◦ ◦ ◦
500 C, and 600 C) were performed during 150–450 C and the results are given in Figure 1A. It is clear
clear thatNiFe-400
that the the NiFe-400
samplesample
showed showed rather
rather low NHlow3 -SCRNH 3-SCR efficiency
efficiency with an obviously
with an obviously narrow
narrow operation
operation
temperature temperature
window. The window.
DeNO The DeNOxand
x activity activity and temperature
temperature window for window for the NiFe-500
the NiFe-500 and
and NiFe-600
NiFe-600 samples
samples were were promoted
promoted dramatically
dramatically in comparison
in comparison to that oftothethat of the NiFe-400
NiFe-400 catalyst.
catalyst. The The
NiFe-600
NiFe-600 catalyst exhibited
catalyst exhibited lower NO lower
x NO conversion
conversion
x than the than the
NiFe-500 NiFe-500
catalyst catalyst
at at temperatures
temperatures below below
330 ◦ C,

330 °C,it while


while behaved it behaved
better in better in the
the higher higher temperature
temperature region,
region, which whichthat
implied implied that the
the higher higher
calcination
calcination
temperature temperature
was conducivewas conducive to high-temperature
to high-temperature SCR activity.SCRAs
activity. As demonstrated
demonstrated in Figurein1B,
Figure 1B,
all NiFe
all NiFe mixed oxides catalysts afforded superior
mixed oxides catalysts afforded superior N 2 N2 selectivity: nearly 98% below 360 °C. When
selectivity: nearly 98% below 360 ◦ C. When temperatures
temperatures
exceeded 360exceeded 360 °C, the N2 selectivity of the NiFe-500 and NiFe-600 samples showed a
◦ C, the N selectivity of the NiFe-500 and NiFe-600 samples showed a slight decline
2
slight decline
compared compared
with with the
the NiFe-400 NiFe-400
catalyst. catalyst. the
Obviously, Obviously,
NiFe-500 thecatalyst
NiFe-500was catalyst waspromising
the most the most
promising
candidate for candidate
NH3 -SCR, for NH3-SCR,
affording aboveaffording
85% DeNO above 85%within
x activity DeNOthe x activity within theregion
widest temperature widest of
temperature
210–360 ◦ C andregion of 210–360
superior °C and superior
N2 selectivity over theNwhole
2 selectivity
testedover the wholerange.
temperature tested temperature range.

Figure 1. Cont.
Catalysts 2018,
Catalysts 2018, 8,
8, 384
x FOR PEER REVIEW of 12
3 of 12

Figure 1. Catalytic performance of the serial NiFe-layered double oxide (LDO) catalysts: (A) nitrogen
oxide (NOx ) conversion; (B) N2 selectivity; (C) stability tests at 300 ◦ C; (D) SO2 /H2 O resistance tests at
Figure
300 ◦ C. 1. Catalytic
Reaction performance
conditions: of theNO,
600 ppm serial
600NiFe-layered
ppm NH3 , 5% double oxide
O2 , 100 ppm(LDO) catalysts:
SO2 (when (A)10%
used), nitrogen
H2 O
oxide (NO
(when x) conversion;
used), balance N2 ,(B)
gasNhourly
2 selectivity;
space (C) stability
velocity tests =at45,000
(GHSV) 300 °C;
h (D)
− 1 . SO2/H2O resistance tests at
300 °C. Reaction conditions: 600 ppm NO, 600 ppm NH3, 5% O2, 100 ppm SO2 (when used), 10% H2O
(when
The used), balance
stability N2, gas hourly
is an important space velocity
indicator (GHSV)
to estimate the =properties
45,000 h-1. of catalysts. The stability tests
were performed at 300 ◦ C for 50 h over each catalyst under the reaction conditions of 600 ppm NO,
600 ppmThe NH
stability
3 , 5.0% is Oan2 ,important
and balanced indicator
with N to2 .estimate
As presented the properties
in Figureof 1C,catalysts.
the DeNO The stabilityoftests
x activity the
were performed
NiFe-500 and NiFe-600 at 300 catalysts
°C for 50 slightly
h over each catalyst
fluctuated under
with onlythe ±1% reaction
variance,conditions of 600
indicating fineppm NO,
stability.
600 ppm NH3, 5.0%
Comparatively, O2, and balanced
the NiFe-400 with N2. As
sample displayed the presented
relatively worstin Figure 1C, the
stability. SuchDeNO x activity
different of the
stabilities
NiFe-500
can and NiFe-600
be ascribed catalysts stabilities
to the different slightly fluctuated
of the mixed with oxides’
only ± 1% variance,Thus,
structures. indicating fine stability.
the NiFe-500 and
Comparatively,
NiFe-600 catalysts thepossessed
NiFe-400 asample displayed
more stable the relatively
structure in comparison worst stability. Such different
with the NiFe-400 stabilities
catalyst.
can be Theascribed
presence to oftheH2different
O and SO stabilities of theexhaust
2 in the actual mixed oxides’
usuallystructures.
inhibits theThus, the NiFe-500
NH3 -SCR of NOx [22]. and
NiFe-600 catalysts
Therefore, it is of great possessed a more to
importance stable structure
evaluate the H in2comparison
O and/or SO with the NiFe-400
2 tolerance undercatalyst.
the reaction
The presence
conditions. The H2 O of and/or
H2O and SOSO
2 2 in the actual
tolerance of the exhaust
serial usually
NiFe mixed inhibits
oxides the NH
catalysts 3-SCR
was of NOx [22].
investigated
Therefore,
◦ it is of great importance to evaluate the H
at 300 C under the reaction conditions of 600 ppm NO, 600 ppm NH3 , 5% O2 , 0 or 100 ppm2O and/or SO 2 tolerance under theSO reaction
2 , 0 or
conditions.
10.0% H2 O, Theand H 2O and/or
balanced SO2Ntolerance
with 2 . As of
depicted the serial
in NiFe
Figure 1D,mixed
at the oxides
first catalysts
stage, the was
NO xinvestigated
conversion
at 300
for the°C under the
NiFe-400, reaction and
NiFe-500, conditions
NiFe-600 of 600 ppm NO,
catalysts was600 ppm NH3at
maintained , 5% O2, 0 or
around 10099%,
85%, ppmand SO2,96%,0 or
10.0% H2O, and
respectively. After balanced
addingwith N2. As
100 ppm SOdepicted
2 into the inreaction
Figure 1D, gas,atthe theNO first stage, the NO
x conversion x conversion
decreased slightly.for
the NiFe-400,
However, NiFe-500, and
the co-existence NiFe-600
of 100 ppm SO catalysts
2 and 10%was H maintained
2 O led to a at around
gradual 85%,
decrease 99%,
to some and 96%,
extent
respectively.
in NOx conversion, After adding where 100 the ppm
decreaseSO2 into
was the only reaction
about 2% gas,forthethe NO x conversion
NiFe-500 and decreased
NiFe-600 samplesslightly.
However,
while aroundthe aco-existence
5% decrease ofwas
100 displayed
ppm SO2 and for 10% H2O led
NiFe-400. to apurging
After gradualoff decrease
SO2 and to Hsome extent
2 O, the NOin x
NOx conversion,
conversion gradually whererecovered
the decrease to thewasoriginal
only about values.2% for the NiFe-500
Thus, the NiFe-500 and NiFe-600
and NiFe-600samples while
catalysts
around a an
possessed 5%excellent
decreaseSOwas 2 and displayed
H2 O resistancefor NiFe-400.
ability in After purging
comparison to theoff NiFe-400
SO2 and catalyst.
H2O, the NOx
conversion
XRD isgradually
an essential recovered
technology to the original values.
to evaluate Thus, of
the structure thecatalysts.
NiFe-500The andXRD
NiFe-600
pattern catalysts
of the
possessed an excellent SO and H O resistance ability in comparison
NiFe-LDH precursor is presented in Figure 2A. The characteristic reflections at 2θ values of 11.7 , 23.2◦ ,
2 2 to the NiFe-400 catalyst. ◦

34.5◦ ,XRD
39.1◦is an ◦essential
, 45.6 , and 59.8technology to evaluate
◦ can be observed, which thewerestructure of catalysts.indexed
correspondingly The XRD pattern
to the (003),of the
(006),
NiFe-LDH
(012), (015), precursor
(018), and is presented
(110) in Figure to
planes according 2A. theThe characteristic
standard card (JCPDS reflections at 2θ values
no.15-0087). of 11.7°,
The absence of
23.2°, 34.5°, 39.1°, 45.6°, and 59.8° can be observed, which were
other crystalline phases hinted at the successful fabrication of NiFe-LDHs with high purity. correspondingly indexed to the (003),
(006),The(012),
FT-IR (015), (018), and
spectrum (110) planes
of NiFe-LDH is according
illustratedtointhe standard
Figure 2B. An card (JCPDS
intense andno.15-0087).
board peakThe at
absence
3429 cm−of other crystalline
1 corresponded to the phases hinted
stretching at the successful
vibration of the -OH fabrication
group in the ofNiFe
NiFe-LDHs
brucite-like withlayers,
high
purity.
the interlayer water molecules, and the lattice water [23]. The peak that occurred at 2987 cm−1 can be
The to
assigned FT-IR
a COspectrum
2 –H2 O bridgingof NiFe-LDH
bond [24]. is illustrated
The vibration in Figure
of the 2B.angularAn intense
deformationand board
of H2peak at 3429
O molecules
was observed at 1601 cm [23]. The peaks at 1385 cm belonged to the stretching vibrationsthe
cm -1 corresponded to the − stretching
1 vibration of the -OH − 1group in the NiFe brucite-like layers, of
interlayer ions
carbonate water molecules,
[25]. Additionally, and the latticelocated
the peak water at [23].
676The cm−peak1 might thatbeoccurred
correlatedatto2987 cm-1 can be
the vibration of
assigned
M-O (Fe-O,to Fe-O-Ni
a CO2–H or2O bridging
Ni-O) on thebondlayer [24].
of theThe vibration
NiFe-LDH of the[26].
samples angular
Both deformation
XRD and FT-IR of data
H2O
molecules was
confirmed that observed
NiFe-LDHatwas 1601prepared
cm-1 [23].successfully
The peaks atwith 1385CO cm23-1−belonged to the stretching
as an interlayer anion. vibrations
of carbonate ions [25]. Additionally, the peak located at 676 cm might be correlated to the vibration-1
Catalysts 2018, 8, x FOR PEER REVIEW 4 of 12

Catalysts 2018, 8, x FOR PEER REVIEW 4 of 12


of M-O 2018,
Catalysts (Fe-O, Fe-O-Ni or Ni-O) on the layer of the NiFe-LDH samples [26]. Both XRD and FT-IR4data
8, 384 of 12
2-
confirmed that NiFe-LDH was prepared successfully with CO as
of M-O (Fe-O, Fe-O-Ni or Ni-O) on the layer of the NiFe-LDH samples
3 an interlayer anion.
[26]. Both XRD and FT-IR data
2-
confirmed that NiFe-LDH was prepared successfully with CO3 as an interlayer anion.

Figure
Figure 2. XRD
2. XRDpattern
pattern(A)(A)
andand FT-IR
FT-IR spectrum
spectrum (B) of(B) of layered
NiFe- NiFe- layered double hydroxide
double hydroxide (LDH)
(LDH) precursor;
Figure 2. XRD pattern (A) and FT-IR spectrum (B) of NiFe- layered double hydroxide (LDH)
precursor;
XRD XRD
patterns ofpatterns
NiFe-LDO of NiFe-LDO
catalysts catalysts (C).
(C).
precursor; XRD patterns of NiFe-LDO catalysts (C).

The
The process
process of
The process
of thermal
of thermaldecomposition
thermal decomposition of
decomposition ofthe
of the NiFe-LDH
NiFe-LDH precursor
precursor into
the NiFe-LDH precursor
into mixed
mixed oxides
into mixed
oxides was
oxides was
wasstudied
studied
studied
by by
by TGTG
TG coupled
coupled
coupled with
withMS
with MS
MS(mass
(massspectrometer)
(mass
spectrometer) analysis
spectrometer)
analysis (TG-MS).
analysis (TG-MS).
(TG-MS). From Fromthe
From theTG
the TGand
TG andDTG
and DTG(derivative
DTG (derivative
(derivative
thermogravimetry)
thermogravimetry)
thermogravimetry) curves
curvesinin
curves inFigure
Figure
Figure 3A,
3A, three
3A, three
three major
major
major weight-loss
weight-loss
weight-loss stages
stages werewere
stages
were observed
observed visually.
observed
visually. The
visually.
The
◦ ◦
initial
The reduction
initial reductionin mass in occurred
mass between
occurred 80
between °C and
80 C 180
and °C (approximately
180 C
initial reduction in mass occurred between 80 °C and 180 °C (approximately 9 wt.%) and arose from (approximately 9 wt.%) 9 and
wt.%) arose
and from
arose
the
fromdesorption
the the
desorption of of
desorption the of
the surface adsorbed
the surface
surface and
adsorbed
adsorbed andinterlayer
and interlayer
interlayer waterwater
and CO
and CO
and molecules.
CO2 molecules.
22molecules. Thesecond
The second mass
The second
mass loss
mass
loss
◦ C (about 13 wt.%) and mainly released H O,
stage
stage
loss occurred
stage occurred at at
occurred thethe
at temperature
temperaturerange
the temperature rangeof of190–350
range 190–350 °C
of °C (about 13
190–350 13 wt.%)
wt.%)and andmainly
mainlyreleased
released HH2O,2O,
CO CO2,2 2,

and
COand2NO
, andNO2, which
, which
2NO were
were
2 , which detected
detected
were bybyonline
detected by MS
online MSanalysis
online analysis (Figure 3B).
MS analysis 3B).This
This3B).
(Figure rapid
rapid and
and
This major
major
rapid mass
mass
and loss
loss
major cancan
mass
be be
loss assigned
assigned
can to to
be assignedthethe dehydroxylation
dehydroxylation
to the dehydroxylation ofofthe
the inorganic
inorganic layers and
of the inorganic and decomposition
decomposition
layers ofofinterlayer
and decomposition interlayeranions
anions
of interlayer
- − 2- 2- 2−
(NO(NO
anions-
3 and
3(NO and 3COCO
and ) [27]
3 )3 [27]
CO accompanied
3 accompanied
) [27] accompanied by the
by the collapse
by collapse
the of the
collapse the hydrotalcite
hydrotalcite
of the hydrotalcite structure.
structure.
structure. AAsmall
Asmall
smallDTGDTG
DTG
exothermic
exothermic
exothermic peakpeak
peak at atabout
at aboutabout395 395
395
◦ C°C observed
°Cobserved
observed ininin the
thethe Figure
Figure
Figure 3A3A 3A corresponds
corresponds
corresponds totothe
to the therelease
release
release ofofCO
of CO 2 CO2 and
and and2
2 NO
NO in the MS curves, which was attributed to the degradation of
NO2 in the MS curves, which was attributed to the degradation of nitrates and carbonates with high
in the 2MS curves, which was attributed to the degradation of nitratesnitrates
and and carbonates
carbonates with with
high high
thermal
thermal
thermal
stability. stability.
stability.
Based theBased
on Based ononthe
above, theabove,
stable above, stable oxides
NiFe stable
mixed NiFe mixed
NiFe mixed
catalystsoxides
oxides
can becatalysts
catalysts
obtained can
can bebeobtained
when obtainedwhenwhen
hydrotalcite-like
hydrotalcite-like
precursors are precursors
calcined at overare calcined
400 ◦
hydrotalcite-like precursors are calcined at over 400 °C. C. at over 400 °C.

Figure
Figure 3. 3. ResultsofofTG
Results TGand
andDTG
DTGstudies
studies (A)
(A) combined
combinedwith
withMS
MSanalysis
analysis(B)
(B)for the
for NiFe-LDH
the sample.
NiFe-LDH sample.
Figure 3. Results of TG and DTG studies (A) combined with MS analysis (B) for the NiFe-LDH sample.
AnAnXRDXRD analysis
analysis waswas performed
performed forserial
for the the serial NiFe mixed
NiFe mixed oxides oxides catalysts,
catalysts, which
which were were
produced
byproduced ◦ C). As exhibited in Figure 2C, the calcination
byanalysis
calcining was
calcining NiFe-LDH
An XRD
at NiFe-LDH
different at different
temperatures
performed for thetemperatures
(400–600
serial NiFe (400–600
mixed°C). As exhibited
oxides catalysts,in which
Figure 2C,
were
the calcination
temperature was temperature
an important
produced by calcining NiFe-LDH was an
factor
at important
affecting
different factor
the affecting
formation
temperatures the
of formation
crystalline
(400–600 °C). of crystalline
phase.
As
As
exhibited
the
inphase. As2C,
calcination
Figure
temperature increases from 400 ◦ C to 600 ◦ C, the diffraction peaks were found to significantly sharpen,
the calcination temperature was an important factor affecting the formation of crystalline phase. As
representing the mushrooming of crystallinity and particle size. Meanwhile, new crystal phases
progressively appeared. For the NiFe-400 sample, all diffraction peaks at 37.0◦ , 43.3◦ , 63.2◦ , 75.7◦ ,
Catalysts 2018, 8, 384 5 of 12

and 78.8◦ could be assigned to NiO phase (PDF # 44-1159). The absence of diffraction peaks of Fe
species, existing in the form of oxides (e.g., FeO, Fe2 O3 , and Fe3 O4 ), manifested their high dispersion or
presence in the crystal lattice of NiO. The indicative diffraction peaks of NiFe2 O4 spinel were emergent
in NiFe-500 and markedly enhanced for the NiFe-600 sample, which were located at 2θ values of 30.4◦ ,
35.6◦ , 53.8◦ , and 57.5◦ (PDF # 10-0325). Notably, according to the literature [28], a NiFe2 O4 spinel
possesses an inverse structure and can be written as Fe[NiFe]O4 , in which half of the Fe3+ occupies
the tetrahedral sites with the octahedral sites comprised of a 1:1 ratio of Ni2+ and Fe3+ cations. It was
reported that such an inverse NiFe2 O4 spinel is a valuable material with structural stability and the
possibility for bifunctional redox properties [28,29], Combining the results in the catalytic performance
tests, the NiFe2 O4 spinel could be confirmed to be the expected phase in this system.
The nitrogen adsorption and desorption isotherms of NiFe mixed oxides catalysts are displayed
in Figure 4A, in which can clearly be observed the typical shape of type IV isotherms curves (IUPAC
classification), indicating the presence of 2–50 nm mesopores [30,31]. The NiFe-400 and NiFe-500
samples displayed a typical type H2 hysteresis loop that verified the existence of an “ink bottle” state
structure, whereas the NiFe-600 catalyst presented the narrow type H3 hysteresis loop, demonstrating
the existence of a “slit”-shaped mesopore [9,32], Meanwhile, the pore diameter distribution of the
serial catalysts can be visually observed from Figure 4B, where NiFe-500 exhibited the more intensive
distribution in the region of 1–6 nm. The Brunauer–Emmett–Teller (BET) surface area and the average
pore diameter of the as-prepared catalysts are listed in Table 1. The BET specific surface areas
calculated by N2 desorption isotherms were clearly seen to drop sharply with the increase of the
calcination temperature in Table 1. However, the order of the catalysts by average pore diameter
was NiFe-600 (15.5 nm) > NiFe-400 (5.1 nm) > NiFe-500 (4.0 nm). As discussed in the XRD analysis,
with the increasing of calcination temperature, the crystallinity and particle size were both increased.
Thus, the BET surface areas were decreased, which is in agreement with the literature [33]. In addition,
in comparison to NiFe-400, NiFe-500 showed a smaller pore diameter, which may be due to the
shrinkage of pores accompanied by the increase in crystallinity. However, for NiFe-600, a high
crystallinity NiFe2 O4 spinel was formed, which may result in the formation of a “stacked hole” with a
larger pore diameter. The relatively larger specific surface area and even porous structures can provide
more catalytic
Catalysts 2018, 8, xcenters,
FOR PEERwhich might account for the better DeNOx performance.
REVIEW 6 of 12

Figure 4.
Figure 4. N
N22 adsorption
adsorption and
and desorption isotherms (A)
desorption isotherms (A) and
and pore
pore diameter
diameter distribution
distribution (B)
(B) of
of the
the serial
serial
NiFe-LDO catalysts.
NiFe-LDO catalysts.

The surface
The surface acidity
acidity and
and acid
acid strength
strength distribution
distribution of of the
the NiFe
NiFe mixed
mixed oxides
oxides catalysts
catalysts were
were
investigated by
investigated by NH
NH33-TPD
-TPDexperiments.
experiments.As Asillustrated
illustratedin in
Figure
Figure5A,5A,thethe
NHNH 3-TPD
3 curves
-TPD showed
curves two
showed
ammonia
two ammoniadesorption peakspeaks
desorption for each
for sample in the in
each sample 70–700 °C range.
the 70–700 ◦ C The firstThe
range. desorption peak centered
first desorption peak
at around 120 °C corresponds to the physisorbed NH3 or weakly acidic sites [34]. The other peak
located at around 480 °C can be assigned to the chemical adsorbed ammonia on strong Lewis and
Brønsted acidity sites [35]. The amount of total NH3 adsorption and the proportion for every type of
acid site were calculated from the integrated areas of the corresponding peaks. The calculation results
were normalized and are listed in Table 2. It is clear that the increase of calcination temperature
Catalysts 2018, 8, 384 6 of 12

Catalysts 2018, 8, x FOR PEER REVIEW 7 of 12


centered at around 120 ◦ C corresponds to the physisorbed NH3 or weakly acidic sites [34]. The other
peak located
each at around
catalyst 480 ◦ C can
were calculated andbeareassigned
shown intoTable
the chemical
3. For all adsorbed
samples, the ammonia
amounton of strong Lewis and
total theoretical
Brønsted acidity sites
H2 consumption was[35]. Thethan
higher amount of the
that of totaltotal
NHactual
3 adsorption and the proportion
H2 consumption, implying the for existence
every type of of
acidan incomplete reduction of active species. Therein, the actual H2 consumption amount of Ni species
site were calculated from the integrated areas of the corresponding peaks. The calculation results
were(peak 1) was higher
normalized and are than thein
listed theoretical
Table 2. Itvalues
is clearfor each
that thecatalyst
increase(Aof1 >calcination
E1), while temperature
Fe species (peak 2)
resulted
in awere the opposite
dramatic reduction (A2of
<E 2). Therefore,
ammonia the firstand
adsorption reduction
surfacepeak mayThe
acidity. be ascribed
desorption to the co-reduction
amount of
of NiFe-500
andNiNiFe-600
as well as partial Feby
decreased species
35% and and 73%,
the second peak may
respectively. be only attributed
In addition, with the to the Fe species.
calcination From
temperature
Table 3,from
increasing it was 400also
◦ clear
C to 600that
◦ the proportion
C, the NiFe-400 and NiFe-500
of weakly catalysts
acidic exhibited
sites shows a similar
an obvious position
rise of
from 34.5%
reduction
to 52.4%, peaks
while theand the NiFe-600
proportion of thecatalyst significantly
strongly acidic sites shifted to high-temperature
decreased from 65.5% tozones, 47.6%.presenting
Combined
withthetheworst reducibility
results of XRD and for BET,
NiFe-600, which can that
we speculated well-explain
the increaseits degraded DeNO
of calcination x activity at resulted
temperature a low
temperature compared with the NiFe-400 and NiFe-500 catalysts.
in severe agglomeration of iron species and the acid center was covered in this process. More acid
sites should be conductive to promote DeNOx activity. However, the NiFe-400 catalyst afforded the
Table 2. Amount and proportion of NH3 desorption of the serial catalysts.
worst NH3 -SCR performance though it owned the maximum acid quantity, suggesting that the number
of acid sites was not the only factor to affect catalytic Proportion of NH3Moreover,
performance. desorptionto (%)
our great interest,
Total amount of
catalystscatalyst possessed thea lowest number
the NiFe-600 Weak acid
acid sites,
sites but its high-temperature
Strong acid DeNO sites x activity
NH3 desorption
was satisfactory. The DeNOx mechanism was (55–300 further °C)analyzed as below. It(300–700 °C)
was confirmed that an
NiFe-400
iron-based mixed oxide catalyst 1 34.5
would follow the Langmuir–Hinshelwood 65.5 under 250 ◦ C,
mechanism
whereNiFe-500
both NH3 and NO 0.65 would be adsorbed to 42.5 all of the acid sites and then57.5 transformed to the
NiFe-600 0.27 52.4
corresponding intermediate [36]. The dramatic decrease of acid quantity for NiFe-600 resulted in the 47.6
a Normalized by the NH3 desorption peaks area of the NiFe-400 sample (28,487.8 a.u.).
absence of adsorption of the reactant; accordingly, the low-temperature activity decreased. At medium
and higher temperatures, the catalyst would fit the Eley–Rideal mechanism [31,37], where only the
Table 3. The reduction peaks temperature (°C) and H2 consumption (mmol g-1) of each catalyst.
adsorption and activation process of NH3 was conducted, generating the reaction between the adsorbed
intermediate and gaseous-state Peak 1 NO. Therefore, Peak
the2residual acid Total
sitesactual
were H still Total theoretical
2 enough to absorb the
catalysts
majority of the NH T1 3 despite
A1 the evident
E1 Tdecrease.
2 A2 E2 consumption H2 consumption
NiFe-400 333 13.99 13.86 427 0.59 0.77 14.58 14.63
NiFe-500 333 14.21 14.05 (BET)
Table 1. Brunauer–Emmett–Teller 428 surface
0.41 areas0.88 14.62diameter of the samples.
and average pore 14.93
NiFe-600 357 13.68 12.10 444 0.95 2 2.62 14.63 14.72
Catalysts BET Surfaces Areas (m /g) Average Pore Diameter (nm)

where T1 and TNiFe-400


2 refer to the reduction peak temperature; A1 and A2 refer to
169.3 5.1the actual H2 consumption
of peak 1 and peak 2, respectively; and E1 and E2 refer to the theoretical4.0
NiFe-500 89.6 H2 consumption of peak 1
NiFe-600 20.9 15.5
and peak 2, respectively.

Figure
Figure 5. NH
5. NH 3-TPD
3 -TPD profiles(A)
profiles (A)and
andH
H22-TPR
-TPR patterns
patterns (B)
(B)of
ofthe
theserial
serialNiFe
NiFecatalysts.
catalysts.

TheXPSH2 analysis was performed


-TPR technique to determine
was employed the surface
to determine thecomponents
reducibilityand valence
of the states ofNiFe
as-prepared elements
mixed
presented
oxides on the
catalysts. catalyst
Over surfaces.
all samples, twoThe XPS spectra
noticeable of Fe 2p
reduction andare
peaks Niexhibited
2p3/2 are shown in Figure
in Figure 6 and
5B. According
the literature
to the corresponding surface
[38,39], atomic concentrations
the reduction peak locatedasatwell as the proportion
the lower temperature ofregion
different valence◦states
(200–400 C) may
be are listed in
assigned toTable 4.
the reduction of Ni2+ (Ni3+ ) to Ni0 (Peak 1), and the reduction peak at the higher
Catalysts 2018, 8, 384 7 of 12

temperature region (400–450 ◦ C) could represent the reduction of Fe species (Peak 2). However, it was
reported that the reduction peaks of mixed oxides usually do not correspond to only one kind of metal
oxide [40]. Hence, the theoretical (denoted as E) and actual (denoted as A) H2 consumption of each
catalyst were calculated and are shown in Table 3. For all samples, the amount of total theoretical
H2 consumption was higher than that of the total actual H2 consumption, implying the existence of
an incomplete reduction of active species. Therein, the actual H2 consumption amount of Ni species
(peak 1) was higher than the theoretical values for each catalyst (A1 > E1 ), while Fe species (peak 2)
were the opposite (A2 < E2 ). Therefore, the first reduction peak may be ascribed to the co-reduction
of Ni as well as partial Fe species and the second peak may be only attributed to the Fe species.
From Table 3, it was also clear that the NiFe-400 and NiFe-500 catalysts exhibited a similar position of
reduction peaks and the NiFe-600 catalyst significantly shifted to high-temperature zones, presenting
the worst reducibility for NiFe-600, which can well-explain its degraded DeNOx activity at a low
temperature compared with the NiFe-400 and NiFe-500 catalysts.

Table 2. Amount and proportion of NH3 desorption of the serial catalysts.

Proportion of NH3 Desorption (%)


Total Amount of NH3
Catalysts
Desorption a Weak Acid Sites Strong Acid Sites
(55–300 ◦ C) (300–700 ◦ C)
Catalysts 2018, 8, x FOR PEER REVIEW 8 of 12
NiFe-400 1 34.5 65.5
NiFe-500 0.65 42.5 57.5
According to Table 4, the amounts of surface Fe species showed a monotonic increase for the
NiFe-600 0.27 52.4 47.6
NiFe-400, NiFe-500, and NiFe-600 catalysts. As discussed in the XRD analysis section, when NiFe-
a Normalized by the NH desorption peaks area of the NiFe-400 sample (28,487.8 a.u.).
LDH was calcined at 400 °C, iron species existed in the form of FeOx, which should be mostly covered
3

by Ni species.
Table 3. With the increment
The reduction of calcination
peaks temperature temperature,
(◦ C) and NiFe2(mmol
H2 consumption O4 spinels
g−1 ) were
of eachgenerated.
catalyst. Fe
species were gradually exposed or transferred to the surface of the catalysts, and the ideal model is
displayed in Figure 6. ItPeak is well-known
1 that more
PeakFe2species could result
Total ActualinH
better
2 high-temperature
Total Theoretical
Catalysts
activity; thus, DeNO T1 x activity
A1 at high
E1 temperatures
T2 A2(>330 °C)
E2 displaying the order of 2NiFe-600 > NiFe-
Consumption H Consumption
500 > NiFe-400
NiFe-400 can be
333 reasonable.
13.99 13.86 427 0.59 0.77 14.58 14.63
NiFe-500 333 14.21 14.05 428 0.41 0.88 14.62 14.93
NiFe-600 357 Table 4. Surface atomic concentration and oxidation
13.68 12.10 444 0.95 2.62 states.
14.63 14.72
where T1 and T2 refer to the reduction peak temperature; A1 and A2 refer to the actual H2 consumption of peak 1
and peak 2, respectively; and E1 and E2 Fe 2pto the theoretical H2 consumptionNiof 2p
refer peak 1 and peak 2, respectively.
catalysts Fe Fe3+ / (Fe2+ + Fe3+) Ni Ni3+ / (Ni2+ + Ni3+)
(%)
XPS analysis was performed (%) the surface(%)
to determine components and (%)valence states of elements
presented on NiFe-400 1.7
the catalyst surfaces. The XPS 51.4
spectra of Fe28.3
2p and Ni 2p3/272.5
are shown in Figure 6 and
NiFe-500 2.2 43.8 30.9
the corresponding surface atomic concentrations as well as the proportion 75.5
of different valence states
NiFe-600
are listed in Table 4. 5.4 66.5 25.6 60.1

Figure 6. The ideal model of catalysts with MOx (M = Ni or Fe) or multiple phases (MOx and a
Figure
NiFe26.O4The ideal model of catalysts with MOx (M = Ni or Fe) or multiple phases (MOx and a NiFe2O4
spinel).
spinel).
According to Table 4, the amounts of surface Fe species showed a monotonic increase for the
For theNiFe-500,
NiFe-400, XPS spectra
and of Fe 2p in
NiFe-600 Figure 7A,
catalysts. two main in
As discussed peaks assigned
the XRD to Fe
analysis 2p3/2 and
section, FeNiFe-LDH
when 2p1/2 can
bewas
observed
calcinedcentered
at 400 C,atiron
◦ a binding energy in
species existed ofthe
approximately
form of FeOx ,711 eV should
which and 724beeV, respectively.
mostly covered byByNi
performing peak-fitting deconvolution, the Fe 2p3/2 spectra were fitted into sub-bands located at
approximately 710.9 eV and 712.7 eV, which corresponded to Fe2+ and Fe3+, respectively [41]. As
shown in Figure 7B, the Ni 2p3/2 spectra can be separated into three characteristic peaks at 854.1, 855.9,
and 861.4 eV, which can be ascribed to the Ni2+, Ni3+, and satellite peaks, respectively [42]. Combined
with the data in Table 2, it was clear that the Ni3+ content on the surface of the NiFe-500 sample (75.5%)
According
displayed to Table
in Figure 6. It4,isthe amounts of
well-known thatsurface
more Fe species
species couldshowed a monotonic
result increase for the
in better high-temperature
LDH was calcined
NiFe-400, at 400 °C,and
NiFe-500, iron species existed
NiFe-600 in the
catalysts. As form of FeO
discussed inx, which should be mostly covered
the XRD analysis section, when >NiFe-
activity; thus, DeNOx activity at high temperatures (>330 °C) displaying the order of NiFe-600 NiFe-
by Ni LDH
species. With the increment of calcination temperature, NiFe 2O4 spinels were generated. Fe
500 >was calcined
NiFe-400 at be
can 400reasonable.
°C, iron species existed in the form of FeOx, which should be mostly covered
speciesbywere gradually
Ni species. exposed
With or transferred
the increment to the surface
of calcination of the catalysts,
temperature, NiFe2Oand the ideal model is
4 spinels were generated. Fe
displayed in Figure 6. It is well-known
species were gradually exposed Table 4. or that more
transferred
Surface Fe species could
to the surface
atomic concentration result
and in
ofoxidation better
the catalysts, high-temperature
states. and the ideal model is
activity; thus, DeNO x activity at high temperatures (>330 °C) displaying
displayed in Figure 6. It is well-known that more Fe species could result in better
Catalysts 2018, 8, 384 the order of NiFe-600 > NiFe-
high-temperature 8 of 12
500 > NiFe-400 can be reasonable. Fe 2p Ni 2p
activity; thus, DeNOx activity at high temperatures (>330 °C) displaying3+the order of NiFe-600 > NiFe-
catalysts Fe Fe3+ / (Fe2+ + Fe3+) Ni Ni / (Ni2+ + Ni3+)
500 > NiFe-400 can be reasonable.
species.Table
With4. the (%)atomic concentration
Surface
increment (%)
of calcination (%) states. NiFe
and oxidation
temperature, (%)O spinels were generated. Fe species
2 4
NiFe-400 1.7 51.4 28.3 72.5
were gradually Table 4. Fe
Surface
exposed 2p oratomic concentration
transferred to the and oxidation
surface
Ni 2p of states.
the catalysts, and the ideal model is displayed
NiFe-500 2.23+ 43.8 30.93+ 75.5
catalysts
in Figure 6.FeIt is well-known
Fe / (Fe 2+
Fe 2p+ Fe
that) more
3+ NiFe species
Ni / (Ni could
2+ + Ni
result
3+ ) in better high-temperature activity;
NiFe-600 5.4 66.5 25.6 ◦ Ni 2p 60.1
thus, catalysts
DeNO (%)
x activity
Fe at (%)
high temperatures
Fe / (Fe + Fe )
3+ 2+ (%)
3+ (>330
Ni C)(%)
Ni / (Ni + Nithe
displaying
3+ 2+ 3+) order of NiFe-600 > NiFe-500 >
NiFe-400
NiFe-400 can 1.7be reasonable.
(%) 51.4 (%) 28.3 (%) 72.5 (%)
NiFe-500NiFe-400 2.2 1.7 43.8 51.4 30.9 28.3 75.5 72.5
NiFe-600NiFe-500 5.4 2.2 66.5 4.43.8
Table Surface 25.6
atomic30.9 60.1 75.5
concentration and oxidation states.
NiFe-600 5.4 66.5 25.6 60.1
Fe 2p Ni 2p
Catalysts
Fe (%) 3+ 2+
Fe / (Fe + Fe ) (%) 3+ Ni (%) Ni3+ / (Ni2+ + Ni3+ ) (%)
NiFe-400 1.7 51.4 28.3 72.5
NiFe-500 2.2 43.8 30.9 75.5
NiFe-600 5.4 66.5 25.6 60.1
Figure 6. The ideal model of catalysts with MOx (M = Ni or Fe) or multiple phases (MOx and a NiFe2O4
spinel).
For the XPS spectra of Fe 2p in Figure 7A, two main peaks assigned to Fe 2p3/2 and Fe 2p1/2 can be
Forobserved
the XPS spectra centered of Feat 2p in Figure
a binding 7A, two
energy of main peaks assigned
approximately 711 eV to Feand 2p724
3/2 andeV,Fe 2p1/2 can By performing
respectively.
Figure 6. The idealcentered
be observed model of catalysts
at a binding with MO x (M = Ni or Fe) or multiple phases (MOx and a NiFe2O4
energy of 2p approximately 711 eV andinto 724 sub-bands
eV, respectively. By at approximately
peak-fitting deconvolution, the Fe 3/2 spectra were fitted located
spinel).
performing peak-fitting deconvolution, the Fe
Figure 6. The ideal model of catalysts with MO x (M2p = 3/2 spectra
Ni or Fe) or were fitted
multiple
2+ phases
3+ into(MO sub-bands
x and a NiFe located
2O4 at
710.9 eV and 712.7 eV, which corresponded to Fe and Fe , respectively [41]. As shown in Figure 7B,
approximately
spinel). 710.9 eV and 712.7 eV, which corresponded to Fe2+ and Fe3+, respectively [41]. As
For the XPSthe spectra
Ni 2pof 3/2 Fe 2p
spectra in Figure
can be 7A, two
separated main peaks
into threeassigned to
characteristic Fe 2p and
peaks
3/2 Fe
at 2p
854.1,
1/2 can 855.9, and 861.4 eV, which
shown in Figure 7B, the Ni 2p3/2 spectra can3+ be separated into three characteristic peaks at 854.1, 855.9,
be observed centered
can be at a binding
ascribed to energy
the Ni of
2+ , approximately
Ni , and satellite711 eV and
peaks, 724 eV,
respectively respectively.
[42]. By
Combined with the data in
andFor theeV,
861.4 XPS spectra
which canof beFe 2p in Figure
ascribed to the 7A, Ni2+two, Ni3+main, and peakssatellite assigned to Fe 2p3/2 and
peaks, respectively [42].FeCombined
2p1/2 can
performing
bewith peak-fitting
observed deconvolution, the Fe 2p3+3/2 spectra were fitted into sub-bands located at
datacentered
theTable in2,Table
it was at
2, itaclear
binding
was thatenergy
clear the the
that Ni of approximately
Nicontent
3+ contenton on the
the 711
surface
surfaceeV and ofof the 724
the eV, respectively.
NiFe-500
NiFe-500 sample sample By(75.5%) was higher
(75.5%)
approximately
performing 710.9 eV and
peak-fitting 712.7 eV, which
deconvolution, corresponded
the Fe 2p to Fethe
spectra
2+ and Fe3+, respectively [41]. 3+
were fitted into sub-bands Asspecies
located at was opposite for
was higher than that of the NiFe-400 sample (72.5%), but the content of the surface Fe species was
than that of the NiFe-400 sample (72.5%), 3/2 but content of the surface 3+Fe
shownapproximately
in Figure 7B, the Ni 2p
710.9 eV3/2 spectra can be separated into three characteristic
and 712.7 eV, which corresponded to Fe 2+ and peaks Fe at 854.1, 855.9,
3+, respectively [41]. As
oppositethe fortwo the catalysts,
two catalysts, which which indicated
indicated thatthat increasing
increasing the thecalcination
calcinationtemperaturetemperature could could result in a redox
and 861.4
showneV, which can betheascribed to the Ni2+ , Nibe 3+, and satellite peaks, respectively [42]. Combined
resultin Figure
inreaction
a redox 7B, reactionNi 2pbetween
3/2 spectra
2+ Ni can
2+ and
3+ separated
Fe 3+ to form into
3+ three
Ni 3+ and characteristic
2+Fe 2+ (Ni2+ 2+ +peaks
Fe3+3+ ↔at 854.1,
Ni 855.9,
Ni +FeFe).2+ ). However, the
3+
3+ + 2+
with the
anddata in Table
861.4 eV, 2, itbetween
which was
can clear
be
Ni the
that
ascribed
andNithe
to
Fe
3+ content
Ni
to form
2+, Ni on
3+, the
and
Nisurface and
satellite
Fe
ofpeaks, (Ni +sample
the NiFe-500 respectively
Fe (75.5%)
[42]. Combined
However, the amount of surface 3+Nidecreased
3+decreasedto to 60.1% with withthe increase inin calcination temperature
temperature from 500 ◦ C
was higher
with than
the that
amount
data of the NiFe-400
of surface Nisample (72.5%), but60.1%the on content of the
the surface
increase Fecalcination
3+ species was
from 500 °Cin toTable
600
◦ °C2, it
forwas theclear
NiFethat the Ni3+
catalyst, content
which can bethe surface
attributed oftothe theNiFe-500
formation sample
of more (75.5%)
high-
opposite
was for thetotwo
higher
600catalysts,
than
C for
that
thewhich NiFe indicated
catalyst, that
which increasing
can be the calcination
attributed to temperature
the formation could of more high-crystallinity
2O4of the NiFe-400 sample (72.5%), but the content ofFethe surface 3+ +Fe species was
3+ ↔ 3+2+
crystallinity NiFe spinels, so2+it was difficult for the reaction (Ni 2+ + Ni Fe ) to occur on
result opposite
in a redox forreaction
the two between
catalysts, Ni anddifficult
itwhich Fe to form
3+
indicated forthat Niincreasing
3+ and Fe (Ni 2+ (Nicalcination
the 2+2+
++Fe Fe ↔ Ni
3+3+
Ni Ni++
2+ + Fe3+ temperature
3+
3+ Fe ). 2+
2+ 2+
NiFe
the surface of2Othe4 spinels,
catalyst. so
Thus, wascomparatively, the
the reaction
redox reaction (Ni ↔ + Fe could
3+ Fe ) )tomayoccur on the surface
However, the
result amount of surface Ni 3+decreased to 60.1% with the increase in calcination temperature
↔ similar
morein a redox
easily
of occur
the reaction
for the Thus,
catalyst. between
NiFe-500 Ni andSuch
2+
sample.
comparatively, Fe interaction
3+ to form
the redox Niin3+ andbimetallic
the
reaction Fe(Ni
2+ (Ni +
2+ 2+ +FeFe was
oxide 3+
3+ Ni
Ni ++to
3+
3+ Fe 2+). ) may more easily
Fethat
2+
from 500 °C to 600
However, the °C for theofNiFe
amount surface catalyst,
Ni which can
3+decreased to be
60.1%attributed
with theto increase
the formation in of moretemperature
calcination high-
previouslyoccur reported [30,43]
for thesoNiFe-500 and it was
sample. considered to be favorable for the creation of a redox cycle and
crystallinity
from NiFe
500 °C2Oto4 spinels,
600 the °C for itthe
was NiFedifficult
catalyst, for Such
the
which
interaction
reaction
can be(Ni
2+ +in Fethe
attributed
3+ ↔ bimetallic
to Ni
3+ + Fe2+oxide
the formation ) to occur wasonsimilar to that previously
of more high-
further promoted
reported catalytic
[30,43] and activity,
it was especially
considered at low
to betemperatures.
favorable for the creation of a redox cycle and further
Catalysts 2018, 8, x FOR PEER REVIEW 9 of 12
the surface of the catalyst.
NiFe2O4 Thus, comparatively, the redox
for thereaction
reaction(Ni (Ni2+ ++ Fe Fe3+ ↔ Ni3+ ++ Fe Fe2+)) to may
2+ 3+ 3+ 2+
crystallinity spinels, so it was difficult ↔ Ni occur on
more easily occur for
promoted the NiFe-500
the catalytic sample. Such
activity, interaction
especially
the surface of the catalyst. Thus, comparatively, the redox reaction (Ni + Fe ↔ Ni + Fe ) mayin the
at bimetallic
low oxide
temperatures. 2+ was 3+ similar 3+to that 2+
previously
morereported
easily occur [30,43]for and it was considered
the NiFe-500 sample. Such to beinteraction
favorable for the bimetallic
in the creation ofoxide a redox was cycle
similarandto that
furtherpreviously
promotedreported
the catalytic activity, especially at low temperatures.
[30,43] and it was considered to be favorable for the creation of a redox cycle and
further promoted the catalytic activity, especially at low temperatures.

Figure 7. XPS
Figure 7. XPS spectra
spectra of
of the
the serial
serial catalysts:
catalysts: (A)
(A) Fe
Fe 2p
2p and
and (B)
(B) Ni
Ni 2p.
2p.

3. Materials and Methods

3.1. Catalyst Preparation


The NiFe hydrotalcite-like precursor with the molar ratio of Ni to Fe being 4 was prepared by
the urea hydrolysis method [44]. First, a urea solution and a mixed solution with Ni(NO3)2·6H2O,
Catalysts 2018, 8, 384 9 of 12

3. Materials and Methods

3.1. Catalyst Preparation


The NiFe hydrotalcite-like precursor with the molar ratio of Ni to Fe being 4 was prepared by
the urea hydrolysis method [44]. First, a urea solution and a mixed solution with Ni(NO3 )2 ·6H2 O,
Fe(NO3 )3 ·9H2 O, and sodium citrate in the corresponding ratio were dissolved fully with deionized
water. Afterwards, the solution was transferred to a beaker and hydrothermally treated at 120 ◦ C for
24 h. The NiFe-LDH precursors were obtained after extraction, filtration, washing, and drying at 60 ◦ C
for 12 h. Subsequently, the precursors were calcined at the required temperature (400–600 ◦ C) for 5 h to
obtain the NiFe mixed oxides. Finally, the NiFe catalysts were crushed and sieved through 40–60 mesh
for catalytic evaluation.

3.2. Catalyst Characterization


XRD patterns of the samples were characterized using a DX-2700 instrument (Dandong Aolong
Radiative Instrument Group Co. Ltd, Liaoning, China) with a Cu Kα radiation source (λ = 1.54184 Å,
40 KV, and 30 mA) in the 2θ range of 5–85◦ at a step of 8◦ min−1 . The FTIR spectrum was recorded
on a TENSOR II FTIR spectrophotometer (Bruker, Billerica, MA, USA). The hydrotalcite-like samples
were pressed into KBr pellets. TG coupled with MS analysis was employed to analyze the thermal
decomposition of the NiFe-LDH precursor. A Mettler Toledo 851® thermobalance system (Balzers
Ltd., Milton Keynes, UK) was used for TG measurements, which were carried out in a flow of Ar
(80 mL min−1 ) for a temperature range of 25–800 ◦ C with a heating rate of 10 K min−1 . A ThermoStar
Balzers MS (Balzers Ltd., Milton Keynes, UK) was used to monitor the evolved gases during the
thermal decomposition process. The textural structures of the NiFe-LDO catalysts were determined
using an ASAP 2460 automated gas sorption (Micromeritics, Norcross, GA, USA) analyzer through the
N2 adsorption-desorption equilibrium at −196 ◦ C. The specific surface area and pore diameter were
determined and calculated by the Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH)
methods, respectively. H2 -TPR and NH3 -TPD were performed on a TP-5080 instrument (Xianquan
Industry and Trade Development Co. Ltd, Tianjin, China) coupled with MS using 0.08 g catalysts.
Prior to the H2 -TPR test, the sample was pre-treated at 300 ◦ C for 1 h in an Ar flow and then cooled to
room temperature. Subsequently, the feeding gas was switched from Ar to 10% H2 /Ar (20 mL min−1 )
and the temperature was increased from 30 ◦ C to 900 ◦ C with a heating rate of 10 K min−1 . In the case
of NH3 -TPD, the samples were also pre-treated at 300 ◦ C for 1 h, cooled to room temperature in a flow
of He, and then saturated with 3% NH3 /He (25 mL min−1 ) for 1 h at 50 ◦ C. After NH3 exposure, the
sample was purged with He until excessive NH3 was removed. Then, the TPD data were collected
from 30 ◦ C to 900 ◦ C at a rate of 10 K min−1 in He flow. XPS were recorded on a Thermo ESCALAB
250XI electron spectrometer (Thermo Fisher Scientific, Waltham, MA, USA) with Al Kα as a radiation
source (1486.6 eV). Binding energies of Ni 2p and Fe 2p were calibrated based on the graphite C 1s
core level at 284.8 eV.

3.3. Catalytic Performance Tests


The NH3 -SCR activities over the catalysts were evaluated in a fixed-bed reactor with 0.38 g
catalysts (40–60 mesh). The feed gas consisted of 600 ppm NO, 600 ppm NH3 , 5.0% O2 , 0 or 10.0%
H2 O, 0 or 100 ppm SO2 , and balanced with N2 at a flow rate of 350 cm3 min−1 , and the gas hourly
space velocity (GHSV) was 45,000 h−1 . The inlet and outlet gas concentrations of NO, N2 O, NO2 ,
and NH3 were detected by an online Fourier-transform-IR spectrometer (MultiGasTM 6030) (MKS,
Andover, MA, USA). The SCR reaction was carried out in the temperature range of 150–450 ◦ C and the
Catalysts 2018, 8, 384 10 of 12

data were recorded when the steady-state reaction was maintained after 30 min at each temperature.
The NOx conversion and N2 selectivity were calculated according to the following expression:

[NO]in − [NO]out
NOX conversion(%) = × 100%
[NO]in

[NO]in + [NH 3 ]in − [NO 2 ]out − 2 [N 2 O]out


N2 selectivity(%) = × 100%
[NO]in + [NH 3 ]in
where [NO]in and [NH3 ]in refer to the inlet concentrations of NO and NH3 , respectively, and [NO]out ,
[NO2 ]out , and [N2 O]out refer to the reactor outlet concentrations of NO, NO2 , and N2 O, respectively.

4. Conclusions
A series of NiFe mixed oxides catalysts derived from hydrotalcite-like precursors were prepared
and novelly employed as NH3 -SCR catalysts. The result proposed that the ideal phase composition
of NiFe mixed oxides catalysts was available via adjusting the calcination temperature of NiFe-LDH,
which had a significant effect on DeNOx activity. The oxide phase formed at a lower calcination
temperature is propitious for a better redox property and low-temperature activity, while the presence
of NiFe2 O4 spinels could contribute to high-temperature activity as well as SO2 resistance and stability.
We testify to NiFe-500 being the optimal catalyst incorporating NiO and NiFe2 O4 spinels, where
the virtues of the two phases were synergistically exerted and the best NH3 -SCR performance
was achieved.

Author Contributions: X.W. and Y.D. designed and administered the experiments. C.Z. and X.L. performed
experiments. R.W. collected and analyzed data. R.W., X.W., and Y. D wrote the manuscript.
Acknowledgments: The project was supported by National Natural Science Foundation of China (No. 21073131),
Shanxi Provincial (No. 201601D10207).
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Gao, F.; Tang, X.; Yi, H.; Zhao, S.; Li, C.; Li, J.; Shi, R.; Meng, X. A review on selective catalytic reduction
of NOx by NH3 over Mn-based catalysts at low temperatures: Catalysts, mechanisms, kinetics and DFT
calculations. Catalysts 2017, 7, 199. [CrossRef]
2. Liu, F.; Shan, W.; Lian, Z.; Liu, J.; He, H. The smart surface modification of Fe2 O3 by WOx for significantly
promoting the selective catalytic reduction of NOx with NH3 . Appl. Catal. B Environ. 2018, 230, 165–176.
[CrossRef]
3. Wang, W.; McCool, G.; Kapur, N.; Yuan, G.; Shan, B.; Nguyen, M.; Graham, UM.; Davis, BH.; Jacobs, G.;
Cho, K.; Hao, X. Mixed-phase oxide catalyst based on Mn-mullite (Sm, Gd) Mn2 O5 for NO oxidation in
diesel exhaust. Science 2012, 337, 832–835. [CrossRef] [PubMed]
4. Boningari, T.; Smirniotis, P.G. Impact of nitrogen oxides on the environment and human health: Mn-based
materials for the NOx abatement. Curr. Opin. Chem. Eng. 2016, 13, 133–141. [CrossRef]
5. Zong, L.; Zhang, G.; Zhao, J.; Dong, F.; Zhang, J.; Tang, Z. Morphology-controlled synthesis of 3D flower-like
TiO2 and the superior performance for selective catalytic reduction of NOx with NH3 . Chem. Eng. J. 2018,
343, 500–511. [CrossRef]
6. Zhang, K.; Yu, F.; Zhu, M.; Dan, J.; Wang, X.; Zhang, J. Enhanced low temperature no reduction performance
via MnOx -Fe2 O3 /vermiculite monolithic honeycomb catalysts. Catalysts 2018, 8, 100. [CrossRef]
7. Rizzotto, V.; Chen, P.; Simon, U. Mobility of NH3 -solvated cull ions in Cu-SSZ-13 and Cu-ZSM-5 NH3 -SCR
catalysts: A comparative impedance spectroscopy study. Catalysts 2018, 8, 162. [CrossRef]
8. Pappas, D.K.; Boningari, T.; Boolchand, P.; Smirniotis, P.G. Novel manganese oxide confined interweaved
titania nanotubes for the low-temperature selective catalytic reduction (SCR) of NOx , by NH3 . J. Catal. 2016,
334, 1–13. [CrossRef]
Catalysts 2018, 8, 384 11 of 12

9. Liu, F.; He, H. Structure-activity relationship of iron titanate catalysts in the selective catalytic reduction of
NOx with NH3 . J. Phys. Chem. C 2010, 114, 16929–16936. [CrossRef]
10. Liu, C.; Yang, S.; Ma, L.; Peng, Y.; Hamidreza, A. Comparison on the performance of α-Fe2 O3 and γ-Fe2 O3
for selective catalytic reduction of nitrogen oxides with ammonia. Catal. Let. 2013, 143, 697–704. [CrossRef]
11. Liu, F.; He, H.; Zhang, C.; Feng, Z.; Zheng, L.; Xie, Y.; Hu, T. Selective catalytic reduction of NO with NH3 over
iron titanate catalyst: Catalytic performance and characterization. Appl. Catal. B Environ. 2010, 96, 408–420.
[CrossRef]
12. Yang, S.; Li, J.; Wang, C.; Chen, J.; Ma, L.; Chang, H.; Yan, N. Fe-Ti spinel for the selective catalytic reduction
of NO with NH3 : Mechanism and structure–activity relationship. Appl. Catal. B Environ. 2012, 117, 73–80.
[CrossRef]
13. Chen, Z.; Wang, F.; Li, H.; Yang, Q.; Wang, L.; Li, X. Low-temperature selective catalytic reduction of NOx
with NH3 over Fe–Mn mixed-oxide catalysts containing Fe3 Mn3 O8 phase. Ind. Eng. Chem. Res. 2012, 51,
202–212. [CrossRef]
14. Pena, D.A.; Uphade, B.S.; Smirniotis, P.G. TiO2 -supported metal oxide catalysts for low-temperature selective
catalytic reduction of NO with NH3 : I. Evaluation and characterization of first row transition metals. J. Catal.
2004, 221, 421–431. [CrossRef]
15. Liu, Z.; Liu, H.; Feng, X.; Ma, L.; Cao, X.; Wang, B. Ni-Ce-Ti as a superior catalyst for the selective catalytic
reduction of NOx with NH3 . Mol. Catal. 2018, 445, 179–186. [CrossRef]
16. Thirupathi, B.; Smirniotis, P.G. Nickel-doped Mn/TiO2 as an efficient catalyst for the low-temperature SCR
of NO with NH3 : Catalytic evaluation and characterizations. J. Catal. 2012, 288, 74–83. [CrossRef]
17. Ueda, K.; Ang, C.A.; Ito, Y.; Ohyama, J.; Satsuma, A. NiFe2 O4 as an active component of platinum-group
metal free automotive three-way catalyst. Catal. Sci. Technol. 2016, 6, 5797–5800. [CrossRef]
18. Chen, L.; Niu, X.; Li, Z.; Dong, Y.; Zhang, Z.; Yuan, F.; Zhu, Y. Promoting catalytic performances of Ni-Mn
spinel for NH3 -SCR by treatment with SO2 and H2 O. Chem. Commun. 2016, 85, 48–51. [CrossRef]
19. Thirupathi, B.; Smirniotis, P.G. Effect of nickel as dopant in Mn/TiO2 , catalysts for the low-temperature
selective reduction of NO with NH3 . Catal. Lett. 2011, 141, 1399–1404. [CrossRef]
20. Deling, Y.; Xinyong, L.; Qidong, Z. Preparation and characterization of Ni-Ti-O mixed oxide for selective
catalytic reduction of NO under lean-burn conditions. Chin. J. Catal. 2013, 34, 1449–1455.
21. Chmielarz, L.; Rutkowska, M.; Kuśtrowski, P.; Drozdek, M.; Piwowarska, Z.; Dudek, B.; Michalik, M.
An influence of thermal treatment conditions of hydrotalcite-like materials on their catalytic activity in the
process of N2 O decomposition. J. Therm. Anal. Calorim. 2011, 105, 161–170. [CrossRef]
22. Tang, X.; Hao, J.; Xu, W.; Li, J. Low temperature selective catalytic reduction of NOx with NH3 over
amorphous MnOx catalysts prepared by three methods. Chem. Commun. 2007, 8, 329–334. [CrossRef]
23. Yan, Q.; Chen, S.; Qiu, L.; Gao, Y.; O'Hare, D.; Wang, Q. The synthesis of Cu y Mnz Al1-z Ox mixed oxide as a
low-temperature NH3 -SCR catalyst with enhanced catalytic performance. Dalton Trans. 2018, 47, 2992–3004.
[CrossRef] [PubMed]
24. Wu, X.; Ci, C.; Du, Y.; Liu, X.; Li, X.; Xie, X. Facile synthesis of NiAl-LDHs with tunable establishment of
acid-base activity sites. Mater. Chem. Phys. 2018, 211, 72–78. [CrossRef]
25. Yan, Q.; Nie, Y.; Yang, R.; Cui, Y.; O’Hare, D.; Wang, Q. Highly dispersed Cuy AlOx , mixed oxides as superior
low-temperature alkali metal and SO2 resistant NH3 -SCR catalysts. Appl. Catal. A Gen. 2017, 538, 37–50.
[CrossRef]
26. Zhang, P.; Qian, G.; Xu, Z.; Shi, H.; Ruan, X.; Yang, J; Frost, R. Effective adsorption of sodium dodecylsulfate
(SDS) by hydrocalumite (CaAl-LDH-Cl) induced by self-dissolution and re-precipitation mechanism.
J. Colloid Interface Sci. 2012, 367, 264–271. [CrossRef] [PubMed]
27. Chmielarz, L.; Kuśtrowski, P.; Rafalska-Łasocha, A.; Dziembaj, R. Influence of Cu, Co and Ni cations
incorporated in brucite-type layers on thermal behaviour of hydrotalcites and reducibility of the derived
mixed oxide systems. Thermochim. Acta 2002, 395, 225–236. [CrossRef]
28. Ballarini, N.; Cavani, F.; Passeri, S.; Pesaresi, L.; Lee, A.F.; Wilson, K. Phenol methylation over nanoparticulate
CoFe2 O4 inverse spinel catalysts: The effect of morphology on catalytic performance. Appl. Catal. A Gen.
2009, 366, 184–192. [CrossRef]
29. Yan, K.; Wu, X.; An, X.; Xie, X. Facile synthesis and catalytic property of spinel ferrites by a template method.
J. Alloy. Compd. 2013, 552, 405–408. [CrossRef]
Catalysts 2018, 8, 384 12 of 12

30. Chin, S.; Park, E.; Kim, M.; Jeong, J.; Bae, G.N.; Jurng, J. Preparation of TiO2 ultrafine nanopowder with large
surface area and its photocatalytic activity for gaseous nitrogen oxides. Powder Technol. 2011, 206, 306–311.
[CrossRef]
31. Zhao, K.; Han, W.; Tang, Z.; Lu, J.; Hu, X. High-Efficiency Environmental-Friendly Fe-W-Ti Catalyst for
Selective Catalytic Reduction of NO with NH3 : The Structure–Activity Relationship. Catal. Surv. Asia 2018,
22, 20–30. [CrossRef]
32. Zhang, Q.; Liu, X.; Ning, P.; Song, Z.; Li, H.; Gu, J. Enhanced performance in NOx reduction by NH3 over
a mesoporous Ce-Ti-MoOx catalyst stabilized by a carbon template. Catal Sci Technol. 2015, 5, 2260–2269.
[CrossRef]
33. Chen, L.; Li, R.; Li, Z.; Yuan, F.; Niu, X.; Zhu, Y. Effect of Ni doping in Nix Mn1-x Ti10 (x = 0.1–0.5) on activity
and SO2 resistance for NH3 -SCR of NO studied with in situ DRIFTS. Catal. Sci. Technol. 2017, 7, 3243–3257.
[CrossRef]
34. Xu, H.; Wang, Y.; Cao, Y.; Fang, Z.; Lin, T.; Gong, M.; Chen, Y. Catalytic performance of acidic zirconium-based
composite oxides monolithic catalyst on selective catalytic reduction of NOx with NH3 . Chem. Eng. J. 2014,
240, 62–73. [CrossRef]
35. Chang, H.; Li, J.; Su, W.; Shao, Y.; Hao, J. A novel mechanism for poisoning of metal oxide SCR catalysts:
Base-acid explanation correlated with redox properties. Chem. Commun. 2014, 50, 10031–10034. [CrossRef]
[PubMed]
36. Zhao, K.; Meng, J.; Lu, J.; He, Y.; Huang, H.; Tang, Z.; Zhen, X. Sol-gel one-pot synthesis of efficient and
environmentally friendly iron-based catalysts for NH3 -SCR. Appl. Sur. Sci. 2018, 445, 454–461. [CrossRef]
37. Wang, H.; Qu, Z.; Dong, S.; Tang, C. Mechanism study of FeW mixed oxides to the selective catalytic
reduction of NOx with NH3 : In situ DRIFTS and MS. Catal. Today 2018, 307, 35–40. [CrossRef]
38. Li, X.; Li, K.; Peng, Y.; Li, X.; Zhang, Y.; Wang, D.; Li, J. Interaction of phosphorus with a FeTiOx catalyst for
selective catalytic reduction of NOx with NH3 : Influence on surface acidity and SCR mechanism. Chem. Eng. J.
2018, 347, 173–183. [CrossRef]
39. Jiang, J.; Pan, H.; Sun, G.; Ye, Q.; Shao, Z.; Shi, Y. Promotion of Ni/H-BEA by Fe for NOx Reduction with
Propane in a Lean-Burn Condition. Energ. Fuel 2011, 25, 4377–4383. [CrossRef]
40. Sun, C.; Liu, H.; Chen, W.; Chen, D.; Yu, S.; Liu, A.; Dong, L.; Feng, S. Insights into the Sm/Zr co-doping
effects on N2 selectivity and SO2 resistance of a MnOx -TiO2 catalyst for the NH3 -SCR reaction. Chem. Eng. J.
2018, 347, 27–40. [CrossRef]
41. Tiwari, S.; Prakash, R.; Choudhary, R.J.; Phase, D.M. Oriented growth of Fe3 O4 thin film on crystalline and
amorphous substrates by pulsed laser deposition. J. Phys. D Appl. Phys. 2007, 40, 4943. [CrossRef]
42. Wan, Y.; Zhao, W.; Tang, Y.; Li, L.; Wang, H.; Cui, Y.; Shi, J. Ni-Mn bi-metal oxide catalysts for the low
temperature SCR removal of NO with NH3 . Appl. Catal. B Environ. 2014, 148, 114–122. [CrossRef]
43. Kang, M.; Park, E.D.; Kim, J.M.; Yie, J.E. Cu-Mn mixed oxides for low temperature NO reduction with NH3 .
Catal. Today 2006, 111, 236–241. [CrossRef]
44. Ogawa, M.; Asai, S. Hydrothermal synthesis of layered double hydroxide-deoxycholate intercalation
compounds. Chem. Mater. 2000, 12, 3253–3255. [CrossRef]

© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).