Next Article in Journal
Two Possible Side Reaction Pathways during Furanic Etherification
Next Article in Special Issue
Study of Chemical and Morphological Transformations during Ni2Mo3N Synthesis via an Oxide Precursor Nitration Route
Previous Article in Journal
Modeling the OEC with Two New Biomimetic Models: Preparations, Structural Characterization, and Water Photolysis Studies of a Ba–Mn Box Type Complex and a Mn4N6 Planar-Diamond Cluster
Previous Article in Special Issue
Highly Loaded and Dispersed Ni2P/Al2O3 Catalyst with High Selectivity for Hydrogenation of Acetophenone
Article Menu
Issue 9 (September) cover image

Export Article

Catalysts 2018, 8(9), 384; doi:10.3390/catal8090384

NOx Removal by Selective Catalytic Reduction with Ammonia over a Hydrotalcite-Derived NiFe Mixed Oxide
College of chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
College of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong 030619, China
Authors to whom correspondence should be addressed.
Received: 24 July 2018 / Accepted: 6 September 2018 / Published: 8 September 2018


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, NiFe2O4 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.
NiFe-LDH; mixed oxide; NiFe2O4 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 [2,3,4]. The most adopted SCR catalysts in practical applications are V-based catalysts, while the toxicity of active vanadium species, together with high N2O 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 [6,7,8]. 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 acidity sites [14] and a favorable ability to increase the N2 selectivity of NH3-SCR reactions [15,16], which was expected to be introduced into the iron-based catalytic system [17]. Furthermore, nickel oxides are considered as valuable materials to induce a synergistic effect with other active species, such as NiMnOx [18,19] and NiTiOx [20], which are very sensitive to the synthesis process.
It was reported that layered double hydroxide (LDHs) materials are excellent precursors for the preparation of metal oxide catalysts with the desired chemical and phase composition [21]. Thermal decomposition of hydrotalcite-like materials could produce layered double oxides (LDOs) possessing a relatively high surface area, which could promote the catalytic performance.
Herein, a series of economical and eco-friendly NiFe mixed oxides catalysts were prepared via calcining a hydrotalcite-like compound at various temperatures. The NH3-SCR activity, SO2 resistance, and stability were evaluated for the different NiFe mixed oxides catalysts. The correlations among phase composition, structure, and catalytic performance were systematically explored by XRD (X-ray diffraction), FT-IR (Fourier Transform Infrared), TG (thermogravimetric analysis), N2 physisorption, NH3-TPD (NH3-Temperature Programmed Desorption), H2-TPR (H2-Temperature Programmed Reduction), and XPS (X-ray Photoelectron Spectroscopy). It was proved that the DeNOx performance was highly dependent on the phase composition of NiFe mixed oxides catalysts, which was available via adjusting the calcination temperature of NiFe-LDH. This work may serve as an important reference for LDH precursors to be tailored for potential applications in adjusting the phase component and catalytic performance.

2. Results and Discussion

NH3-SCR reactions over NiFe mixed oxides catalysts at various calcination temperatures (400 °C, 500 °C, and 600 °C) were performed during 150–450 °C and the results are given in Figure 1A. It is clear that the NiFe-400 sample showed rather low NH3-SCR efficiency with an obviously narrow operation temperature window. The DeNOx activity and temperature window for the NiFe-500 and NiFe-600 samples were promoted dramatically in comparison to that of the NiFe-400 catalyst. The NiFe-600 catalyst exhibited lower NOx conversion than the NiFe-500 catalyst at temperatures below 330 °C, while it behaved better in the higher temperature region, which implied that the higher calcination temperature was conducive to high-temperature SCR activity. As demonstrated in Figure 1B, all NiFe mixed oxides catalysts afforded superior N2 selectivity: nearly 98% below 360 °C. When temperatures exceeded 360 °C, the N2 selectivity of the NiFe-500 and NiFe-600 samples showed a slight decline compared with the NiFe-400 catalyst. Obviously, the NiFe-500 catalyst was the most promising candidate for NH3-SCR, affording above 85% DeNOx activity within the widest temperature region of 210–360 °C and superior N2 selectivity over the whole tested temperature range.
The stability is an important indicator to estimate the properties 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 ppm NH3, 5.0% O2, and balanced with N2. As presented in Figure 1C, the DeNOx activity of the NiFe-500 and NiFe-600 catalysts slightly fluctuated with only ±1% variance, indicating fine stability. Comparatively, the NiFe-400 sample displayed the relatively worst stability. Such different stabilities can be ascribed to the different stabilities of the mixed oxides’ structures. Thus, the NiFe-500 and NiFe-600 catalysts possessed a more stable structure in comparison with the NiFe-400 catalyst.
The presence of H2O and SO2 in the actual exhaust usually inhibits the NH3-SCR of NOx [22]. Therefore, it is of great importance to evaluate the H2O and/or SO2 tolerance under the reaction conditions. The H2O and/or SO2 tolerance of the serial NiFe mixed oxides catalysts was investigated at 300 °C under the reaction conditions of 600 ppm NO, 600 ppm NH3, 5% O2, 0 or 100 ppm SO2, 0 or 10.0% H2O, and balanced with N2. As depicted in Figure 1D, at the first stage, the NOx conversion for the NiFe-400, NiFe-500, and NiFe-600 catalysts was maintained at around 85%, 99%, and 96%, respectively. After adding 100 ppm SO2 into the reaction gas, the NOx conversion decreased slightly. However, the co-existence of 100 ppm SO2 and 10% H2O led to a gradual decrease to some extent in NOx conversion, where the decrease was only about 2% for the NiFe-500 and NiFe-600 samples while around a 5% decrease was displayed for NiFe-400. After purging off SO2 and H2O, the NOx conversion gradually recovered to the original values. Thus, the NiFe-500 and NiFe-600 catalysts possessed an excellent SO2 and H2O resistance ability in comparison to the NiFe-400 catalyst.
XRD is an essential technology to evaluate the structure of catalysts. The XRD pattern of the NiFe-LDH precursor is presented in Figure 2A. The characteristic reflections at 2θ values of 11.7°, 23.2°, 34.5°, 39.1°, 45.6°, and 59.8° can be observed, which were correspondingly indexed to the (003), (006), (012), (015), (018), and (110) planes according to the standard card (JCPDS no.15-0087). The absence of other crystalline phases hinted at the successful fabrication of NiFe-LDHs with high purity.
The FT-IR spectrum of NiFe-LDH is illustrated in Figure 2B. An intense and board peak at 3429 cm−1 corresponded to the stretching vibration of the -OH group in the NiFe brucite-like layers, the interlayer water molecules, and the lattice water [23]. The peak that occurred at 2987 cm−1 can be assigned to a CO2–H2O bridging bond [24]. The vibration of the angular deformation of H2O molecules was observed at 1601 cm−1 [23]. The peaks at 1385 cm−1 belonged to the stretching vibrations of carbonate ions [25]. Additionally, the peak located at 676 cm−1 might be correlated to the vibration of M-O (Fe-O, Fe-O-Ni or Ni-O) on the layer of the NiFe-LDH samples [26]. Both XRD and FT-IR data confirmed that NiFe-LDH was prepared successfully with C O 3 2 - as an interlayer anion.
The process of thermal decomposition of the NiFe-LDH precursor into mixed oxides was studied by TG coupled with MS (mass spectrometer) analysis (TG-MS). From the TG and DTG (derivative thermogravimetry) curves in Figure 3A, three major weight-loss stages were observed visually. The initial reduction in mass occurred between 80 °C and 180 °C (approximately 9 wt.%) and arose from the desorption of the surface adsorbed and interlayer water and CO2 molecules. The second mass loss stage occurred at the temperature range of 190–350 °C (about 13 wt.%) and mainly released H2O, CO2, and NO2, which were detected by online MS analysis (Figure 3B). This rapid and major mass loss can be assigned to the dehydroxylation of the inorganic layers and decomposition of interlayer anions ( N O 3 - and C O 3 2 - ) [27] accompanied by the collapse of the hydrotalcite structure. A small DTG exothermic peak at about 395 °C observed in the Figure 3A corresponds to the release of CO2 and NO2 in the MS curves, which was attributed to the degradation of nitrates and carbonates with high thermal stability. Based on the above, stable NiFe mixed oxides catalysts can be obtained when hydrotalcite-like precursors are calcined at over 400 °C.
An XRD analysis was performed for the serial NiFe mixed oxides catalysts, which were produced by calcining NiFe-LDH at different temperatures (400–600 °C). As exhibited in Figure 2C, the calcination temperature was an important factor affecting the formation of crystalline phase. As the calcination temperature increases from 400 °C to 600 °C, the diffraction peaks were found to significantly sharpen, 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°, 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, Fe2O3, and Fe3O4), manifested their high dispersion or presence in the crystal lattice of NiO. The indicative diffraction peaks of NiFe2O4 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 NiFe2O4 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 NiFe2O4 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 NiFe2O4 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 NiFe2O4 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 centers, which might account for the better DeNOx performance.
The surface acidity and acid strength distribution of the NiFe mixed oxides catalysts were investigated by NH3-TPD experiments. As illustrated in Figure 5A, the NH3-TPD curves showed two ammonia desorption peaks for each sample in the 70–700 °C range. The first desorption peak centered 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 resulted in a dramatic reduction of ammonia adsorption and surface acidity. The desorption amount of NiFe-500 and NiFe-600 decreased by 35% and 73%, respectively. In addition, with the calcination temperature increasing from 400 °C to 600 °C, the proportion of weakly acidic sites shows an obvious rise from 34.5% to 52.4%, while the proportion of the strongly acidic sites decreased from 65.5% to 47.6%. Combined with the results of XRD and BET, we speculated that the increase of calcination temperature resulted 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 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 performance. Moreover, to our great interest, the NiFe-600 catalyst possessed the lowest number acid sites, but its high-temperature DeNOx activity was satisfactory. The DeNOx mechanism was further analyzed as below. It was confirmed that an iron-based mixed oxide catalyst would follow the Langmuir–Hinshelwood mechanism under 250 °C, where both NH3 and NO would be adsorbed to all of the acid sites and then transformed to the corresponding intermediate [36]. The dramatic decrease of acid quantity for NiFe-600 resulted in the 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 adsorption and activation process of NH3 was conducted, generating the reaction between the adsorbed intermediate and gaseous-state NO. Therefore, the residual acid sites were still enough to absorb the majority of the NH3 despite the evident decrease.
The H2-TPR technique was employed to determine the reducibility of the as-prepared NiFe mixed oxides catalysts. Over all samples, two noticeable reduction peaks are exhibited in Figure 5B. According to the literature [38,39], the reduction peak located at the lower temperature region (200–400 °C) may be assigned to the reduction of Ni2+ (Ni3+) to Ni0 (Peak 1), and the reduction peak at the higher 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.
XPS analysis was performed to determine the surface components and valence states of elements presented on the catalyst surfaces. The XPS spectra of Fe 2p and Ni 2p3/2 are shown in Figure 6 and the corresponding surface atomic concentrations as well as the proportion of different valence states are listed in Table 4.
According to Table 4, the amounts of surface Fe species showed a monotonic increase for the NiFe-400, NiFe-500, and NiFe-600 catalysts. As discussed in the XRD analysis section, when NiFe-LDH was calcined at 400 °C, iron species existed in the form of FeOx, which should be mostly covered by Ni species. With the increment of calcination temperature, NiFe2O4 spinels were generated. Fe species were gradually exposed or transferred to the surface of the catalysts, and the ideal model is displayed in Figure 6. It is well-known that more Fe species could result in better high-temperature activity; thus, DeNOx activity at high temperatures (>330 °C) displaying the order of NiFe-600 > NiFe-500 > NiFe-400 can be reasonable.
For the XPS spectra of Fe 2p in Figure 7A, two main peaks assigned to Fe 2p3/2 and Fe 2p1/2 can be observed centered at a binding energy of approximately 711 eV and 724 eV, respectively. By 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%) was higher than that of the NiFe-400 sample (72.5%), but the content of the surface Fe3+ species was opposite for the two catalysts, which indicated that increasing the calcination temperature could result in a redox reaction between Ni2+ and Fe3+ to form Ni3+ and Fe2+ (Ni2+ + Fe3+ Catalysts 08 00384 i001 Ni3+ + Fe2+). However, the amount of surface Ni3+ decreased to 60.1% with the increase in calcination temperature from 500 °C to 600 °C for the NiFe catalyst, which can be attributed to the formation of more high-crystallinity NiFe2O4 spinels, so it was difficult for the reaction (Ni2+ + Fe3+ Catalysts 08 00384 i001 Ni3+ + Fe2+) to occur on the surface of the catalyst. Thus, comparatively, the redox reaction (Ni2+ + Fe3+ Catalysts 08 00384 i001 Ni3+ + Fe2+) may more easily occur for the NiFe-500 sample. Such interaction in the bimetallic oxide was similar to that previously reported [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.

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, Fe(NO3)3·9H2O, 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% H2O, 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, N2O, 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 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 X   conversion ( % ) = [ NO ] in [ NO ] out [ NO ] in × 100 %
N 2   selectivity ( % ) = [ NO ] in + [ NH 3 ] in [ NO 2 ] out 2 [ N 2 O ] out [ NO ] in + [ NH 3 ] in × 100 %
where [NO]in and [NH3]in refer to the inlet concentrations of NO and NH3, respectively, and [NO]out, [NO2]out, and [N2O]out refer to the reactor outlet concentrations of NO, NO2, and N2O, 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 NiFe2O4 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 NiFe2O4 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.


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.


  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. [Google Scholar] [CrossRef]
  2. Liu, F.; Shan, W.; Lian, Z.; Liu, J.; He, H. The smart surface modification of Fe2O3 by WOx for significantly promoting the selective catalytic reduction of NOx with NH3. Appl. Catal. B Environ. 2018, 230, 165–176. [Google Scholar] [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) Mn2O5 for NO oxidation in diesel exhaust. Science 2012, 337, 832–835. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [CrossRef]
  6. Zhang, K.; Yu, F.; Zhu, M.; Dan, J.; Wang, X.; Zhang, J. Enhanced low temperature no reduction performance via MnOx-Fe2O3/vermiculite monolithic honeycomb catalysts. Catalysts 2018, 8, 100. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [CrossRef]
  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. [Google Scholar] [CrossRef]
  10. Liu, C.; Yang, S.; Ma, L.; Peng, Y.; Hamidreza, A. Comparison on the performance of α-Fe2O3 and γ-Fe2O3 for selective catalytic reduction of nitrogen oxides with ammonia. Catal. Let. 2013, 143, 697–704. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [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 Fe3Mn3O8 phase. Ind. Eng. Chem. Res. 2012, 51, 202–212. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [CrossRef]
  17. Ueda, K.; Ang, C.A.; Ito, Y.; Ohyama, J.; Satsuma, A. NiFe2O4 as an active component of platinum-group metal free automotive three-way catalyst. Catal. Sci. Technol. 2016, 6, 5797–5800. [Google Scholar] [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 H2O. Chem. Commun. 2016, 85, 48–51. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar]
  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 N2O decomposition. J. Therm. Anal. Calorim. 2011, 105, 161–170. [Google Scholar] [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. [Google Scholar] [CrossRef]
  23. Yan, Q.; Chen, S.; Qiu, L.; Gao, Y.; O'Hare, D.; Wang, Q. The synthesis of Cu y MnzAl1-zOx mixed oxide as a low-temperature NH3-SCR catalyst with enhanced catalytic performance. Dalton Trans. 2018, 47, 2992–3004. [Google Scholar] [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. [Google Scholar] [CrossRef]
  25. Yan, Q.; Nie, Y.; Yang, R.; Cui, Y.; O’Hare, D.; Wang, Q. Highly dispersed CuyAlOx, mixed oxides as superior low-temperature alkali metal and SO2 resistant NH3-SCR catalysts. Appl. Catal. A Gen. 2017, 538, 37–50. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [CrossRef]
  28. Ballarini, N.; Cavani, F.; Passeri, S.; Pesaresi, L.; Lee, A.F.; Wilson, K. Phenol methylation over nanoparticulate CoFe2O4 inverse spinel catalysts: The effect of morphology on catalytic performance. Appl. Catal. A Gen. 2009, 366, 184–192. [Google Scholar] [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. [Google Scholar] [CrossRef]
  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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [CrossRef]
  33. Chen, L.; Li, R.; Li, Z.; Yuan, F.; Niu, X.; Zhu, Y. Effect of Ni doping in NixMn1-xTi10 (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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [CrossRef]
  41. Tiwari, S.; Prakash, R.; Choudhary, R.J.; Phase, D.M. Oriented growth of Fe3O4 thin film on crystalline and amorphous substrates by pulsed laser deposition. J. Phys. D Appl. Phys. 2007, 40, 4943. [Google Scholar] [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. [Google Scholar] [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. [Google Scholar] [CrossRef]
  44. Ogawa, M.; Asai, S. Hydrothermal synthesis of layered double hydroxide-deoxycholate intercalation compounds. Chem. Mater. 2000, 12, 3253–3255. [Google Scholar] [CrossRef]
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/H2O resistance tests at 300 °C. Reaction conditions: 600 ppm NO, 600 ppm NH3, 5% O2, 100 ppm SO2 (when used), 10% H2O (when used), balance N2, gas hourly space velocity (GHSV) = 45,000 h−1.
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/H2O resistance tests at 300 °C. Reaction conditions: 600 ppm NO, 600 ppm NH3, 5% O2, 100 ppm SO2 (when used), 10% H2O (when used), balance N2, gas hourly space velocity (GHSV) = 45,000 h−1.
Catalysts 08 00384 g001aCatalysts 08 00384 g001b
Figure 2. XRD pattern (A) and FT-IR spectrum (B) of NiFe- layered double hydroxide (LDH) precursor; XRD patterns of NiFe-LDO catalysts (C).
Figure 2. XRD pattern (A) and FT-IR spectrum (B) of NiFe- layered double hydroxide (LDH) precursor; XRD patterns of NiFe-LDO catalysts (C).
Catalysts 08 00384 g002
Figure 3. Results of TG and DTG studies (A) combined with MS analysis (B) for the NiFe-LDH sample.
Figure 3. Results of TG and DTG studies (A) combined with MS analysis (B) for the NiFe-LDH sample.
Catalysts 08 00384 g003
Figure 4. N2 adsorption and desorption isotherms (A) and pore diameter distribution (B) of the serial NiFe-LDO catalysts.
Figure 4. N2 adsorption and desorption isotherms (A) and pore diameter distribution (B) of the serial NiFe-LDO catalysts.
Catalysts 08 00384 g004
Figure 5. NH3-TPD profiles (A) and H2-TPR patterns (B) of the serial NiFe catalysts.
Figure 5. NH3-TPD profiles (A) and H2-TPR patterns (B) of the serial NiFe catalysts.
Catalysts 08 00384 g005
Figure 6. The ideal model of catalysts with MOx (M = Ni or Fe) or multiple phases (MOx and a NiFe2O4 spinel).
Figure 6. The ideal model of catalysts with MOx (M = Ni or Fe) or multiple phases (MOx and a NiFe2O4 spinel).
Catalysts 08 00384 g006
Figure 7. XPS spectra of the serial catalysts: (A) Fe 2p and (B) Ni 2p.
Figure 7. XPS spectra of the serial catalysts: (A) Fe 2p and (B) Ni 2p.
Catalysts 08 00384 g007
Table 1. Brunauer–Emmett–Teller (BET) surface areas and average pore diameter of the samples.
Table 1. Brunauer–Emmett–Teller (BET) surface areas and average pore diameter of the samples.
CatalystsBET Surfaces Areas (m2/g)Average Pore Diameter (nm)
Table 2. Amount and proportion of NH3 desorption of the serial catalysts.
Table 2. Amount and proportion of NH3 desorption of the serial catalysts.
CatalystsTotal Amount of NH3 Desorption aProportion of NH3 Desorption (%)
Weak Acid Sites (55–300 °C)Strong Acid Sites (300–700 °C)
a Normalized by the NH3 desorption peaks area of the NiFe-400 sample (28,487.8 a.u.).
Table 3. The reduction peaks temperature (°C) and H2 consumption (mmol g−1) of each catalyst.
Table 3. The reduction peaks temperature (°C) and H2 consumption (mmol g−1) of each catalyst.
CatalystsPeak 1Peak 2Total Actual H2 ConsumptionTotal Theoretical H2 Consumption
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 refer to the theoretical H2 consumption of peak 1 and peak 2, respectively.
Table 4. Surface atomic concentration and oxidation states.
Table 4. Surface atomic concentration and oxidation states.
CatalystsFe 2pNi 2p
Fe (%)Fe3+ / (Fe2+ + Fe3+) (%)Ni (%)Ni3+ / (Ni2+ + Ni3+) (%)

© 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 (
Catalysts EISSN 2073-4344 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top