Morphology-controlled synthesis of 3D

flower-like TiO2 and the superior

performance for selective catalytic
reduction of NOx with NH3 Luyao Zong
& Guodong Zhang & Jiuhu Zhao & Fang
Dong & Jiyi Zhang & Zhicheng Tang
Visit to download the full and correct content document:
https://ebookmass.com/product/morphology-controlled-synthesis-of-3d-flower-like-tio2
-and-the-superior-performance-for-selective-catalytic-reduction-of-nox-with-nh3-luyao
-zong-guodong-zhang-jiuhu-zhao-fang-dong-jiyi-zhang/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Elsevier Weekblad - Week 26 - 2022 Gebruiker

https://ebookmass.com/product/elsevier-weekblad-
week-26-2022-gebruiker/

Jock Seeks Geek: The Holidates Series Book #26 Jill

Brashear

https://ebookmass.com/product/jock-seeks-geek-the-holidates-
series-book-26-jill-brashear/

The New York Review of Books – N. 09, May 26 2022

Various Authors

https://ebookmass.com/product/the-new-york-review-of-
books-n-09-may-26-2022-various-authors/

Calculate with Confidence, 8e (Oct 26,

2021)_(0323696953)_(Elsevier) 8th Edition Morris Rn
Bsn Ma Lnc

https://ebookmass.com/product/calculate-with-
confidence-8e-oct-26-2021_0323696953_elsevier-8th-edition-morris-
rn-bsn-ma-lnc/
Theory and practice of metal oxide catalyst design for
the selective catalytic reduction of NOx with NH3 Wenpo
Shan & Yunbo Yu & Yan Zhang & Guangzhi He & Yue Peng &
Junhua Li & Hong He
https://ebookmass.com/product/theory-and-practice-of-metal-oxide-
catalyst-design-for-the-selective-catalytic-reduction-of-nox-
with-nh3-wenpo-shan-yunbo-yu-yan-zhang-guangzhi-he-yue-peng-
junhua-li-hong-he/

1 st International Congress and Exhibition on

Sustainability in Music, Art, Textile and Fashion
(ICESMATF 2023) January, 26-27 Madrid, Spain Exhibition
Book 1st Edition Tatiana Lissa
https://ebookmass.com/product/1-st-international-congress-and-
exhibition-on-sustainability-in-music-art-textile-and-fashion-
icesmatf-2023-january-26-27-madrid-spain-exhibition-book-1st-
edition-tatiana-lissa/

Morphology controlled synthesis of Co(OH)2/TiO2 p-n

heterojunction photoelectrodes for efficient
photocathodic protection of 304 stainless steel Xiayu
Lu & Li Liu & Jianwen Ge & Yu Cui & Fuhui Wang
https://ebookmass.com/product/morphology-controlled-synthesis-of-
cooh2-tio2-p-n-heterojunction-photoelectrodes-for-efficient-
photocathodic-protection-of-304-stainless-steel-xiayu-lu-li-liu-
jianwen-ge-yu-cui-fuhui-wang/

Morphology effect of MnO2 promoter to the catalytic

performance of Pt toward methanol electrooxidation
reaction Yuan-Yuan Feng & Gui-Hua Song & Qiang Zhang &
Jian-Ning Lv & Xi-Yu Hu & Yu-Long He & Xin Shen
https://ebookmass.com/product/morphology-effect-of-mno2-promoter-
to-the-catalytic-performance-of-pt-toward-methanol-
electrooxidation-reaction-yuan-yuan-feng-gui-hua-song-qiang-
zhang-jian-ning-lv-xi-yu-hu-yu-long-he-xin/

Customized Production Through 3D Printing in Cloud

Manufacturing Lin Zhang

https://ebookmass.com/product/customized-production-
through-3d-printing-in-cloud-manufacturing-lin-zhang/
 Chemical Engineering Journal 343 (2018) 500–511

Contents lists available at ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Morphology-controlled synthesis of 3D flower-like TiO2 and the superior T

performance for selective catalytic reduction of NOx with NH3
⁎
Luyao Zonga,b, Guodong Zhanga, Jiuhu Zhaoa,b, Fang Donga, Jiyi Zhangb, Zhicheng Tanga,
a
State Key Laboratory for Oxo Synthesis and Selective Oxidation, National Engineering Research Center for Fine Petrochemical Intermediates, Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
b
School of Petroleum and Chemical, Lanzhou University of Technology, Lanzhou 730050, China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• lated
Flower-like TiO support was regu-
2
by modulating hydrothermal
In this paper, the morphology of 3D TiO2 support was regulated by modulating the hydrothermal time, and
CeO2-WO3/TiO2 catalysts catalyst was synthesized by impregnation method and used for selective catalytic
time. reduction of NOx with NH3. The whole formation process of flower-like TiO2 might be influenced by the changed
• Flower-like structure influenced
surface atomic ration of Ce / 3+
the of the hydrothermal time and also be made.

(Ce3+ + Ce4+).
• The surface atomic ration of Ce3+/
(Ce3+ + Ce4+) influenced the SCR
performance.
• The catalysts showed satisfactory
water-resistance and certain SO2 tol-
erance.

A R T I C LE I N FO A B S T R A C T

Keywords: Morphology of 3D TiO2 support was regulated by modulating the hydrothermal time. Notably, the increase of
Hydrothermal method hydrothermal time could greatly promote the transformation of rod-like TiO2 to flower-like TiO2, while the
Flower-like continuous increase of hydrothermal time damaged the integrity of flower-like TiO2 and led to the appearance of
Formation process large TiO2 particles. After that, a series of CeO2-WO3/TiO2 catalysts were prepared by a typical impregnation
CeO2-WO3/TiO2
method. The catalytic performance of these CeO2-WO3/TiO2 catalysts for the selective catalytic reduction of
Ce3+/(Ce3+ + Ce4+)
nitrogen oxides (NH3-SCR) verified that NOx conversion was greatly related to morphological integrity of flower-
like TiO2. Prominently, activity of CeO2-WO3/TiO2-8 catalyst was still excellent after introducing H2O and SO2,
and thus the combined CeO2-WO3/TiO2-8 catalyst showed high catalytic activity and good resistance to H2O and
SO2. Various characterizations indicated that the integrity of flower-like structure could evidently alter the
surface atomic ratio of Ce3+/(Ce3+ + Ce4+) as well as acid sites. With the increase of surface atomic ratio of
Ce3+/(Ce3+ + Ce4+), the SCR performance of the catalysts was obviously improved. In short, the superior
catalytic performance of CeO2-WO3/TiO2 for the SCR of NOx was related to the morphology of TiO2 support, the
highly dispersed active species, the valence of Ce, acid sites and lots of surface adsorbed oxygen.

⁎
Corresponding author.
E-mail address: tangzhicheng@licp.cas.cn (Z. Tang).

https://doi.org/10.1016/j.cej.2018.03.035
Received 20 October 2017; Received in revised form 5 March 2018; Accepted 6 March 2018
Available online 07 March 2018
1385-8947/ © 2018 Elsevier B.V. All rights reserved.
L. Zong et al.
1. Introduction
The emission of nitrogen oxides (NO and NO2) from coal fired
power plants and automobiles is becoming more and more serious.
More importantly, nitrogen oxides can also cause the haze, photo-
chemical smog, acid rain and make a secondary particulate matter
[1–3]. Therefore, the removal of these nitrogen oxides is vitally im-
portant for ameliorating and protecting the environment. Notably, the
selective catalytic reduction of nitrogen oxides with NH3 (NH3-SCR) has
been widely used for the removal of nitrogen oxides [4–6]. It was re-
ported that V2O5-WO3/TiO2 is the most promising NH3-SCR catalyst
according to lots of literatures [7,8]. However, V2O5-WO3/TiO2 catalyst
still exists various disadvantages, such as poor thermal stability, narrow
operating temperature window, toxicity of vanadium species, high ac-
tivity for the oxidation of SO2 to SO3 and the alkali metal poison [9]. In
addition, V2O5-WO3/TiO2 catalyst could also result in the unselective
oxidation of NH3. Unfortunately, in this unselective oxidation of NH3,
some ozone-depleting, greenhouse gas and N2O would be generated,
which could destroy the balance of the environment [10,11]. Due to
these disadvantages, no vanadium catalyst arise great attention [12].
For replacing the vanadium, cerium has been considered as an ex-
cellent constituent, which could be additives and carriers. However,
cerium-based catalyst has some advantages contrasting with the vana-
dium catalyst [13–15]. Generally, cerium-based catalyst exist Ce4+ and
Ce3+ species. Especially, Ce3+ species is the main existence, which is
beneficial for the NH3-SCR. Generally, Ce4+ and Ce3+ species in
cerium-based catalysts could convert into each other during the cata-
lytic reaction. In this process, some active oxygen would be released
and promoted the NH3-SCR reaction [16–18]. On the other hand,
cerium-based catalysts also have some disadvantages, such as their
sulfur tolerance. When SO2 was pumped into the reaction, Ce3+ would
react with the SO2 to form Ce2(SO4)3 and the decrease of active cerium
species [19]. Thus, the sulfur tolerance of catalysts could be improved
through various means.
Fortunately, there are two means to improve and avoid the above
disadvantages. On one hand, the addition of assistant could avoid the
reaction of cerium and SO2. On the other hand, the modulation of
surface properties of support materials is vitally important for elevating
the activity and stability of catalysts [20–23]. Various literatures
[24–27] reported that the morphology and surface area of catalyst
could alter the surface composition, the valence of element, the defect
sites and acid-based sites of catalysts. For example, flower-like support
material is very promising because of the special morphology and the
big surface area. Li et al. [28] synthesized 3D flower-like NiMnFe mixed
oxides as monolith catalysts for NH3-SCR and found that the structure
of 3D flower-like NiMnFe mixed oxides could enhance evidently per-
formance for the NH3-SCR. Ma et al. [29] synthesized a series of
MoS2@TiO2 nanohybrids for catalytic hydrogen evolution via simple
hydrothermal processes using MOF as precursor for the first time. Be-
sides, Khalid et al. [30] synthesized TiO2 nano-flowers by hydrothermal
method and found that the particles size of flower-like structure in-
creased as the increasing of hydrothermal time. Wang et al. [31] also
synthesized 3D flower-like TiO2 microsphere/composite through a
polyvinyl pyrrolidone (PVP) assisted one-step hydrothermal method by
using the titanium (IV) isopropoxide (TTIP) and grapheme oxide (GO)
as precursors. Thus, it can be concluded that hydrothermal method is a
usual strategy for the synthesis of flower-like TiO2. Although many
researchers have successfully synthesized 3D flower-like TiO2, some of
them only considered how to synthesize and rarely considered how to
use the advantages of 3D flower-like in NH3-SCR, such as large specific
surface area, high dispersion. Thus those advantages were carefully
considered in our work so that further promoted the SCR performance
and the ability of catalysts.
In this work, we synthesized a series of TiO2 with different mor-
phology by hydrothermal method. It was discovered that hydrothermal
time played a key role in determining the morphology and structure of
501
Chemical Engineering Journal 343 (2018) 500–511
TiO2. In further detail, the active components Ce and W were doped and
anchored in these TiO2 with special morphology to obtain a series of
CeO2-WO3/TiO2 catalysts. Furthermore, the influence of hydrothermal
time in the morphology of TiO2, the formation process of flower-like
TiO2, the SCR performance as well as the tolerance to H2O and SO2 of
the CeO2-WO3/TiO2 catalysts were investigated by various character-
izations. It was discovered that CeO2-WO3/TiO2-8 catalyst had the su-
perior activity and stability.
2. Experimental
2.1. Preparation of support materials
In this study, we prepared support materials (TiO2) by hydrothermal
method and synthesized different support materials by changing the
hydrothermal time. In detail, 0.7 g titanium (IV) isopropoxide (TTIP)
was added into 75 mL acetic acid with vigorous stirring for 30 min.
After that, the solution was transferred into 100 mL stainless steel au-
toclave and treated at 160 °C for 12 h. The suspension cooled at room
temperature. The obtained filter cake was washed with deionized water
and ethanol for three times, after that it was dried in an electricity heat
drum wind drying oven at 100 °C for 6 h. The dried yellow powder was
calcined at 500 °C for 1 h in air with a rate of 1 °C min−1. At last, the
support material TiO2 was obtained. Due to the hydrothermal time
were 12 h, thus this support material TiO2 was named as TiO2-12. In
addition, we also prepared the TiO2 under the hydrothermal time were
4 h, 8 h and 16 h, and also named those TiO2 as TiO2-4, TiO2-8 and
TiO2-16.
2.2. Preparation of CeO2-WO3/TiO2 catalyst
The CeO2-WO3/TiO2 catalysts were prepared by impregnation
method. In our study, the loadings of tungsten were 5 wt% and that of
cerium were 10 wt%. In detail, 0.08 g of ammonium metatungstate
((NH4)6H2W12O40·XH2O) and 0.37 g of cerium nitrate (Ce(NO3)3·6H2O)
were dissolved in 1.5 mL (15 wt%) oxalic acid solution for 30 min, and
then TiO2 powder was slowly added into the above solution under
vigorous stirring for 24 h. After that, the mixture was dried at 100 °C for
6 h. The dried yellow powder was calcined at 550 °C for 5 h in air at a
rate of 1 °C min−1. Hereafter, they are denoted as CeO2-WO3/TiO2-x,
where x represents the hydrothermal time. As a contrast, industrial ti-
tanium dioxide was used as support instead of TiO2-x for synthesis
CeO2-WO3/TiO2-IT catalyst by same method, where IT was the ab-
breviation of industrial titanium dioxide.
2.3. NH3-SCR catalytic test
The NH3-SCR activity measurement was carried out in a fixed bed
reactor operating in a steady state flow mode. 0.40 g of the catalysts
were sieved with a 20–40 mesh and used in each test. The reaction
conditions were exhibited as follows: 500 ppm of NO, 500 ppm of NH3,
3 vol% of O2 and balance N2. The total flow rate was 200 mL min−1 and
a gas hourly space velocity (GHSV) of 30,000 h−1 was obtained. The
temperature increased from 200 to 480 °C. At each temperature step,
the data were recorded after steady state. The concentration of NOx in
the inlet and outlet gas was measured by a KM9106 flue gas analyzer. In
here, NOx meant the NO and NO2. The NOx conversion was calculated
according to the following expression:
[NOx ]in −[NOx ]out
NOx conversion (%) = × 100%
[NOx ]in
2.4. Characterization of the catalysts
The morphology of the catalysts was obtained by using a scanning
electron microscope (SEM). The SEM images were recorded on a JSM-
L. Zong et al.
6701F emission scanning electron microscopy.
Transmission electron microscopy (TEM) experiments were carried
out on a JEOL JEM-2010 transmission electron microscope equipped
with an Oxford energy dispersive X-ray (EDX) spectrometer attachment
operating at 200 kV.
The specific surface area of the catalysts determined by nitrogen
adsorption in accordance with the Brunauer, Emmett and Teller (BET)
method, with a Micromeritics ASAP 2010 instrument. The BET surface
area determinations were based on six measurements at relative pres-
sures of N2 in the range of 0.05–1.00.
X-ray diffraction (XRD) analysis was performed to verify the crys-
tallographic phase present in the catalysts. XRD patterns of the samples
were recorded on a Rigaku D/MAX-RB X-ray diffractometer with a
target of Mg Kα operated at 60 kV and 55 mA with a scanning speed of
0.5° min−1. The 2θ of wide-angle ranged from 5° to 85°.
H2-Temperature program reduction (H2-TPR) measurements were
performed by DAS-7000 automatic multi-function adsorption appa-
ratus. The reducing gas was 5 vol% H2 balanced by N2, and a flow rate
of 30 mL min−1 was used. The quartz tube reactor was loaded with
50 mg sample in powder form. The test was carried out from room
temperature to 800 °C at a heating rate of 10 °C min−1. Before each
measurement, the sample was purged with N2 at 300 °C for 1 h.
Chemical states of the atoms in the catalyst surface were in-
vestigated by X-ray photoelectron spectroscopy (XPS) on a VG
ESCALAB 210 Electron Spectrometer (Mg Ka radiation;
hv = 1253.6 eV). XPS data were calibrated using the binding energy of
C 1s (284.6 eV) as the standard.
NH3-Temperature program desorption (NH3-TPD) measurements
were performed by DAS-7000 automatic multi-function adsorption
apparatus. The adsorbing gas was 5 vol% NH3 balanced by N2, and a
flow rate of 30 mL min−1 was used. The quartz tube reactor was loaded
with 100 mg sample in powder form. The test was carried out from
150 °C to 850 °C at a heating rate of 10 °C min−1. Before each mea-
surement, the sample was purged with N2 gas at 300 °C for 1 h.
Fourier Transform Infrared Spectroscopy (FT-IR, Nexus 870) having
a resolution of 4 cm−1. The samples were mixed and ground with KBr
to give a 1:100 sample to KBr ratio. Each sample was scanned at a range
of 400–4000 cm−1.
3. Results and discussion
3.1. The synthesis of TiO2 support with special morphology
Morphology of TiO2-4, TiO2-8, TiO2-12 and TiO2-16 was examined
by SEM and TEM. With the change of hydrothermal time, it was dis-
covered that the morphology of TiO2 support had an obvious difference.
In detail, the SEM images of TiO2-4 mainly exhibited a rod-like struc-
ture (Fig. 1a). It was interesting that the little of flower-like TiO2 was
doped in the rod-like TiO2 (Fig. 1b). Obviously, those rod-like TiO2 was
composed by the particle. To further confirm, TEM of TiO2-4 was shown
in Fig. 2a and b. It could also be easily seen that TiO2-4 emerged rod-
like composed by the particle, which was consistent with the results of
SEM.
For TiO2-8, SEM images presented the integrity flower-like structure
(Fig. 1c). Notably, the flower-like structure of TiO2 was composed with
the strip (Fig. 1d). In order to investigate its structure in detail, the TEM
of TiO2-8 was shown in Fig. 2c and d. It was concluded that the
structure of TiO2-8 also appeared the integrity flower-like (Fig. 2c).
Besides, the TEM of flower-like TiO2 was made to identify the structural
unit at the high magnification, which showed in Fig. 2d. Obviously, the
strip structure was composed by the particle in accordance with TEM
images. To summarize, the whole flower-like structure was formed by
the directional growth of particle.
SEM and TEM images of TiO2-12 also were shown in Fig. 1e–f and
502
Chemical Engineering Journal 343 (2018) 500–511
Fig. 2e–f, respectively. Compared with TiO2-8, TiO2-12 also presented
flower-like structure, but it was composed by the slice (Fig. 1e). Fur-
thermore, it was discovered that the flower-like structure of TiO2-12
was composed by the single slice, and then the slice and slice were
connected to each other (Fig. 1f). According to Fig. 2c and e, the edge
blank area of flower-like TiO2-12 was smaller than the TiO2-8 in-
dicating that the connection between the slice and slice more closely,
which was consistent with the result of SEM. It could also be concluded
that the flower-like structure of TiO2-12 was composed by the slice,
while the slice was composed by the particle.
Meanwhile, SEM and TEM tests for the TiO2-16 were shown in
Fig. 1g–h and Fig. 2g–h, respectively. Compared with the TiO2-8 and
TiO2-12, although TiO2-16 presented some flower-like TiO2, the whole
morphology of TiO2-16 had some change. There was the obvious ag-
gregation of particles (Fig. 1g). It could be seen that some flower-like
TiO2 transformed to the large particle (Fig. 1h). At the same time, the
slice of TiO2 filled up the whole structure (Fig. 2h). Combine with the
SEM result of TiO2-16, this phenomenon might be attributed to the
aggregation of particles. Based on the above discussion, the morphology
of materials TiO2 were summarized in Table 1. In detail, TiO2-4 pre-
sented rod-like and had some rudiment of flower-like. TiO2-8 presented
flower-like, which was composed by the strip. While TiO2-12 presented
flower-like, it was composed by the slice. TiO2-16 presented flower-like
and appeared the aggregation of particles. For the different morphology
of TiO2, they were formed by the accumulation of particle.
For further investigating the formation mechanism of flower-like
TiO2, BET test was made. The BET surface areas of TiO2-4, TiO2-8, TiO2-
12 and TiO2-16 were 94.09 m2 g−1, 113.61 m2 g−1, 132.97 m2 g−1 and
120.18 m2 g−1, respectively. Notably, the morphology of TiO2 ob-
viously influenced the BET surface areas. In detail, the BET surface
areas increased with the increase of hydrothermal time, then decreased
with the continuous increase of hydrothermal time. When the hydro-
thermal time was 12 h, flower-like TiO2 exhibited the largest BET sur-
face area. For the increase of BET surface areas, this might be due to the
formation of flower-like TiO2. In detail, TiO2-4 presented rod-like and
appeared the rudiment of flower-like, and it had less expose surface.
Thus the BET surface area of TiO2-4 was the minimum. When the hy-
drothermal time reached to 8 h, the rod-like TiO2 existed in the inter-
action each other and then formed the morphology of flower-like. Due
to the appearance of TiO2 particles TiO2-8 had larger BET surface area.
Compared with the morphology of TiO2-8, the flower-like TiO2-12 was
composed with the slice, while the flower-like TiO2-8 was only com-
posed with the strip. Generally, slice could expose the bigger surface
than strip. According to the TEM result of TiO2-8 and TiO2-12 (Fig. 2d
and f), the slice of TiO2-12 was composed by the strip, and the BET
surface of TiO2-12 was larger than TiO2-8. When the hydrothermal time
reached to 16 h, the BET surface area of TiO2-16 decreased contrasting
with the TiO2-12, and TiO2-16 had appeared some state of aggregation
of the particles. Beside the BET surface area, the morphology might also
be affected the pore structure of catalysts.
Fig. 3 showed the N2 physisorption curves of TiO2-4, TiO2-8, TiO2-
12 and TiO2-16. The isotherms of the four samples were attributed to
type IV with H1 hysteresis loop according to IUPAC classifications,
indicating that four samples exhibited the typical mesoporous structure.
Thus the average pore diameter was made to further analyze the for-
mation mechanism of different morphology TiO2. As shown in Table 1,
average pore diameter of TiO2-4, TiO2-8, TiO2-12 and TiO2-16 were
17.20 nm, 16.05 nm, 13.82 nm and 17.75 nm, respectively. Obviously,
when the hydrothermal time increased from 4 h to 12 h, the average
pore diameter had an obvious decrease. This might be because of the
interaction of particles in the whole formation of flower-like TiO2. With
the increase of the hydrothermal time, the morphology of flower-like
TiO2 became more complete, and the constituent part altered and
transformed from particle to strip, then transformed to slice. At this
L. Zong et al. Chemical Engineering Journal 343 (2018) 500–511

Fig. 1. SEM micrographs of support materials: TiO2-4 (a and b), TiO2-8 (c and d), TiO2-12 (e and f) and TiO2-16 (g and h).

process, the unit also became more closely and the average pore dia-
meter had an obvious decrease. When the hydrothermal time reached
to 16 h, average pore diameter increased. This might be because of the
co-existence of the flower-like TiO2 and large TiO2 particles, which
resulted in the increase of average pore diameter.
Based on the above analysis, the formation process of flower-like
TiO2 might be altered by the modulation of hydrothermal time, and the
respective formation mechanism of flower-like TiO2 was shown in
Scheme 1. Due to the special flower-like structure of support TiO2, it
could promote the dispersion of the active component, which was
beneficial for the improvement of catalytic performance of TiO2-based
catalyst in NH3-SCR.

503
L. Zong et al. Chemical Engineering Journal 343 (2018) 500–511

Fig. 2. TEM images of support materials: TiO2-4 (a and b), TiO2-8 (c and d), TiO2-12 (e and f), and TiO2-16 (g and h).

Table 1
The morphology, characteristic and BET results of support materials.

Supporting materials Morphologya Characteristicb SBET (m2 g−1)c Average pore diameter (nm)c Pore volume (cm3 g−1)c

TiO2-4 Rod-like Had some rudiment of flower-like 94.09 17.20 0.40

TiO2-8 Flower-like Composed with the strip 113.61 16.05 0.46
TiO2-12 Flower-like Composed with the slice 132.97 13.82 0.46
TiO2-16 Flower-like and particles Present some state of aggregation of the particles 120.18 17.75 0.53
CeO2-WO3/TiO2-8 Flower-like Composed with the strip 90.07 9.59 0.28

a
The morphology of samples was determined by the SEM results.
b
The characteristic of samples was determined by the SEM and TEM results.
c
Determined by the BET results.

504
L. Zong et al.
Fig. 3. N2 physisorption isotherms of samples.
3.2. Characterization and catalytic performance of CeO2-WO3/TiO2
catalyst
3.2.1. Catalytic performance of CeO2-WO3/TiO2 catalyst
The SCR activity of TiO2 support and CeO2-WO3/TiO2 catalysts was
shown in Fig. 4. For bare TiO2 support, they all presented the bad
catalytic activity (Fig. 4a). In detail, the NOx conversion rate kept at
below 80% in the temperature range of 180–400 °C. Above 400 °C, the
SCR performance had an increase, but the highest NOx conversion rate
only was 84.62%. When the temperature was raised to 440 °C, the SCR
performance of four TiO2 supports all decreased. From the SEM and
TEM result of TiO2 supports, they showed different morphology. After
loading active ingredient, the morphology of TiO2 might be altered due
to the interaction of active ingredient with TiO2 supports, which would
result in the particles size and valence of active component. The cata-
lytic activity of CeO2-WO3/TiO2 catalysts was shown in Fig. 4b. In the
temperature range of 180–220 °C, it was discovered the SCR
Scheme 1. Formation process of flower-like TiO2.
505
Chemical Engineering Journal 343 (2018) 500–511
performance of catalysts was observed followed the order CeO2-WO3/
TiO2-8 > CeO2-WO3/TiO2-4 > CeO2-WO3/TiO2-12 > CeO2-WO3/
TiO2-16, but the SCR performance were all lower to 56%. Besides, in
the temperature range of 240–280 °C, the SCR performance of catalysts
was observed to follow the order CeO2-WO3/TiO2-8 > CeO2-WO3/
TiO2-12 > CeO2-WO3/TiO2-16 > CeO2-WO3/TiO2-4, and CeO2-WO3/
TiO2-8 also showed the best SCR performance and the NOx conversion
increased from 65 to 88%. In the temperature range of 320–440 °C,
besides CeO2-WO3/TiO2-16 catalyst, the other catalysts showed a si-
milar SCR performance above 90%. Over 440 °C, the SCR performance
of four catalysts all decreased. In conclusion, CeO2-WO3/TiO2-8 showed
the best SCR performance.
In further, the effect of gas hourly space velocity (GHSV) for the
NH3-SCR reaction over CeO2-WO3/TiO2-8 was studied and the results
were shown in Fig. 4c. With the increase of the GHSV, the NOx con-
version decreased. At the temperature range of 180–260 °C, the NOx
conversion had a high decrease under the high GHSV of 60000 h−1 and
100000 h−1. Afterwards, the downward trend of NOx conversion was
slowing down and the catalysts still had over 80% NOx conversion at
the temperature of 320–440 °C, indicating that CeO2-WO3/TiO2-8 cat-
alysts had a better SCR performance at the high temperature and the
bigger GHSV. For further exploring the influence factors of activity, a
series of characterization was made.
3.2.2. Characterization of CeO2-WO3/TiO2 catalyst
The XRD result of TiO2 support and CeO2-WO3/TiO2 catalysts were
shown in Fig. 5. It was discovered that the diffraction peaks of TiO2
support were not obviously different (Fig. 5a), which meant that the
hydrothermal time did not affect the crystal of TiO2. In detail, the
distinct diffraction peaks at 25.28°, 37.80°, 48.05°, 53.89°, 55.06°,
62.68°, 68.76°, 70.31°, 75.03° and 82.65° were observed, which indexed
to the (1 0 1), (0 0 4), (2 0 0), (1 0 5), (2 1 1), (2 0 4), (1 1 6), (2 2 0), (2 1 5)
and (2 2 4) lattice planes of anatase titanium structure of TiO2 (PDF#21-
1272). In Fig. 5b, beside the peaks of TiO2, four samples also exhibited
two peaks at 28.55° and 33.08°, which were attributed to (1 1 1) and
(2 0 0) lattice plane of CeO2 (PDF#34-0394). Notably, the diffraction of
WOx phases were not observed on four catalysts, suggesting that
tungsten oxide was highly dispersed on the catalyst surface. By contrast
L. Zong et al. Chemical Engineering Journal 343 (2018) 500–511

Fig. 4. NOx conversion of (a) TiO2 support; (b) CeO2-WO3/TiO2 catalysts; (c) The effect of GHSV over CeO2-WO3/TiO2-8 catalyst; (d) CeO2-WO3/TiO2-8 and CeO2-WO3/TiO2-IT catalyst.

with Fig. 5a and b, the crystal of TiO2 did not occurred change, which
meant that the loading of active ingredient did not affect the crystal of
TiO2. In addition, the BET results of CeO2-WO3/TiO2-8h catalyst were
made in Table 1. After loading active ingredient, it was discovered the
surface area, average pore diameter and pore volume all had a certain
decrease, which might be due to flower-like structure promoted the
dispersion of active ingredient. In order to investigate the redox per-
formance of catalyst, H2-TPR analysis was conducted on these catalysts.
H2-TPR results of CeO2-WO3/TiO2-4, CeO2-WO3/TiO2-8, CeO2-
WO3/TiO2-12 and CeO2-WO3/TiO2-16 catalysts were illustrated in
Fig. 6. For the four catalysts, they did not show the evident peaks of
TiO2 and WO3. For CeO2, they both had three reduction peaks at
330.31 °C, 522.59 °C and 548.36 °C, which could be assigned to the
reduction of surface species (surface Ce4+ to Ce3+) [36,37]. The four
catalysts all had three reduction peaks, but the intensity of reduction
peaks was different. The difference for the H2-TPR profile of four cat-
alysts might be due to the difference of the interaction between the
cerium oxide species and the different morphology TiO2. From the SEM,
BET and TEM results of samples, the flower-like structure of TiO2-8
would result in the satisfactory dispersion of cerium. On the other hand,
according to the results of H2-TPR and the NOx conversion of catalysts,
the cerium oxide species might be mainly influence the SCR perfor-
mance of catalysts [38]. Generally, the cerium oxide species and the
different morphology TiO2 both altered the SCR performance. For fur-
ther clarifying the chemical state of element, XPS analysis was con-
ducted on four catalysts.

Fig. 5. Wide angle XRD patterns: (a) TiO2 supports; (b) CeO2-WO3/TiO2 catalysts.

506
L. Zong et al. Chemical Engineering Journal 343 (2018) 500–511

Table 2
The peak-fitting results of O1s, W 4f, Ce 3d spectra.

Catalyst CeO2-WO3/TiO2

4 ha 8 ha 12 ha 16 ha

Oα/(Oα + Oβ) × 100%b 10.6 15.6 12.4 15.5

Ce3+/(Ce4+ + Ce3+) × 100%b 24.7 42.9 33.5 24.3
W 4f5/2/(W 4f5/2 + W 4f7/2)%b 74.9 70.9 74.3 69.6

a
The hydrothermal time.
b
The surface atomic ratio was determined by the XPS results.

529.44–530.90 eV were assigned to lattice oxygen Oβ and the peaks

Fig. 6. H2-TPR profiles of CeO2-WO3/TiO2 catalysts.
The XPS spectra of CeO2-WO3/TiO2-4, CeO2-WO3/TiO2-8, CeO2-
WO3/TiO2-12 and CeO2-WO3/TiO2-16 catalysts were shown in Fig. 7.
Fig. 7a showed the Ti 2p XPS results and there was no obvious differ-
ence in four catalysts.
Fig. 7b showed the O 1s XPS results of samples. The O 1s could be
divided into two peaks. The peaks centered in the range of
centered in the range of 531.00–532.50 eV were assigned to chemical
adsorbed oxygen Oα [39]. The surface atomic ratio of Ox/(Oα + Oβ)
were listed in Table 2. For CeO2-WO3/TiO2-4, CeO2-WO3/TiO2-8, CeO2-
WO3/TiO2-12 and CeO2-WO3/TiO2-16 catalysts, the surface atomic
ratio of Oα/(Oα + Oβ) were 10.6%, 15.6%, 12.4% and 15.5%, respec-
tively. For Oα, it had higher mobility compared with Oβ and then more
surface oxygen vacancies were produced, which would be beneficial for
the SCR performance [40]. For the SCR performance of CeO2-WO3/
TiO2-4, CeO2-WO3/TiO2-8 and CeO2-WO3/TiO2-12 catalysts, with the
increase of the surface atomic ratio of Oα/(Oα + Oβ), the NOx conver-
sion also improved. Based on the above analysis, the atomic ratio of Oα/
(Oα + Oβ) might not be the main influence factor for the different SCR
performance of the catalysts.
Fig. 7c showed the W 4f XPS results of samples. The W4f could be

Fig. 7. XPS spectra of CeO2-WO3/TiO2 catalysts: (a) Ti 2p; (b) O 1s; (c) W 4f; (d) Ce 3d.

507
L. Zong et al. Chemical Engineering Journal 343 (2018) 500–511

divided into two peaks. The peaks appeared at around 35.60 and
37.40 eV binding energies could be assigned to W4f7/2 and 4f5/2, re-
spectively [41]. For CeO2-WO3/TiO2-4, CeO2-WO3/TiO2-8, CeO2-WO3/
TiO2-12 and CeO2-WO3/TiO2-16 catalysts, the surface atomic ratio of W
4fx/(W 4f5/2 + W 4f7/2) were listed in Table 2. It was interesting that
the surface atomic ratio of W 4f7/2/(W 4f5/2 + W 4f7/2) had a similar
law with the atomic ratio of Oα/(Oα + Oβ) for the catalytic activity.
Besides CeO2-WO3/TiO2-16 catalysts, with the increase of the surface
atomic ratio of W 4f7/2/(W 4f5/2 + W 4f7/2), the NOx conversion of
CeO2-WO3/TiO2-4, CeO2-WO3/TiO2-8 and CeO2-WO3/TiO2-12 cata-
lysts also increased. This might be due to Oα could produce the surface
oxygen vacancies and it could promote the reduction of W6+ to W5+.
Based on the above analysis, the atomic ratio of W 4f7/2/(W 4f5/2 + W
4f7/2) might not be the main influence factor for the difference SCR
performance of the catalysts.
Fig. 7d showed the Ce 3d XPS results of samples. The XPS spectra of
Ce 3d could be divided into eight peaks denoted as v (882.4 eV), v′
(885.9 eV), v″ (889.8 eV), v‴ (898.7 eV), u (901.3 eV), u′ (904.5 eV), u″
(907.8 eV) and u‴ (917.1 eV) [40]. In more details, the peaks of v, v″,
Fig. 9. NH3-TPD profiles of CeO2-WO3/TiO2 catalysts.
v‴, u, u″ and u‴ could be assigned to the 3d104f0 initial electronic state
which named as Ce4+ species, the peaks of v′ and u′ could be assigned
to the 3d104f1 initial electronic state which named as Ce3+ species. The SCR performance of catalysts, thus the NH3-TPD test was conducted.
surface atomic ratios of Cex+/(Ce3+ + Ce4+) were listed in Table 2. Fig. 9 showed the NH3-TPD results of CeO2-WO3/TiO2-4, CeO2-
For CeO2-WO3/TiO2-4, CeO2-WO3/TiO2-8, CeO2-WO3/TiO2-12 and WO3/TiO2-8, CeO2-WO3/TiO2-12 and CeO2-WO3/TiO2-16 catalysts. For
CeO2-WO3/TiO2-16 catalysts, the surface atomic ratio of Ce3+/ CeO2-WO3/TiO2-4, CeO2-WO3/TiO2-8 and CeO2-WO3/TiO2-12 cata-
(Ce3+ + Ce4+) were 24.7%, 42.9%, 33.5% and 24.3%, respectively. At lysts, they all had three NH3 desorption peaks in the range of
the same time, for the SCR performance of catalysts, when the NOx 100–550 °C, and CeO2-WO3/TiO2-16 catalysts only had two NH3 des-
conversion reached to 80%, the temperature of CeO2-WO3/TiO2-4, orption peaks. This might be one of the reasons for the difference of
CeO2-WO3/TiO2-8, CeO2-WO3/TiO2-12 and CeO2-WO3/TiO2-16 cata- NOx conversion. On the other hand, for the CeO2-WO3/TiO2-4, CeO2-
lysts were 271 °C, 295 °C, 292 °C and 257 °C, respectively. Obviously, WO3/TiO2-8 and CeO2-WO3/TiO2-12 catalysts, with the increase of
with the increase of the surface atomic ratio of Ce3+/(Ce3+ + Ce4+), hydrothermal time, the three NH3 desorption peaks occurred some shift
the NOx conversion temperature also increased in Fig. 8. For the Ce3+, towards to the higher temperature, which meant the acidic property of
it could result in a charge imbalance, which would lead to oxygen va- catalysts increased [32–35]. For the SCR performance of catalysts, the
cancies and unsaturated chemical bonds. Based on this, the surface of stronger acid sites were benefit to promote the conversion of NOx.
the catalysts would emerge with some additional chemisorbed oxygen According the Fig. 4b, the SCR performance of CeO2-WO3/TiO2-8 cat-
or weakly adsorbed oxygen species, which would be beneficial for the alyst was the best, and that of CeO2-WO3/TiO2-12 catalyst was lower
SCR performance [42,43]. Combining with the morphology of four than CeO2-WO3/TiO2-8 catalyst, this might be have other factors in-
catalysts, CeO2-WO3/TiO2-8 and CeO2-WO3/TiO2-12 catalysts ex- fluenced the SCR performance of catalysts. Therefore, the acid sites of
hibited the flower-like structure, and the surface atomic ratio of Ce3+/ these samples played the important roles in NH3-SCR reaction.
(Ce3+ + Ce4+) were also higher. In total, the flower-like structure To sum up, due to the big surface area of flower-like TiO2 and the
might be enhance the surface atomic ratio of Ce3+/(Ce3+ + Ce4+). In high dispersion of active component, there was more cerium loaded on
addition, the acid site could also play the significant role in deciding the the surface of TiO2. Based on the above factors, the surface atomic ratio
of Ce3+/(Ce3+ + Ce4+) on flower-like TiO2 surface would increase. For
the SCR performance of catalysts, the surface atomic ratio of Ce3+/
(Ce3+ + Ce4+) acted as a promoter. At the same time, the flower-like
TiO2 also could provide more acid site, which would promote the SCR
performance. Furthermore, the stability of the best CeO2-WO3/TiO2-8
catalysts was investigated at the existence of H2O and SO2.

3.3. The stability of H2O and SO2 resisting properties

As we all know, there had been a part of water and sulfur dioxide in
the air pollution, since they should also be considered. The H2O and
SO2 resistance of CeO2-WO3/TiO2-8 catalysts had been exhibited in
Fig. 10a. In the first 10 h, when H2O was pumped in the reactant, the
NOx conversion had no change, indicating that CeO2-WO3/TiO2-8 cat-
alysts had satisfactory water-resistance. After that, we stopped the ad-
dition of H2O and pumped in SO2. At the first hour, the NOx conversion
of CeO2-WO3/TiO2-8 catalysts decreased from 94.23% to 86.35%.
Subsequently, the NOx conversion of CeO2-WO3/TiO2-8 catalyst had no
evident change. For the deactivated catalysts, under the existence of
Fig. 8. The relationship between the surface atomic ratio of Ce3+/(Ce4+ + Ce3+) with
SO2, the NOx would react with O2 and oxidize SO2 into (NH4)2SO4 or
the NOx conversion temperature under the 80% NOx conversion temperature.
(NH4)2SO3 [44]. Based on this, the SCR reaction would be restrain, so

508
L. Zong et al.
Fig. 10. Stability, H2O or SO2 resistance test at 320 °C: (a) CeO2-WO3/TiO2-8 catalyst; (b) CeO2-WO3/TiO2-IT catalyst.
Fig. 11. FT-IR results of CeO2-WO3/TiO2 catalysts.
that the NOx conversion declined. Although the NOx conversion of
CeO2-WO3/TiO2-8 catalyst decreased, the declining quantity was faint.
After stopping the pump of SO2, the NOx conversion had a little en-
hancement. Based on the above results, the CeO2-WO3/TiO2-8 catalyst
had certain SO2 tolerance. Finally, we simultaneously pumped in H2O
and SO2. At the first hour, the NOx conversion of CeO2-WO3/TiO2-8
catalyst decreased from 94.23% to 65.48%. After the next hour, the
NOx conversion increased from 65.48% to 75.48%. Subsequently, the
NOx conversion of CeO2-WO3/TiO2-8 catalyst had no evident change. In
order to better explain the reasons, the H2O and SO2 resistance of CeO2-
WO3/TiO2-8 catalyst were test at the same conditions in Fig. 10b. When
H2O were pumped in the reactor, the catalytic activity had no change,
indicating that CeO2-WO3/TiO2-IT catalyst had satisfactory water-re-
sistance. But when pumped in SO2 or pumped in H2O and SO2, the SCR
performance of CeO2-WO3/TiO2-IT catalyst showed a clear downward
trend and even the NOx conversion decreased below 70% after 2 h.
However, CeO2-WO3/TiO2-IT catalyst had a better catalytic activity
than CeO2-WO3/TiO2-8 catalyst (Fig. 4d). Based on the above results,
CeO2-WO3/TiO2-8 catalyst had satisfactory water-resistance and certain
SO2 tolerance.
For exploring the effect of H2O and SO2 for the NOx conversion of
CeO2-WO3/TiO2-8 catalyst, the FT-IR test was conducted on the used
509
Chemical Engineering Journal 343 (2018) 500–511
catalyst in Fig. 11. Firstly, the bands at 1291.67 cm−1 and
1625.28 cm−1 were assigned to the Lewis acid sites [45–47]. In Fig. 11,
CeO2-WO3/TiO2-8 catalyst had stronger Lewis acid sites than the de-
activated catalyst. For the SCR performance, stronger Lewis acid sites
would promote the SCR reaction, and the catalyst would show excellent
catalytic activity. The bands at 1403.88 cm−1 and 1727.52 cm−1 were
assigned to the NH3+ species on Brønsted acid sites [48]. Second, for
the Brønsted acid sites, CeO2-WO3/TiO2-8 catalyst and the deactivated
catalyst had no obvious difference. This meant that Brønsted acid sites
were not the main reason for the deactivation of catalyst. Finally, the
bands at 3381.24 cm−1 was assigned to the surface -OH stretching
frequencies [49]. Therefore, the strength of Lewis acid sites had evi-
dently influenced the SCR performance of catalysts, and the pump of
SO2 might result in the decrease of Lewis acid sites.
For further investigating the reason of the deactivation for CeO2-
WO3/TiO2-8 catalyst, XPS spectra of deactivation catalysts and the
fresh CeO2-WO3/TiO2-8 catalyst were shown in Fig. 12. At the same
time, the surface element content was listed in Table 3. The surface
element content of deactivation catalyst appeared some sulfur. It might
be due to the pump of the H2O and SO2, and Ce would react with the
SO2 to form Ce2(SO4)3. Therefore, there would result in the decrease of
Ce, which participated with the SCR performance, and this might be the
reason that the decrease of SCR performance for catalysts under the
pump of the H2O and SO2. Besides, the atomic ratio of Ce3+/
(Ce3+ + Ce4+) for catalyst was shown in Table 3. For the CeO2-WO3/
TiO2-8 catalyst and the deactivated catalyst, the surface atomic ratio of
Ce3+/(Ce3+ + Ce4+) were 42.9% and 38.1%, respectively. This also
illustrated that a part of Ce reacted with SO2 and resulted in the de-
crease of the surface atomic ratio of Ce3+/(Ce3+ + Ce4+).
4. Conclusion
In conclusion, an integrity 3D flower-like TiO2 support had been
directly synthesized by the modulation of hydrothermal time. Notably,
the CeO2-WO3/TiO2-8 catalyst (hydrothermal time = 8 h) prepared in
further by the impregnation method showed the best catalytic perfor-
mance for the selective catalytic reduction of NOx with NH3. Besides,
CeO2-WO3/TiO2-8 catalyst also exhibited the better resistance to H2O
and SO2. The excellent catalytic performance of CeO2-WO3/TiO2-8
catalyst was attributed to the higher atomic ratio of Ce3+/
(Ce3+ + Ce4+) on the catalyst surface, the highly dispersed active
species, proper acid sites and lots of surface adsorbed oxygen.
L. Zong et al. Chemical Engineering Journal 343 (2018) 500–511

Fig. 12. XPS spectra of CeO2-WO3/TiO2 catalysts: (a) Ti 2p; (b) O 1s; (c) W 4f; (d) Ce 3d; m: after active test, n: after enduring H2O and SO2 test.

Table 3 [3] G. Qi, R.T. Yang, R. Chang, MNO-CeO2 mixed oxides prepared by co-precipitation
The content of Ti, O, W, Ce and S of catalysts. for selective catalytic reduction of NO with NH3 at low temperatures, Appl. Catal. B:
Environ. 51 (2004) 93–106.
Catalysts Surface composition (at.%)c Ce3+/ [4] W. Shan, Y. Geng, X. Chen, N. Huang, F. Liu, S. Yang, A highly efficient CeWOx
(Ce4+ + Ce3+) × 100%d catalyst for the selective catalytic reduction of NO with NH3, Catal. Sci. Technol. 6
Ti O W Ce S (2016) 1195–1200.
[5] X. Li, J. Li, Y. Peng, T. Zhang, S. Liu, J. Hao, Selective catalytic reduction of NO with
NH3 over novel iron-tungsten mixed oxide catalyst in a broad temperature range,
Fresha 8.71 70.87 8.71 1.31 0 42.9
Catal. Sci. Technol. 5 (2015) 4556–4564.
Spentb 19.38 63.61 7.06 0.28 9.67 38.1
[6] X. Li, J. Li, Y. Peng, X. Li, K. Li, J. Hao, Comparison of the structures and mechanism
a
of arsenic deactivation of CeO2-MoO3 and CeO2-WO3 SCR catalysts, J. Phys. Chem.
The fresh catalysts before pumped into H2O and SO2. C 120 (2016) 18005–18014.
b
The spent catalysts after pumped into H2O and SO2. [7] C. Li, M. Shen, T. Yu, J. Wang, J. Wang, Y. Zhai, The mechanism of ammonium
c
The surface composition of samples was determined by the XPS results. bisulfate formation and decomposition over V/WTi catalysts for NH3-selective
d catalytic reduction at various temperatures, Phys. Chem. Chem. Phys. 19 (2017)
The surface atomic ratio of samples was determined by the XPS results.
15194–15206.
[8] D. Marani, R.H. Silva, A. Dankeaw, K. Norrman, R.M.L. Werchmeister, D. Ippolito,
Therefore, this novel strategy could be extended to construct other M. Gudik-Sørensen, K. Hansen, V. Esposito, NO selective catalytic reduction (SCR)
catalysts for practical application. on self-supported V-W-doped TiO2 nanofibers, New J. Chem. 41 (2017) 3466–3472.
[9] F. Liu, Y. Yu, H. He, Environmentally-benign catalysts for the selective catalytic
reduction of NO from diesel engines: structure-activity relationship and reaction
Acknowledgments mechanism aspects, Chem. Commun. 50 (2014) 8445–8463.
[10] S. Yang, C. Wang, L. Ma, Y. Peng, Z. Qu, N. Yan, J. Chen, H. Chang, J. Li,
The authors acknowledge the support of Science and Technology Substitution of WO3 in V2O5/WO3-TiO2 by Fe2O3 for selective catalytic reduction of
NO with NH3, Catal. Sci. Technol. 3 (2013) 161–168.
Service Network Initiative (STS) of Chinese Academy of Science (KFJ- [11] X. Li, J. Li, Y. Peng, X. Li, K. Li, J. Hao, Selective catalytic reduction of NO with NH3
SW-STS-149), the National Natural Science Foundation of China over novel iron-tungsten mixed oxide catalyst in a broad temperature range, Catal.
(21407154, 21507137) and Province Natural Science Foundation of Sci. Technol. 3 (2013) 161–168.
[12] C. Tang, H. Zhang, L. Dong, Ceria-based catalysts for low-temperature selective
GanSu (17jRSRA317) and Science and Technology Program of Lanzhou catalytic reduction of NO with NH3, Catal. Sci. Technol. 6 (2016) 1248–1264.
City (2017-4-111). [13] S. Gao, P. Wang, F. Yu, H. Wang, Z. Wu, Dual resistance to alkali metals and SO2:
vanadium and cerium supported on sulfated zirconia as an efficient catalyst for
NH3-SCR, Catal. Sci. Technol. 6 (2016) 8148–8156.
References [14] H. Huang, W. Shan, S. Yang, J. Zhang, Novel approach for a cerium-based highly-
efficient catalyst with excellent NH3-SCR performance, Catal. Sci. Technol. 4 (2014)
[1] Y. Geng, W. Shan, S. Xiong, Y. Liao, S. Yang, F. Liu, Effect of CeO2 for a high- 3611–3614.
efficiency CeO2/WO3-TiO2 catalyst on N2O formation in NH3-SCR: a kinetic study, [15] N.Y. Topsrae, Mechanism of the selective catalytic reduction of nitric oxide by
Catal. Sci. Technol. 6 (2016) 3149–3155. ammonia elucidated by in situ on-line fourier transform infrared spectroscopy,
[2] Z. Liu, J. Zhu, J. Li, L. Ma, S.I. Woo, Novel Mn-Ce-Ti mixed-oxide catalyst for the Science 265 (1994) 1217–1219.
selective catalytic reduction of NO with NH3, ACS Appl. Mater. Interfaces 6 (2014) [16] Y. Jiang, Z. Xing, X. Wang, S. Huang, X. Wang, Q. Liu, Activity and characterization
14500–14508. of a Ce-W-Ti oxide catalyst prepared by a single step sol-gel method for selective

510
L. Zong et al.
catalytic reduction of NO with NH3, Fuel 151 (2015) 124–129.
[17] Q. Zhang, X. Liu, P. Ning, Z. Song, H. Li, J. Gu, Enhanced performance in NO re-
duction by NH3 over a mesoporous Ce-Ti-MoOx catalyst stabilized by a carbon
template, Catal. Sci. Technol. 5 (2015) 2260–2269.
[18] X. Gao, Y. Jiang, Y. Fu, Y. Zhong, Z. Luo, K. Cen, Preparation and characterization
of CeO2/TiO2 catalysts for selective catalytic reduction of NO with NH3, Catal.
Commun. 11 (2010) 465–469.
[19] W. Xu, H. He, Y. Yu, Deactivation of a Ce/TiO2 catalyst by SO2 in the selective
catalytic reduction of NO by NH3, J. Phys. Chem. C 113 (2009) 4426–4432.
[20] H. Huang, K. Liu, K. Chen, Y. Zhang, Y. Zhang, S. Wang, Ce and F comodification on
the crystal structure and enhanced photocatalytic activity of Bi2WO6 photocatalyst
under visible light irradiation, J. Phys. Chem. C 118 (2014) 14379–14387.
[21] D. Zhang, L. Zhang, L. Shi, C. Fang, H. Li, R. Gao, L. Huang, J. Zhang, In situ
supported MNO-CeOx on carbon nanotubes for the low-temperature selective cat-
alytic reduction of NO with NH3, Nanoscale 5 (2013) 1127–1136.
[22] J.H. Sinfelt, D.J.C. Yates, Catalytic hydrogenolysis of ethane over the noble metals
of Group VIII, J. Catal. 8 (1967) 82–90.
[23] Z. Huang, Z. Zhu, Z. Liu, Combined effect of H2O and SO2 on V2O5/AC catalysts for
NO reduction with ammonia at lower temperatures, Appl. Catal. B 39 (2002)
361–368.
[24] M. Gao, L. Zhu, W.L. Ong, J. Wang, G.W. Ho, Structural design of TiO2-based
photocatalyst for H2 production and degradation applications, Catal. Sci. Technol. 5
(2015) 4703–4726.
[25] M. Wang, J. Ioccozia, L. Sun, C. Lin, Z. Lin, Inorganic-modified semiconductor TiO2
nanotube arrays for photocatalysis, Energy Environ. Sci. 7 (2014) 2182–2202.
[26] N. Xu, L. Hu, Q. Zhang, X. Xiao, H. Yang, E. Yu, Significantly enhanced dielectric
performance of poly(vinylidene fluoride-co-hexafluoropylene)-based composites
filled with hierarchical flower-like TiO2 particles, ACS Appl. Mater. Interfaces 7
(2015) 27373–27381.
[27] G. Wu, J. Wang, D.F. Thomas, A. Chen, Synthesis of F-doped flower-like TiO2 na-
nostructures with high photoelectrochemical activity, Langmuir 24 (2008)
3503–3509.
[28] T. Han, Y. Chen, G. Tian, W. Zhou, Y. Xiao, J. Li, H. Fu, In situ synthesis of 3D
flower-like NiMnFe mixed oxides as monolith catalysts for selective catalytic re-
duction of NO with NH3, Sci. China Mater. 59 (2016) 1003–1016.
[29] B. Ma, P. Guan, Q. Li, M. Zhang, S. Zang, MOF-derived flower-like MoS2@TiO2
nanohybrids with enhanced activity for hydrogen evolution, ACS Appl. Mater.
Interfaces 8 (2016) 26794–26800.
[30] N.S. Khalid, W.S. WanZaki, M.K. Ahmad, Growth of rutile phased titanium dioxide
(TiO2) nanoflowers for HeLa cells treatment, IFMBE Proc. 46 (2015) 243–246.
[31] Y. Wang, Z. Mo, P. Zhang, C. Zhang, L. Han, R. Guo, H. Gou, X. Wei, R. Hu,
Synthesis of flower-like TiO2 microsphere/graphene composite for removal of or-
ganic dye from water, Mater. Design 99 (2016) 378–438.
[32] Y. Peng, W. Si, X. Li, J. Chen, J. Li, J. Crittenden, J. Hao, Investigation of the
poisoning mechanism of lead on the CeO2-WO3 catalyst for the NH3-SCR reaction
via in situ IR and raman spectroscopy measurement, Environ. Sci. Technol. 50
(2016) 9576–9582.
[33] X. Liu, P. Ning, H. Li, Z. Song, Y. Wang, J. Zhang, X. Tang, M. Wang, Q. Zhang,
511
Chemical Engineering Journal 343 (2018) 500–511
Probing NH3-SCR catalytic activity and SO2 resistance over aqueous-phase syn-
thesized Ce-W@TiO2 catalyst, J. Fuel Chem. Technol. 44 (2016) 225–231.
[34] K.A. Michalow-Mauke, Y. Lu, K. Kowalski, T. Graule, M. Nachtegaal, O. Kröcher,
D. Ferri, Flame-made WO3/CeOx-TiO2 catalysts for selective catalytic reduction of
NO by NH3, ACS Catal. 5 (2015) 5657–5672.
[35] S. Gao, P. Wang, F. Yu, H. Wang, Z. Wu, Dual resistance to alkali metals and SO2:
vanadium and cerium supported on sulfated zirconia as an efficient catalyst for
NH3-SCR, Catal. Sci. Technol. 6 (2016) 8148–8156.
[36] Y. Peng, J. Li, L. Chen, J. Chen, J. Han, H. Zhang, W. Han, Alkali metal poisoning of
a CeO2-WO3 catalyst used in the selective catalytic reduction of NO with NH3: an
experimental and theoretical study, Environ. Sci. Technol. 46 (2012) 2864–2869.
[37] S. Djerad, L. Tifouti, M. Crocoll, W. Weisweiler, Effect of vanadia and tungsten
loadings on the physical and chemical characteristics of V2O5-WO3/TiO2 catalysts,
J. Mol. Catal. A: Chem. 208 (2004) 257–265.
[38] Y. Geng, H. Huang, X. Chen, H. Ding, S. Yang, F. Liu, W. Shan, The effect of Ce on a
high-efficiency CeO2/WO3-TiO2 catalyst for the selective catalytic reduction of NO
with NH3, RSC Adv. 6 (2016) 64803–64810.
[39] J.C. Dupin, D. Gonbeau, P. Vinatier, A. Levasseur, Systematic XPS studies of metal
oxides, hydroxides and peroxides, Phys. Chem. Chem. Phys. 2 (2000) 1319–1324.
[40] G. Zhang, W. Han, F. Dong, L. Zong, G. Lu, Z. Tang, One pot synthesis of a highly
efficient mesoporous ceria-titanium catalyst for selective catalytic reduction of NO,
RSC Adv. 6 (2016) 76556–76567.
[41] R. Camposeco, S. Castillo, V. Mugica, I. Mejía-Centeno, Role of V2O5-WO3/H2Ti3O7-
nanotube-model catalysts in the enhancement of the catalytic activity for the SCR-
NH3 process, J. Marín Chem. Eng. J. 242 (2014) 313–320.
[42] P.R. Ettireddy, N. Ettireddy, T. Boningari, R. Pardemann, P.G. Smirniotis,
Investigation of the selective catalytic reduction of nitric oxide with ammonia over
Mn/TiO2 catalysts through transient isotopic labeling and in situ FT-IR studies, J.
Catal. 292 (2012) 53–63.
[43] D. Jin, Z. Hou, L. Zhang, X. Zheng, Selective synthesis of para-para′-dimethyldi-
phenylmethane over H-beta zeolite, Catal. Today 131 (2008) 378–384.
[44] Y. Shi, S. Tan, S. Li, J. Zhao, Y. Xia, B. Lv, W. Lia, Inhibitory effect of SO2 on side
reactions of NH3-SCR over olivine, Catal. Sci. Technol. 5 (2015) 3613–3623.
[45] M.A. Centeno, I. Carrizosa, J.A. Odriozola, NO-NH3 coadsorption on vanadia/ti-
tania catalysts: determination of the reduction degree of vanadium, Appl. Catal. B:
Environ. 29 (2001) 307–314.
[46] A.S. Mamede, E. Payen, P. Grange, G. Poncelet, A. Ion, M. Alifanti, V.I. Pârvulescu,
Flame-made WO3/CeOx-TiO2 catalysts for selective catalytic reduction of NO by
NH3, J. Catal. 223 (2004) 1–12.
[47] K. Wijayanti, K. Leistner, S. Chand, A. Kumar, K. Kamasamudram, N.W. Currier,
A. Yezerets, L. Olsson, Deactivation of Cu-SSZ-13 by SO2 exposure under SCR
conditions, Catal. Sci. Technol. 6 (2016) 2565–2579.
[48] Y. He, M.E. Ford, M. Zhu, Q. Liu, Z. Wu, I.E. Wachs, Selective catalytic reduction of
NO by NH3 with WO3-TiO2 catalysts: influence of catalyst synthesis method, Appl.
Catal. B: Environ. 188 (2016) 123–133.
[49] L. Chen, R. Li, Z. Li, F. Yuan, X. Niu, Y. Zhu, 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. 7 (2017) 3243–3257.
Another random document with
no related content on Scribd:
Like feendes of hell, the guiltles to betray,
But yee chiefly his kinsmen most vnkinde,
Which gaue consent to make him so away,
That vnto God, with all my heart I pray,
Vengeaunce may light on him that caused all,
Beaufort, I meane, that cursed cardinall.

27.

Which bastard priest of th’house[692] of Lancaster,

Sonne to duke Iohn, surnamed Iohn of Gaunt,
Was first create byshop of Winchester,
For no learning whereof hee might well vaunt,
Ne for vertue, which hee did neuer haunt,
But for his gold and sommes that were not small,
Payde to the pope, was made a cardinall.

28.

Proud Lucifer, which from the heauens on high

Downe to the pit of hell belowe was cast,
And being once an aungell bright in sky,
For his high pride in hell is chained fast
In deepe darknes that euermore shall last,
More hawt of heart was not before his fall,
Then was this proud and pompous cardinall:

29.

Whose life, good Baldwine, paynt out in his pickle,

And blase this Baal and belligod most blinde,
An hypocrite, all faythles, false, and fickle,
A wicked wretch, a kinsman most vnkind,
A deuill incarnat, all deuishly enclinde,
And (to discharge my conscience all at once)
The deuill him gnawe, both body, bloud, and bones.

30.
The spitefull prieste would needes make mee a witch,
As would to God I had beene for his sake,
I would haue claw’d him where hee did not itche,
I would haue playde the lady of the lake,
And as Merline was, cloasde him in a brake,
Ye a meridian to lul him by day light,
And a night mare to ride on him by night.

31.

The fiery feends with feuers hot and frenzy,

The ayery heggs with stench and carren sauoures,
The watry ghostes with gowtes and with dropsy,
The earthy goblines, with aches at all houres,
Furyes and fayryes, with all infernall powers,
I would haue stir’d from the darke dungeon
Of hell centre, as deepe as demagorgon.

32.

Or had I now the skill of dame Erichto,

Whose dreadfull charmes (as Lucan doth expresse)
All feendes did feare, so far forth as prince Pluto,
Was at her call for dread of more distresse,
Then would I send of helhoundes more and lesse
A legion at least, at him to cry and yel,
And with that chyrme, herrie him downe to hell.

33.

Which neede not, for sure I thinke that hee

Who here in earth leades Epicurus’ life,
As farre from God as possible may be,
With whome all sinne and vices are most rife,
Using at will both widdow, mayde, and wife,
But that some deuill his body doth possesse,
His life is such as men can iudge no lesse.
 34.

And God forgieue my wrath and wreakefull minde,

Such is my hate to that most wicked wretch,
Dye when hee shall, in heart I could well finde
Out of the graue his corps agayne to fetch,
And racke his limmes as long as they would stretch,
And take delight to listen euery day
How hee could sing a masse of welaway.

35.

The ile of Man was the apoynted place

To penaunce mee for euer in exile,
Thither in haste they poasted mee apace,
And douting scape, they pind mee in a pyle,
Close by my selfe in care, alas, the while,
There felt I first poore prysoner’s hungry fare,
Much want, thinges skant, and stone walles harde and
bare.

36.

The chaunge was straunge, from sylke and cloth of gold

To rugged fryze my carcas for to cloath,
From prince’s fare, and daynties hot and cold,
To rotten fish, and meates that one would loath,
The diet and dressing were much alike boath,
Bedding and lodging were all alike fine,
Such downe it was as serued well for swyne.

37.

Neyther doe I myne owne case thus complayne,

Which I confesse came partly by desert:
The only cause which doubleth all my payne,
And which most neere goeth now vnto my hearte,
Is that my fault did finally reuert
 To him that was least guilty of the same,
Whose death it was, though I abode the shame.

38.

Whose fatall fall when I doe call to minde,

And how by mee his mischiefe first began,
So ofte I cry on fortune most vnkinde,
And my mishap most vtterly doe banne,
That euer I to such a noble man,
Who from my crime was innocent and cleare,
Should bee a cause to buy his loue so deare.

39.

Oh, to my heart how greeuous is the wounde,

Calling to minde this dismall deadly case:
I would I had beene doluen vnder ground
When hee first saw or looked on my face,
Or tooke delight in any kinde of grace
Seeming in mee, that him did stir or moue
To fancy mee, or set his heart to loue.

40.

Farewell, Greenewych, my pallace of delight,

Where I was wont to see the christall streames
Of royall Thames, most plesaunt to my sight:
And farewell, Kent, right famous in all realmes,
A thousand times I minde you in my dreames,
And when I wake most griefe it is to mee,
That neuer more agayne I shall you see.[693]

41.

In the night time when I should take my rest

I weepe, I wayle, I weat my bed with teares,
And when dead sleape my spirites hath opprest,
Troubled with dreames I fantazy vayne feares,
Myne husband’s voyce then ringeth at mine eares,
Crying for help: “O saue mee from the death,
These vilaynes here doe seeke to stop my breath.”

42.

Yea, and sometimes mee thinkes his drery ghost

Appeares in sight, and shewes mee in what wise
Those fell tyraunts with torments had emboost
His winde and breath, to abuse people’s eyes,
So as no doubt or question should arise
Among rude folke, which litle vnderstand,
But that his death came only by God’s hand.

43.

I playne in vayne, where eares bee none to heare,

But roring seas, and blustring of the winde,
And of redresse am near a whit the neere,
But with waste wordes to feede my mournfull minde,
Wishing full oft the Parcas had vntwinde
My vitall stringes, or Atropose with knife
Had cut the lyne of my most wretched life.

44.

Oh that Neptune, and Æolus also,

Th’one god of seas, the other of weather,
Ere mine arriuall into that ile of woe,
Had sunke the ship wherein I sayled thether,
(The shipmen saued) so as I together
With my good duke, might haue beene deade afore
Fortune had wroken her wrath on vs so sore.

45.

Or els that God, when my first passage was

Into exile along Saynt Albon’s towne,
Had neuer let mee further for to passe,
But in the streete with death had strucke mee downe:
Then had I sped of my desired bowne,
That my poore corps mought there haue lien with his
Both in one graue, and so haue gone to blisse.

46.

But I, alas, the greater is my greefe,

Am past that hope to haue my sepulture
Nere vnto him, which was to mee most leefe,
But in an ile and country most obscure,
To pyne in payne whilst my poore life will dure,
And being dead, all honourlesse to lye
In simple graue, as other poore that dye.

47.

My tale is tolde, and time it is to ceasse

Of troubles past, all which haue had theyr end:
My graue I trust shall purchase mee such peace[694]
In such a world, where no wight doth contend
For higher place, whereto all flesh shall wend:
And so I end, vsing one word for all
As I began, that pryde will haue a fall.

Quod G. F.[695]
 [“Svrely,” sayd one of the company, “this lady hath done much to
moue the hearers to pitye her, and hath very well knit vp her[696]
tragedy according to the beginning: but I meruayl much where shee
learned all this poetry touched in her tale, for in her dayes learning
was not common, but a rare thing, namely in women.” “Yes,” quod
Maister Ferrers, “that might shee very well learne of the duke her
husband, who was a prince so excellently learned, as the like of his
degree was no where to bee founde. And not only so, but was also a
patron to poets and orators, much like as Mecenas was in the time of
Augustus Cæsar. This duke was founder of the diuinity schole in
Oxford, whereas he caused Aristotle’s workes to bee translated out
of Greeke into Latin, and caused many other thinges to bee done for
aduauncement of learning, hauing alwayes learned men nere about
him, no meruayl therefore though the duchesse brought some pece
away.” “Mee-thinke,” quod another, “shee passeth boundes of a
ladye’s modesty, to inuey so cruelly against the cardinall Beaufort.”
“Not a whit,” quod another, “hauing such cause as shee had, and
somwhat ye must beare with women’s passions. Therefore leaue
wee her to eternall rest, and let vs heare what Maister Ferrers will
say for the duke her husband, whose case was the more lamentable,
in that hee suffered without cause. And surely though the cardinall
against nature was the duke’s mortall foe, yet the chiefe causers of
his confusion was the queene and William Delapoole, earle of
Suffolke, and afterwardes duke, whose counsayle was chiefly
followed in the contriuing of this noble man’s destruction. Shee
through ambition to haue soueraynty and rule, and hee through
flattery to purchase honour and promotion, which as hee in short
time obtayned, so in as short time he lost agayne, and his life withall
by the iust iudgement of God, receiuing such measure as he before
met to this good prince. This drift of his turned to the vtter
ouerthrowe of the king himselfe, the queene his wife, and Edward
theyr son a most goodly prince, and to the subuersion of the whole
house of Lancaster, as you may see at large in the cronicles: but
now let vs heare what the duke will say.”]
 Howe Hvmfrey Plantagenet Duke of
Glocester Protector of England,
during the minority of his nephue
King Henry the sixt, (commonly called
the good Duke) by practise of
enemyes was brought to confusion.
1.

As highest hilles with tempestes beene most touched,

And tops of trees most subiect vnto winde,
And as great towers with stone strongly cowched,
Haue heauy falles when they be vndermynde,
Euen so by proofe in worldly thinges wee finde,
That such as clime the top of high degree
From perill of falling neuer can bee free.

2.

To proue this true, good Baldwine, hearken hyther,

See, and behold mee vnhappy Humfrey,[697]
England’s protector and duke of Glocester,
Who in the time of the sixt king Henry,
Ruled this realme yeares moe then twenty:
Note well the cause of my decay and fall,
And make a myrour for magistrates all.[698]

3.
In theyr moste weale to beware of vnhap,[699]
And not to sleepe in slumbring sickernes,
Whilst fortune false doth lul them in her lap
Drowned in dreames of brittle blessednesse,
But then to feare her freakes and ficklenesse
Accompting still the higher they ascend,
More nigh to bee to daunger in the end.

4.

And that vayne trust in bloud or royall race,

Abuse them not with careles assuraunce[700]
To trust fortune,[701] but waying well my case,
When shee most smyleth to haue in remembraunce[702]
My sodayne fall, who in all apparaunce[703]
Hauing most stayes which man[704] in state
mayntayne,
Haue found the same vntrusty and most vayne.

5.

Better then I none may the same affirme,[705]

Who trusting all in height of high estate,
Led by the eares with false flatterie’s chyrme,[706]
Which neuer prince could banish from his gate,
Did litle thinke on such a sodayne mate,
Not heeding, lesse breeding, all vnaware,
By foes least feared was trapt in a snare.

6.

If noble byrth or high autority,

Nombre of friendes, kinred, or alliaunce,
If wisedome, learning, [or] worldly pollicy,
Mought haue beene stayers to fortune’s variaunce,
None stoode more strong, in worldly countenaunce,
 For all these helpes had I to auayle mee,
And yet in fine, all the same did fayle mee.[707]

7.

Of king Henry the fourth,[708] fourth sonne I was,

Brother to Henry, the fift of that name,[709]
And uncle to Henry the sixt,[710] but, alas,
What cause had I to presume on[711] the same?
Or for vayne glory, aduauncing my[712] fame
My selfe to call in recordes and writinges,
The sonne, brother, and vncle vnto kinges.

8.

This was my boast, which lastly was my bane,

Yet not this boast was it that brought me downe:
The very cause which made my weale to wane
So neere of kin that I was to the crowne,
That was the rock that made my ship to drowne
A rule there is not fayling, but most sure,
Kingdome no kin doth know, ne can indure.

9.

For after my brother, the fift Henry,[713]

Wan by conquest the royall realme of Fraunce,
And of two kingdoms made one monarchy
Before his death, for better obaysaunce
To his yong sonne, not ripe to gouernaunce,
Protector of England I was by testament,
And Iohn my brother in Fraunce made regent.

10.

To whome if God had lent a longer life,

Our house to haue[714] kept from stormes of inward strife,
Or it had beene the Lord Almightie’s will
Plantagenet[te’s name] in state had standen still:
But deadly discord, which kingdomes great doth spill[715]
Bred by desire of high domination,
Brought our whole house to playne desolation.

11.

It is for truth in an history founde,

That Henry Plantagenet, first of our name,
Who called was king Henry the second,
Sonne of dame Mawde, the empresse of high fame,
Would oft report that his auncient grandame,
Though seeming in shape a woman naturall,
Was a feend of the kind that (Succubæ) some call.

12.

Which old fable, so long time told before,

When this kinge’s sonnes against him did rebell,
Hee cald to minde, and being greeued sore,
“Loe! now,” quod hee, “I see and proue full well
The story true, which folk of old did tell,
That from the deuill[716] descended all our race,
And now my children verify[717] the case.”

13.

Whereof to leaue a long memoriall

In minde of man euermore[718] to rest,
A picture hee made and hung it in his hall
Of a pellicane sitting on his nest,
With four yong byrdes, three pecking at his brest,
With bloudy beakes, and furder did deuise,
The yongest byrde to pecke the father’s eyes.

14.
Meaning hereby his rebell children three,
Henry and Richard, [who] bet him on the breast:
(Ieffrey onely from that offence was free)
Henry dyed of England’s crowne possest:
Richard liued his father to molest,
Iohn the yongest pect [still] his father’s eye,
Whose deedes vnkind the sooner made him dye.

15.

This king (some write) in his sicknes last

Sayde, as it were by way of prophecye,
How that the deuill a darnell grayne had cast
Among his kin, to encrease enmity,
Which should remayne in theyr posterity
Till mischiefe and murder had spent them all,
Not leauing one to pisse against the wall.

16.

And yet from him in order did succeede

In England here of crowned kinges, fourteene
Of that surname, and of that line and seede,
With dukes and earles, and many a noble queene,
The numbre such as all the world would weene,
So many ympes could neuer so be spent,
But some heyr male should bee of that discent.

17.

Which to bee true if any stand in doubt,

Because I meane not further to digresse,
Let him peruse the storyes[719] throughout
Of English kinges whom practise did oppresse,
And hee shall finde the cause of theyr distresse
From first to last, vnkindly to begin
Alwayes by those that next were of the kin.
 18.

Was not Richard, of whom I spake before,

A rebell playne vntill his father dyed,
And Iohn likewise an enmy euermore
To Richard agayne, and for a rebell tryed?
After whose death, it cannot bee denied,
Agaynst all right this Iohn most cruelly,
His brother’s children caused for to dye.

19.

Arthur and Isabell (I meane) that were

Ieffrey’s children, then duke of Britayne,
Henrye’s thyrd sonne, by one degree more neere
Then was this Iohn, as storyes shew most playne,
Which two children were famisht or els slayne
By Iohn theyr eame, cald Saunzterre by name,
Of whose foule act all countreys speake great shame.

20.

Edward and Richard, second both by name,

Kinges of this land, fell downe by fatall fate:
What was the cause that princes of such fame
Did leese at last theyr honour, life, and state?
Nothing at all, but discord and debate,
Which when it haps in kinred, or in bloud,
Erynnis rage was neuer halfe so wood.

21.

Be sure therefore, ye kinges and princes all,

That concord in kingdomes is chiefe assuraunce,
And that your families doe neuer fall,
But where discord doth leade the doubtfull daunce
With busy brawles, and turnes of variaunce:
Where malice is minstrel, the pype ill report,
 The maske mischiefe, and so endes the sport.

22.

But now to come to my purpose agayne,

Whilst I my charge applyed in England,
My brother in Fraunce long time did remayne,
Cardinal Beauford tooke proudly in hand,
In causes publique agaynst mee to stand,
Who of great malice, so much as hee might,
Sought in all thinges to doe mee despite.

23.

Which prowde prelate to mee was bastard eame,

Sonne to duke Iohn of Gaunt as they did fayne,
Who being made high chauncellour of the realme,
Not like a priest, but like a prince did raigne,
Nothing wanting which might his pryde maynteine,
Bishop besides of Winchester hee was,
And cardinall of Rome which angels brought to passe.

24.

Not God’s angels, but angels of old gold,

Lift him aloft in whome no cause there was
By iust desert so high to bee extold,
(Riches except) whereby this golden asse
At home and abroad all matters brought to passe,
Namely at Rome, hauing no meane but that
To purchase there his crimzin cardinall hat.

25.

Which thing the king my father him forbad

Playnly saying, that hee could not abide
Within his realme a subiect to bee had
His prince’s peere, yet such was this man’s pride,
That hee forthwith, after my father died,
(The king then young) obtayned of the pope
That honour high, which erst hee could not hope.

26.

Whose prowde attemptes because that I withstood,

My bounde duty the better to acquite,
This holy father waxed welnere wood,
Of meere malice deuising day and night
To worke to mee dishonour and despite,
Whereby there fell betweene vs such a iarre,
As in this land was like a ciuill warre.

27.

My brother Iohn, which lay this while in Fraunce,

Heard of this hurle, and past the seas in hast,
By whose traueil this troublesome distaunce
Ceassed a while, but nethelesse[720] in wast:
For rooted hate will hardly bee displast
Out of high hartes, and namely where debate,
Happeneth amongst great persons of estate.

28.

For like as a match doth lye and smolder

Long time before it commeth to the trayne:
But yet when fire hath caught in the poulder,
No arte is able the flames to restrayne:
Euen so the sparkes of enuy and disdayne,
Out of the smoke burst forth in such a flame,
That Fraunce and England yet may rue the same.

29.

So when of two realmes the regiment royall,

Betweene brothers was parted equally,
One placed in Fraunce for affayres martiall,
And I at home for ciuill pollicy:
To serue the state, wee both did so apply,
As honour and fame to both did encrease,
To him for the warre, to mee for the peace.

30.

Whence enuy sprang, and specially because

This proud prelate could not abide a peere
Within the land to rule the state by lawes,
Wherefore sifting my life and actes most neere,
Hee neuer ceast, vntill, as you shall heare,
By practise foule of him and his allies,
My death was wrought in most vnworthy wise.

31.

And first hee sought my doings to defame,

By rumours false, which hee and his did sowe:
Letters and billes to my reproach and shame
Hee did deuise, and all about bestowe,
Whereby my troth in doubt should daily growe,
In England first, and afterward in Fraunce,
Mouing all meanes to bring mee to mischaunce.

32.

One quarell was, that where by common lawe

Murder and theft beene punisht all alike,
So as manslears, which bloudy blades doe drawe,
Suffer no more then hee that doth but pike,
Mee thought the same no order pollitike,
In setting paynes to make no difference,
Betweene the lesser and greater offence.

33.
I being seene somewhat in ciuill lawe,
The rules thereof reputed much better:[721]
Wherefore to keepe offenders more in awe,
Like as the fault was smaller or greater,
So set I paynes more easier or bitter,
Waying the quality of euery offence,
And so according pronounced sentence.

34.

Amongst my other Delicta Iuuentutis,

Whilst rage of youth my reason did subdue,
I must confesse as the very truth is,
Driuen by desire, fond fancies to ensue,
A thing I did whereof great trouble grewe,
Abusing one, to my no small rebuke,
Which wife was than to Iohn, of Brabant duke.

35.

Called shee was lady Iaquet the fayre,

Delightfull in loue like Helene of Troy:
To the duke of Bauier sole daughter and heyre,
Her did I marry to my great annoy:[722]
Yet for a time, this dame I did enioy,
With her whole landes, witholding them by force,
Till Martin the pope, betweene vs made diuorce.

36.

Yet all these blastes not able were to moue

The anchor strong, whereby my ship did stay,
Some other shift to seeke him did behoue,
Whereto ere long ill fortune made the way,
Which finally was cause of my decay
And cruell death, contriued by my foes,
Which fell out thus, as now I shall disclose.
 37.

Elianor my wife, my duches only deare,

I knowe not howe, but as the nature is
Of women all, aye curious to enquire
Of thinges to come (though I confesse in this
Her fault not small) and that shee did amisse,
By witche’s skill, which sorcery some call,
Would knowe of thinges which after should befall.

38.

And for that cause made her selfe acquainted

With mother Madge, called the witch of Eye,
And with a clerke that after was attaynted,
Bolenbroke hee hight, that learned was that way,
With other moe, which famous were that day,
As well in science called mathematicall,
As also in magique [and] skill supernaturall.

39.

These cunning folkes shee set on worke to knowe

The time how long the king should liue and raygne,
Some by the starres, and some by deuills[723] belowe,
Some by witchcraft sought knowledge to attayne,
With like fancies, friuolous, fond, and vayne,
Whereof though I knewe least of any man,
Yet by that meane my mischiefe first began.

40.

Yet besides this there was a greater thing,

How shee in waxe, by councell of the witch,
An image made, crowned like a king,
With sword in hand, in shape and likenes syche
As was the king, which daily they did pitch
Against a fire, that as the waxe did melt,
 So should his life consume away vnfelt.

41.

My duchesse thus accused of this cryme,

As shee that should such practise first begin,
My part was then to yeelde vnto the time,
Geuing her leaue to deale alone therein:
And since the cause concerned deadly sinne,
Which to the clergie onely doth pertayne,
To deale therein I playnely did refrayne.

42.

And suffered them her person to ascite

Into their courtes, to aunswere and appeare,
Which to my hart was sure the greatest spight
That could be wrought, and touched mee most neare,
To see my wife, and lady leefe and deare,
To my reproch, and playne before my face,
Entreated so, as one of sort most base.

43.

The clergie then examining her cause,

Conuinced[724] her, as guilty in the same,
And sentence gaue, according to their lawes,
That shee and they whom I before did name
Should suffer death, or els some open shame:
Of which penaunce my wife by sentence had
To suffer shame, of both the two, more bad.

44.

And first shee must by dayes together three,

Through London streetes passe all along in sight
Barelegd and barefoote, that all the world might see,
Bearing in hand a burning taper bright,
And not content with this extreme despite,
To worke mee woe in all they may or can,
Exilde shee was into the ile of Man.

45.

This heynous crime and open worldly shame,

Was[725] such rigour shewed vnto my wife,
With[726] a fine fetch further thinges to frame,
And nothing els but a preparatiue
First from office, and finally from life
Mee to depriue, and so passing further,
What lawe could not, to execute by murther.

46.

Which by slie driftes and windlaces aloofe,

They brought about, perswading first the queene,
That in effect it was the kinge’s reproofe,
And her’s also, to bee exempted cleane
From princely rule, or that it should be seene
A king of yeares, still gouerned to bee
Like a pupill, that nothing could foresee.

47.

The daunger more, considering the king

Was without childe, I being his next heyre,
To rule the realme as prince in euery thing
Without restraynt, and all the sway to beare:
With people’s loue, whereby it was to feare
That my haut heart, vnbrideled in desire,
Time would preuent, and to the crowne aspire.

48.

These with such like were put into her heade,

Who of her selfe was thereto soone enclind,