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 Catalysis Today xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Theory and practice of metal oxide catalyst design for the selective catalytic
reduction of NOx with NH3
Wenpo Shana, Yunbo Yua,b,c, Yan Zhanga, Guangzhi Heb, Yue Pengd, Junhua Lid, Hong Hea,b,c,*
a
Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China
b
State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing
100085, China
c
University of Chinese Academy of Sciences, Beijing 100049, China
d
School of Environment, Tsinghua University, Beijing 100084, China

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

Keywords: For NOx control in the presence of excess oxygen, selective catalytic reduction with ammonia (NH3-SCR) has
Selective catalytic reduction been successfully applied in the purification of coal-fired flue gas and diesel vehicle exhaust on a large scale. For
Catalyst design both cases, various NH3-SCR catalysts have been developed, with the incorporation of desirable catalytic
Redox sites properties being the central issue. However, the fundamental principle for designing NH3-SCR catalysts with
Acid sites
high activity, selectivity, and stability remain unclear. Generally, in the NH3-SCR reaction, the redox and acid
Nitrogen oxides abatement
sites on the catalyst are prerequisites that need to work together. Therefore, the close coupling of these dual
functional sites is imperative for the design of NH3-SCR catalysts with high NOx removal efficiency. Taking this
intrinsic principle into account, we successfully designed and developed various novel catalysts with excellent
NH3-SCR performance. This review will focus on the theory and practice of designing metal oxide catalysts for
NH3-SCR.

1. Introduction ammonia/urea (NH3-SCR) is the dominant technology for NOx control

Nitrogen oxides (NOx) play key roles in atmospheric chemistry and
can induce the formation of photochemical smog, haze, and acid rain.
Man-made NOx emissions are primarily produced during combustion
processes from stationary sources such as coal-fired power plants and
mobile sources such as motor vehicles. With rapid industrialization and
urbanization in the recent decades, increasing fossil fuel consumption
has led to severe air pollution worldwide, especially in China, with its
air pollution attracting global attention. Regional air pollution com-
plexes, combined with coal-combustion and vehicle-exhaust pollution,
have emerged in key city clusters of China, with haze and photo-
chemical pollution frequently appearing in winter and summer, re-
spectively. Due to its crucial contribution to the formation of haze and
photochemical smog, the control of NOx emissions is of great im-
portance for the overall improvement of ambient air quality.
The catalytic purification of NOx emissions from stationary sources
and diesel engines is essential [1–3]. In both cases, the common pre-
sence of excess oxygen, water vapor, and sulfur oxides provide difficult
conditions for NOx removal. Selective catalytic reduction of NOx with
and has been successfully applied for the purification of coal-fired flue
gas and diesel vehicle exhaust on a large scale. However, to meet the
increasingly stringent emission regulations, serious issues still need to
be resolved for NH3-SCR technology.
Research on NH3-SCR has increased in recent years, with the related
catalysts playing key roles in the development of this technology. Metal
oxides with variable valence are active in NH3-SCR. Therefore, various
metal oxides with different properties, such as V, Mn, Fe, Ce-based
oxides, have been developed for the control of NOx emissions from
different sources over the past several decades [2,4]. Various metal-
exchanged zeolites, such as Fe or Cu exchanged ZSM-5, SSZ-13, or
SAPO-34, have also been developed for application in diesel vehicles
due to their hydrothermal properties. Several papers have compre-
hensively reviewed research progress on zeolite catalysts for NH3-SCR
[5–7]. Therefore, the current review will focus on metal oxide catalysts,
which have been widely applied in industries for the removal of NOx
from both stationary and mobile sources.
The chemical and mechanistic aspects of NH3-SCR on metal oxide
catalysts were comprehensively reviewed 20 years ago, with catalytic

⁎
Corresponding author at: Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen
361021, China.
E-mail address: honghe@rcees.ac.cn (H. He).

https://doi.org/10.1016/j.cattod.2020.05.015
Received 19 March 2020; Received in revised form 30 April 2020; Accepted 5 May 2020
0920-5861/ © 2020 Elsevier B.V. All rights reserved.

Please cite this article as: Wenpo Shan, et al., Catalysis Today, https://doi.org/10.1016/j.cattod.2020.05.015
W. Shan, et al. Catalysis Today xxx (xxxx) xxx–xxx

systems based on supported V2O5 and catalysts containing Fe2O3, CuO,

MnOx, or CrOx discussed [2]. After that, some review papers focused on
V-based catalysts [8], V-free catalysts [4], Ce-based catalysts [9], and
Mn-based catalysts [10], respectively, were published. In addition, the
low-temperature performance and poisoning resistance of NH3-SCR
catalysts were particularly reviewed [11–13]. However, an overview of
the different types of metal oxide catalysts that connect structure-ac-
tivity relationships and reaction mechanisms with catalyst design and a
summary of the universal principle for high performance catalysts for
NH3-SCR are yet to be reported. To fill these gaps and guide catalyst
development and improvement, this review will focus on the theory and
practice of metal oxide catalyst design for NH3-SCR and establish fun-
damental principle for catalyst design.

2. Key reactions of NH3-SCR

The primary pollutant of NOx directly emitted from combustion

Fig. 1. Key reactions of NH3-SCR.
processes is NO, together with a small proportion of NO2. Therefore, the
main reaction under NH3-SCR conditions is the standard SCR reaction
(reaction 1):

4NH3 + 4NO + O2 → 4N2 + 6H2O (1)

In this reaction, the two N atoms in the formed N2 are due to a

coupling of one nitrogen atom from NO and one from NH3 [2]. When
half of the NOx consists of NO2, the conversion of NOx is remarkably
enhanced, especially at low temperatures, due to the fast SCR reaction
(reaction 2):

2NH3 + NO + NO2 → 2N2 + 3H2O (2)

To obtain high NOx conversion, NO is sometimes partially pre-oxi-

dized to NO2 before NH3-SCR; for example, by diesel oxidation catalyst
(DOC) for diesel vehicles.
In addition to the standard and fast SCR reactions, several side re-
actions also occur simultaneously. In low-temperature regions, NH4NO3 Fig. 2. Typical compositions of industrial vanadia-based catalyst and the main
may accumulate through reaction 3: functions of each component.

2NH3 + 2NO2 → NH4NO3 + N2 + H2O (3)

In high-temperature regions, the non-selective catalytic reduction
(reaction 4) and catalytic oxidation of NH3 (reactions 5 and 6) will
occur:
4NH3 + 4NO + 3O2 → 4N2O + 6H2O (4)
4NH3 + 5O2 → 4NO + 6H2O (5)
4NH3 + 7O2 → 4NO2 + 6H2O (6)
Reactions 4–6 favor the formation of N2O, NO, and NO2, respec-
tively, which reduces N2 selectivity and NOx conversion [14]. There-
fore, the development of NH3-SCR catalysts with good performance
needs to promote reactions 1 and 2 while inhibiting reactions 4–6
(Fig. 1).
3. Metal oxide catalysts for NH3-SCR
3.1. Vanadia-based oxide catalysts
Vanadia-based oxide catalysts, especially WO3- or MoO3-doped
V2O5/TiO2, with excellent SO2 resistibility, have been widely used for
the removal of NOx generated from stationary sources since the 1970s
[2]. With proper modification of catalytic properties, vanadia-based
catalysts have also been used for the SCR of NOx from diesel engines
[1,15].
Industrial vanadia-based catalysts usually use V2O5 as the main
active component, TiO2 as the support, and WO3/MoO3 as the promoter
[8]. The typical compositions of this catalyst and main functions of each
component are shown in Fig. 2. V2O5 is very active for NH3-SCR
reactions due to its redox properties and acidity, with the vanadia
species in the V5+ oxidation state as active sites for NH3-SCR reaction
[8,16]. In addition, it is an industrial catalyst for oxidizing SO2 to SO3 in
sulfuric acid production. Therefore, V2O5 has an extraordinary inherent
resistibility to sulfur poisoning in the NH3-SCR reaction. During the
development of vanadia-based catalysts, various metal oxides, such as
Al2O3, SiO2, ZrO2, and TiO2, have been tried as the support, with
anatase TiO2 finally selected. The low decomposition temperature of
titanium sulfate endues TiO2 with inherent resistibility to sulfur poi-
soning. Previous studies have also indicated that anatase TiO2 is fa-
vorable for good dispersion of active V2O5 and can supply acid sites for
NH3-SCR reactions [2]. The addition of MoO3 can inhibit the poisoning
effects of As compounds [2]. The WO3 can act as a structural promoter
to inhibit the phase transformation of anatase TiO2, which is favorable
for the improvement of thermal stability [8]. It can also act as a che-
mical promoter to increase surface acid sites, which helps inhibit the
over oxidation of NH3 and undesired oxidation of SO2, and thereby
enhances high-temperature NOx conversion, N2 selectivity, and SO2
resistance [17].
To promote the performance of traditional vanadia-based catalysts,
many studies have attempted to improve the catalyst from the aspects
of preparation method, support, and promoter, resulting in the devel-
opment of various catalysts, including V2O5/TiO2-PILC [18,19], V2O5/
microporous TiO2 [20], V2O5/TiO2-SiO2 [21], V2O5-WO3-TiO2-SiO2
[22], V2O5/Ce1-xTixO2 [23], V2O5/AC [24], and V2O5/CNTs [25]. The
coupling of V2O5 with a secondary metal species with good redox
properties (such as Fe, Ce, Mn, and Cu) has also been investigated to
obtain catalysts with dual redox functions, such as FeVO4 [26], FeVO4/
TiO2 [27], FeVO4/TiO2-WO3-SiO2 [28], CeVO4 [29], CeVO4/TiO2 [30],

2
W. Shan, et al.
Zr-promoted CeVO4 [31], W-promoted CeVO4 [32], MnOx-V2O5/TiO2
[33], CuO-V2O5/WO3-TiO2 [34], and Sb-promoted Cu3V2O8/TiO2 [35].
These improvements were mainly associated with the tuning of the
acidic and/or redox functions of the catalyst. Most of these modified
catalysts were developed for the control of NOx emissions from sta-
tionary sources and targeted the enhancement of low-temperature
performance and resistance to poisoning effects. On the other hand, the
improvement of vanadia-based catalyst for application on diesel ve-
hicles mainly aims to enhance the thermal stability and widen the
temperature window.
Although high V2O5 loading may result in high activity, high V2O5
content can simultaneously decrease thermal stability and N2 selectivity
and facilitate the catalytic oxidation of SO2 to SO3 [2,21]. The forma-
tion of SO3 can induce severe problems for equipment due to corrosion
and for the catalyst due to ammonium bisulfate (ABS) blocking.
Therefore, the development of an active vanadia-based catalyst with
low V2O5 loading is crucial. With experimental and computational
studies, it was found that polymeric vanadyl species possess much
higher NH3-SCR activity than monomeric vanadyl species [8,36,37].
Thus, polymeric vanadyl species, rather than monomeric vanadyl spe-
cies, determined NH3-SCR performance under low-temperature condi-
tions. The polymerization of vanadyl species can be enhanced by the
introduction of sulfate, thereby obtaining low-vanadia catalyst with
excellent low-temperature performance [37,38]. It has been reported
that, both VOx and WOx components are almost exclusively segregated
to the surface of the TiO2 support upon calcination of the V2O5-WO3/
TiO2 catalyst, and thus WOx can facilitate the polymerization of VOx
and enhance NH3-SCR performance as well [8,39]. Based on these
previous fundamental results, we successfully realized the in-
dustrialization of the designed vanadia-based catalyst for diesel ve-
hicles [40]. These SCR catalytic converters can meet the China IV and V
standards for diesel vehicles and have been applied widely for heavy-
duty diesel vehicles.
Although vanadia-based catalysts have been applied for 40 years,
several issues remain with this type of catalyst, such as the toxicity of
active vanadium species, narrow temperature window, and low thermal
stability (Fig. 3). Therefore, great efforts have been made on the de-
velopment of vanadium-free oxide catalysts for NH3-SCR in the last
decades [4].
3.2. Vanadium-free oxide catalysts
Variable-valence metal oxides are generally active in NH3-SCR. Mn-,
Fe-, and Ce-based oxides are three representative types of vanadium-
free oxide catalysts those have attracted most attentions [4,9,10]. To
Fig. 3. The advantages / disadvantages of vanadia-based catalysts.
3
Catalysis Today xxx (xxxx) xxx–xxx
Fig. 4. Main compositions of vanadium-free oxide catalysts.
enhance catalytic performance, acid metal oxides, such as TiO2, WO3
and MoO3, can be coupled with variable-valence metal oxides (Fig. 4).
3.2.1. Mn-based oxide catalysts
With the wide application of NH3-SCR in coal-fired power plants,
the control of NOx emissions from non-electric industries has become
increasingly important. For example, NOx emissions from electrical
power plants decreased by 81.1 % due to the application of NH3-SCR
during the 12th Five-Year Plan period (2010–2015) in China. However,
considerable challenges remain for the control of NOx emissions from
coking, iron and steel metallurgy, cement, ceramics, and industrial
boilers. Flue gas from non-electric industries is characterized by low
temperature (120–300 °C); as such, the traditional medium temperature
(300–400 °C) for NH3-SCR catalysts in power plants cannot be directly
used. Therefore, substantial efforts have been made to develop NH3-
SCR catalysts with good performance in the low-temperature range.
In addition to improvement of vanadia-based catalysts, Mn oxides,
with unique redox functions, have attracted substantial attention for
the control of NOx from industrial flue gas [41,42]. Pure MnOx pos-
sesses prominent low-temperature performance, with 100 % NOx con-
version even achieved at ≤100 °C under extremely high space velocity
of 700,000 h−1 [43]. Different preparation methods [43,44] and pre-
cipitants [45] have been used to prepare different types of MnOx, with
amorphous structure and high surface area found to be important for
the excellent catalytic performance at low temperatures. However, the
high redox property also induces some negative effects, such as high
selectivity to N2O in NH3-SCR reactions and narrow temperature
window [14].
To improve NH3-SCR performance, different types of supports have
W. Shan, et al.
been used for Mn-based oxide catalysts, such as MnOx/TiO2 [46–48],
MnOx/SiO2 [47], MnOx/Al2O3 [49], MnOx/AC [50], and MnOx/CeO2-
ZrO2-Al2O3 [51]. In addition, metal oxides with milder redox properties
and/or metal oxides with higher acidity have been used to modify
MnOx, thus obtaining Mn-Fe/TiO2 [52], Mn/Fe-Ti spinel [53], Mn-Ce/
TiO2 [54], Mn-Ni/TiO2 [55], MnCoOx [56,57], Mn-Ce oxide [58,59],
Mn-W oxide [60], Mn-Fe oxide [61], Mn-Zr oxide [62], and Mn-Cu
oxide [63] with better activity, N2 selectivity, or poisoning resistance.
During the last several decades, considerable efforts have been made to
improve Mn-based catalysts for industrial application for low-tem-
perature NH3-SCR, although the poisoning effects of SO2 remain a
challenge. The formation of NH4HSO4 and (NH4)2SO4 can block surface
active sites, and the sulfation of Mn can interrupt the redox cycle be-
tween Mn4+ and Mn3+ [10,42,64]. For the poisoning effects, S4+ of
SO2 needs to be transformed to S6+. Therefore, it is important to de-
press the oxidation of SO2 over the catalyst for the enhancement of
sulfur resistance. At the same time, the NO oxidation capability needs to
be maintained for the NH3-SCR process. Thus, Mn-based oxide catalysts
still need to be designed and modified under theory guidance.
3.2.2. Fe-based oxide catalysts
Fe-based oxides have been investigated as NH3-SCR catalysts for
several decades [4]. The catalytic performance of Fe2O3 can be en-
hanced by tuning the crystal phase and shape at the nanometer level
[65]. More frequently and efficiently, Fe oxide is promoted by acidic
oxides, such as TiO2 and WO3, and the obtained Fe-Ti oxide [66–69]
and Fe-W oxide [70,71] catalysts usually possess high NOx conversion,
N2 selectivity, and SO2 durability in the medium temperature range.
Some Fe-based oxides with more complex components have also been
developed, such as Fe-TiO2-PILC [72], Fe2(SO4)3/TiO2 [73], Fe-Ce-Ti
oxides [74], Fe-Cu-Ti oxides [75], Fe-W-Ti oxides [76], Fe-W-Ce oxides
[77], and Fe-W-Zr oxides [78,79].
To obtain high NH3-SCR activity, we developed an FeTiOx catalyst
in which Fe and Ti oxides were combined at the atomic level by co-
precipitation [68]. The FeTiOx catalyst showed much better catalytic
performance than the Fe2O3/TiO2 catalyst prepared by impregnation
(Fig. 5) [80]. Iron titanate crystallite with a specific Fe-O-Ti structure
was reported to be the main active phase for the FeTiOx catalyst, and
the synergistic effects between iron and titanium (as acid sites) species
at the atomic scale resulted in high activity. Based on systemic char-
acterizations, including N2 physisorption, XRD, XPS, H2-TPR, UV–vis
DRS, Raman spectroscopy, and XAFS, a specific edge-shared Fe3+-(O)2-
Ti4+ structure was proposed (Fig. 5) [81]. At low temperatures, NO is
oxidized to nitrate species on Fe3+ (as redox sites) and then reacts with
adjacent adsorbed NH4+ species on Ti4+−OH Brønsted acid sites to
Fig. 5. Activity and microstructural model of Fe-Ti oxide catalyst [80,81]. Reaction conditions: [NO] = [NH3] =500 ppm, [O2] =5 vol.%, N2 balance, and
GHSV = 50,000 h−1.
4
Catalysis Today xxx (xxxx) xxx–xxx
form intermediate ammonium nitrate species, followed by the final
reaction with gaseous NO to produce N2 and H2O [82]. At high tem-
peratures, the adsorbed NH3 species on Ti4+ can be activated to -NH2
species by neighboring Fe3+ sites, and then react with gaseous NO to
form a NH2NO intermediate and finally decompose into N2 and H2O
[82].
Very recently, a single-atom Mo/Fe2O3 catalyst was developed by
anchoring single Mo ions on (001) surfaces of reducible α-Fe2O3, and
the individual Mo ion and one neighboring Fe ion were thus con-
structed as one dinuclear site [83]. Since the Mo and Fe ions can pro-
vide acidic and redox functions, respectively, the dinuclear site acts as a
highly active acid-redox site for NH3-SCR.
3.2.3. Ce-based oxide catalysts
Due to its excellent oxygen release/storage properties, the rare-
earth metal oxide ceria is widely used as a promoter to enhance per-
formance of various catalysts [9,84]. For NH3-SCR catalysts, ceria is
also an effective promoter for vanadium-based catalysts [85], zeolite
catalysts [86], and Mn-based low-temperature catalysts [54]. Ce oxide
has excellent redox properties due to the redox shift between Ce3+ and
Ce4+. Through the combination of Ce with acidic components, we de-
veloped a Ce-based NH3-SCR catalyst ten years ago, resulting in the
preparation of a Ce-Ti oxide (Ce/TiO2) catalyst by impregnation [87].
Ce oxide has since been widely used as the main active component in
NH3-SCR catalysts, and the study of Ce-based catalysts has become an
important research area for NH3-SCR [9].
Preparation methods play crucial roles in the determination of the
interaction between the components of a catalyst, and thereby influence
catalytic performance for NH3-SCR. To improve the catalytic perfor-
mance of Ce-Ti oxides, different preparation methods have been em-
ployed, such as sol-gel [88], co-precipitation [89], homogenous pre-
cipitation [90], flame-spray [91], and spontaneous deposition [92].
These methods produce catalysts with different structural properties
and combination types of components. The Ce-O-Ti short-range order
species with interaction between Ce and Ti at the atomic scale are
proposed to be active sites [89]. Generally, to obtain highly efficient
catalysts, the preparation process must achieve high dispersion of active
CeO2. Different promoters have been used to improve NH3-SCR activity,
N2 selectivity, poisoning resistance, and thermal stability of Ce-Ti oxide
catalysts [9]. As a result, Ce-Fe-Ti oxides [93], Ce-Cu-Ti oxides [94], Ce-
Co-Ti oxides [95], Ce-Bi-Ti oxides [96], Ce-Sn-Ti oxides [97], Ce-W-Ti
oxides [98,99], Ce-Mo-Ti oxides [100,101], Ce-Nb-Ti oxides [102], Ce-
Zr-Ti oxides [103,104], and Ce-Si-Ti oxides [105] have been developed.
These added promoters mainly enhance the redox and acidic functions
of the catalyst.
W. Shan, et al.
To improve surface acidity, different acids have been used to modify
CeO2. Sulfuric acid and phosphoric acid are very effective at improving
the catalytic performance of CeO2 [106–108]. Different metal oxides,
such as the oxides of W [109–111], Mo [112], and Nb [113], have also
been used to modify CeO2 for NH3-SCR. Among them, WO3 with intense
acidity is highly compatible for coupling with CeO2, with the obtained
Ce-W oxide catalysts presenting excellent NOx conversion, N2 se-
lectivity, and poisoning resistance in a wide temperature range, even
under high space velocity [109,110,114]. The synergistic interactions
between well-dispersed Ce and W oxide phases, with CeO2 acting as a
redox site and WO3 acting as an acid site, are crucial for excellent
catalytic performance [91,115]. With the close coupling of CeO2 and
WO3, a CeWOx catalyst prepared by homogenous precipitation exhibit
much better catalytic performance than the industrially applied V2O5-
WO3/TiO2 and Fe-ZSM-5 catalysts [109], and NH3-SCR systems based
on the CeWOx catalyst ensure that the NOx emissions from a heavy duty
diesel engine meet the Euro V limit (Chinese V limit), without the need
for any other aftertreatment device, in an engine bench test [116].
4. Reaction mechanism of NH3-SCR
To gain insight into NH3-SCR reactions over metal oxide catalysts,
extensive research has been devoted to the reaction mechanisms on
different catalysts, such as the abovementioned V-based, Mn-based, Fe-
based, and Ce-based catalysts, by various methods, such as spectro-
scopy, adsorption-desorption, kinetics, and computational studies
[2,4,8,117]. Different hypotheses have been proposed for different
catalyst components, metal loadings, and test conditions.
A well-known catalytic cycle for the SCR reaction over V-based
catalysts involving both acid-based and redox functions was proposed
by Topsøe, which indicated that both redox and acid sites are needed
for NH3-SCR [118]. Redox functions and surface acid properties play
key roles in NH3-SCR performance at low and high temperatures, re-
spectively [119]. Although significant progress has been achieved in
regards to our understanding of NH3-SCR reactions over V-based cata-
lysts, debate remains for some issues, including the dominant role of
isolated vs. oligomeric surface vanadia sites, importance of Brønsted vs.
Lewis acid sites, and nature of surface reaction intermediate complexes
[16,120,121].
Based on DFT calculations and experimental evidence, we deduced
the entire NH3-SCR mechanism over monomeric and polymeric
Fig. 6. Mechanism of standard NH3-SCR reaction. (A) Reactions over monomeric V2O5/TiO2 surfaces. (B) Reactions over dimeric V2O5/TiO2 surfaces. Reactants are
marked in red; products are marked in blue [37] (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article).
5
Catalysis Today xxx (xxxx) xxx–xxx
vanadia/TiO2 surfaces (Fig. 6). The computational results showed that
the coupling effect of the polymeric vanadyl species markedly reduced
the overall reaction barrier of the catalytic cycle. Therefore, the dimeric
vanadyl species, rather than the monomeric vanadyl species, de-
termined the low-temperature performance of V-based catalysts for
NH3-SCR, being in consistent with the experimental results [36–38].
The requirement for redox and acid sites for NH3-SCR over V-based
catalysts also accounts for vanadium-free oxide catalysts. For example,
previous study has suggested that the NH3-SCR reaction mechanism for
CeO2-WO3 catalysts consists of two independent cycles, i.e., a redox
cycle due to the excellent oxygen storage capability and reducibility of
CeO2 and an acid site cycle resulting from Brønsted acid sites formed on
the WeOeW species of Ce2(WO4)3 [122]. In addition, an NH3-SCR
cycle pathway over β-MnO2 catalysts has been reported on the basis of
DFT calculations [43]. NH3 tends to be adsorbed at the Lewis acid Mn
site on MnO2 surfaces. Adsorbed NH3 is activated by the transfer of a H
atom to surface lattice O and subsequently reacts with NO in the gas
phase, resulting in the formation of an NH2NO intermediate. NH2NO is
further changed into N2 through dehydrogenation/hydrogenation. The
rate-limiting step is the removal of surface H atoms. This reaction
mechanism is somewhat similar to that proposed by us for the V-based
catalyst system (Fig. 6).
Although there is still some debate on the reaction mechanisms of
NH3-SCR, it is well accepted that two types of reaction mechanisms
exist for metal oxide catalysts, i.e., the Langmuir-Hinshelwood (L-H)
mechanism (reaction between adsorbed NOx and NH3 species) at low
temperature and Eley-Rideal (E–R) mechanism (reaction between ad-
sorbed NH3 species and gaseous NO) at high temperature. For example,
the NH3-SCR mechanisms for FeTiOx catalysts with a specific Fe-O-Ti
structure at different temperature ranges have been proposed (Fig. 7)
[82]. Both Brønsted and Lewis acid sites are involved in the reaction.
NH3 is mainly adsorbed on Ti sites in the form of ionic NH4+ and co-
ordinated NH3, whereas NOx is mainly adsorbed on Fe sites in the form
of monodentate nitrate. At low temperatures (< 200 °C), the reactive
surface species are mainly NH4+ and monodentate nitrate, and the
reaction mainly follows the L-H mechanism, in which the formation of
monodentate nitrate from NO oxidation by O2 over Fe3+ is the rate-
determining step. On the other hand, at high temperatures (> 200 °C),
the reaction mainly follows the E–R mechanism, in which the formation
of NH2NO intermediate species following H-abstraction of NH3 by
neighboring Fe3+ is the rate-determining step.
W. Shan, et al.
Fig. 7. Proposed NH3-SCR reaction mechanisms over FeTiOx catalysts at different temperature ranges [82].
Fig. 8. Design principle of NH3-SCR oxide catalysts.
Based on the NH3-SCR reaction mechanisms over metal oxide cat-
alysts, it can be concluded that the key points for the adjustments of
low-temperature and high-temperature performances are redox func-
tions and acid properties, respectively.
The deactivations induced by chemical poisons, such as alkali/al-
kaline earth metals and SO2, are important issues for NH3-SCR catalysts.
The deactivation effects of alkali/alkaline earth metals on NH3-SCR
catalysts are attributed to the decrease of surface acidity and re-
ducibility, which are the key for the adsorption and activation of NH3
and NOx [123–125]. The formation of metal sulfates, due to the exist of
SO2, can induce irreversible poisoning effects owing to the loss of redox
functions and the cutoff of L-H reaction pathway [12,126–129]. In ad-
dition, thermal aging can also induce decline of redox ability and sur-
face acidity for NH3-SCR catalysts, as well as segregation of redox and
acid sites, and thus results in deactivations [91,130–132]. Therefore,
the stabilization of redox and acid sites is the key to design NH3-SCR
catalyst with good poisoning resistance and high thermal stability.
6
Catalysis Today xxx (xxxx) xxx–xxx
5. Design principle and applications of NH3-SCR oxide catalysts
In recent years, considerable efforts have been devoted to the de-
velopment of environmentally benign, highly efficient, and thermally
stable NH3-SCR catalysts. However, theoretical guidance for the de-
velopment of a highly efficient NH3-SCR catalyst is still lacking, and
design principle for NH3-SCR catalysts is urgently required. Based on
extensive understanding of the structure-activity relationship of NH3-
SCR catalysts and the reaction mechanism at different temperature
ranges, we established a high dispersion-close coupling (HDCC) prin-
ciple for the design of NH3-SCR catalysts that involves the close cou-
pling of redox and acid sites, thus guiding the development of mixed
oxide catalysts with excellent performance.
The NH3-SCR reaction is determined by the redox properties of the
catalyst. Thus, we propose that metal oxides with variable valence are
active in NH3-SCR and V-, Mn-, Fe-, and Ce-based oxides can exhibit
good NH3-SCR performance. On the other hand, an acid component is
needed to guarantee the occurrence of the reaction. In the NH3-SCR
reaction, the redox and acid sites must work together. Therefore, high
dispersion of sites with the same function and close coupling of sites
with different functions are key factors for the design of a highly effi-
cient NH3-SCR catalyst (Fig. 8).
Using the variable-valence metals V, Fe, Ce, and Mn as redox
components, and Ti, W, and Mo as acid components, we closely coupled
the two types of components with a short-range ordered and highly
dispersed structure. Thereby, novel V-S-Ti [37], V-Nb-Ce [133], Fe-Ti
[80], Fe-Mn-Ti [134], Fe-W [71], Mn-W [60], Mn-Nb [135], Ce-Ti
[136], Ce-W-Ti [99], Ce-W [109], Ce-Nb [137], Ce-W-Zr [138], and Ce-
Mo-Zr [139] oxide catalysts with excellent NH3-SCR performance were
developed. These achievements provide a theoretical basis and prac-
tical examples for the development of novel and highly efficient NH3-
SCR catalysts.
To explain the application of the design principle for highly efficient
NH3-SCR catalysts, the development of Ce-based catalysts under theo-
retical guidance was used as an example (Fig. 9).
Through the combination of redox and acidic components, a Ce/
TiO2 catalyst was firstly prepared by an impregnation method [87].
W. Shan, et al.
Fig. 9. Development of Ce-based catalysts under guidance of design principle [87,99,134]. Reaction conditions: [NO] = [NH3] =500 ppm, [O2] =5 vol.%, N2
balance, and GHSV = 100,000 h−1.
Both the pure ceria and titanium dioxide showed rather poor SCR
performance in the whole temperature range, whereas the Ce/TiO2
catalyst showed good performance over a relatively wide temperature
range, indicating the synergistic effects between the redox component
of ceria and acidic component of titanium dioxide due to the formation
of active Ce-O-Ti species [89].
For the purpose of enhancing the coupling degree of cerium and
titanium oxides, the preparation method was improved. The catalyst
prepared by impregnation showed clear phase separation, whereas
homogenous precipitation was able to closely couple the cerium and
titanium oxides [134]. Therefore, the catalyst prepared by homogenous
precipitation exhibited enhanced SCR activity.
To further improve the catalytic performance, tungsten was used as
a catalyst promoter [99]. The addition of tungsten enhanced the dis-
persion of surface cerium and the formation of surface oxygen va-
cancies, and thereby improved low-temperature performance due to
enhanced redox functions. On the other hand, the addition of tungsten
enhanced the adsorption of NH3 and inhibited the unselective oxidation
of NH3 due to its strong acidity and weak oxidizability, and thus high-
temperature NOx conversion and N2 selectivity were both improved.
6. Summary and outlook
Research on NH3-SCR catalysts and reactions has attracted great
interest worldwide, especially in recent years due to the increasingly
stringent standards for NOx emissions. Metal oxides with variable va-
lence are generally active in NH3-SCR. Various NH3-SCR catalysts with
different properties have been developed for the control of NOx emis-
sions from different sources over the past few decades, including V-,
Mn-, Fe-, and Ce-based oxides with high NH3-SCR activity. Based on
extensive understanding of the structure-activity relationship of NH3-
SCR catalysts and the reaction mechanism at different temperature
ranges, we established a principle for the design of NH3-SCR catalysts to
guide the development of mixed oxide catalysts with excellent perfor-
mance. In the NH3-SCR reaction, the redox and acid sites must work
together. Therefore, high dispersion of sites with the same function and
close coupling of sites with different functions are key factors for the
design of a highly efficient NH3-SCR catalyst.
Due to the urgent demand for NOx control in the non-electric in-
dustry, the development of NH3-SCR catalysts with good performance
at low-temperature range, together with resistance to the poisoning
effects of SO2, H2O, and alkaline particulates, is crucial for denitration
from stationary sources. Low-temperature performance is also very
important for diesel vehicles to meet the increasingly stringent stan-
dards for NOx emissions. There are limitations in regard to the catalyst
7
Catalysis Today xxx (xxxx) xxx–xxx
volume that can be placed on board, which requires that the catalyst
works efficiently for NH3-SCR. In addition, the hydrothermal stability
of catalysts on diesel vehicles is of great importance due to the com-
bining of SCR with DPF (diesel particulate filter).
Although various metal oxides have been investigated for NH3-SCR
over the past several decades, there are still many challenges in this
area. For low-temperature NOx abatement from flue gas, the SCR per-
formance of traditional vanadia-based catalysts needs to be enhanced
together with depression of SO2 oxidation activity, and the resistance of
Mn-based oxide catalysts to SO2 poisoning needs to be substantially
improved. Improvement of hydrothermal stability is also required for
V-, Fe-, and Ce-based oxides catalysts, which is a primary factor re-
stricting their practical application in diesel vehicles.
Under the guidance of the HDCC design principle, close coupling of
the redox and acid sites is a key factor for the design of highly efficient
NH3-SCR catalysts. The balance and stabilization of redox and acid
functions are also key for the improvement of poisoning resistance, N2
selectivity, and thermal stability of NH3-SCR catalysts. In addition,
enhancing our fundamental understanding of the structure-activity re-
lationships and the NH3-SCR reaction mechanisms is important for
improving catalyst design theory.
Declaration of competing interest
None.
CRediT authorship contribution statement
Wenpo Shan: Writing - original draft, Writing - review & editing,
Funding acquisition. Yunbo Yu: Writing - review & editing. Yan
Zhang: Writing - review & editing. Guangzhi He: Writing - review &
editing. Yue Peng: Writing - review & editing. Junhua Li: Writing -
review & editing. Hong He: Conceptualization, Writing - review &
editing, Funding acquisition.
Acknowledgment
This work was financially supported by the National Natural Science
Foundation of China (21637005, 51822811).
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ses bagages, et frissonna de terreur en en voyant les murailles nues
comme si le feu y eût été mis. Les admirables boiseries sculptées
par Van-Huysium et le portrait du Président avaient été vendus, dit-
on, à lord Spencer. La salle à manger était vide, il ne s’y trouvait plus
que deux chaises de paille et une table commune sur laquelle
Marguerite aperçut avec effroi deux assiettes, deux bols, deux
couverts d’argent, et sur un plat les restes d’un hareng saur que
Claës et son valet de chambre venaient sans doute de partager. En
un instant elle parcourut la maison, dont chaque pièce lui offrit le
désolant spectacle d’une nudité pareille à celle du parloir et de la
salle à manger. L’idée de l’Absolu avait passé partout comme un
incendie. Pour tout mobilier, la chambre de son père avait un lit, une
chaise et une table sur laquelle était un mauvais chandelier de
cuivre où la veille avait expiré un bout de chandelle de la plus
mauvaise espèce. Le dénûment était si complet qu’il ne s’y trouvait
plus de rideaux aux fenêtres. Les moindres objets qui pouvaient
avoir une valeur dans la maison, tout, jusqu’aux ustensiles de
cuisine, avait été vendu. Émue par la curiosité qui ne nous
abandonne même pas dans le malheur, Marguerite entra chez
Lemulquinier, dont la chambre était aussi nue que celle de son
maître. Dans le tiroir à demi fermé de la table, elle aperçut une
reconnaissance du Mont-de-Piété qui attestait que le valet avait mis
sa montre en gage quelques jours auparavant. Elle courut au
laboratoire, et vit cette pièce pleine d’instruments de science comme
par le passé. Elle se fit ouvrir son appartement, son père y avait tout
respecté.
Au premier coup d’œil qu’elle y jeta, Marguerite fondit en larmes
et pardonna tout à son père. Au milieu de cette fureur dévastatrice, il
avait donc été arrêté par le sentiment paternel et par la
reconnaissance qu’il devait à sa fille! Cette preuve de tendresse
reçue dans un moment où le désespoir de Marguerite était au
comble, détermina l’une de ces réactions morales contre lesquelles
les cœurs les plus froids sont sans force. Elle descendit au parloir et
y attendit l’arrivée de son père, dans une anxiété que le doute
augmentait affreusement. Comment allait-elle le revoir? Détruit,
décrépit, souffrant, affaibli par les jeûnes qu’il subissait par orgueil?
Mais aurait-il sa raison? Des larmes coulaient de ses yeux sans
qu’elle s’en aperçût en retrouvant ce sanctuaire dévasté. Les images
de toute sa vie, ses efforts, ses précautions inutiles, son enfance, sa
mère heureuse et malheureuse, tout, jusqu’à la vue de son petit
Joseph qui souriait à ce spectacle de désolation, lui composait un
poème de déchirantes mélancolies. Mais, quoiqu’elle prévît des
malheurs, elle ne s’attendait pas au dénoûment qui devait couronner
la vie de son père, cette vie à la fois si grandiose et si misérable.
L’état dans lequel se trouvait monsieur Claës n’était un secret pour
personne. A la honte des hommes, il ne se rencontrait pas à Douai
deux cœurs généreux qui rendissent honneur à sa persévérance
d’homme de génie. Pour toute la société, Balthazar était un homme
à interdire, un mauvais père, qui avait mangé six fortunes, des
millions, et qui cherchait la pierre philosophale, au Dix-Neuvième
Siècle, ce siècle éclairé, ce siècle incrédule, ce siècle, etc... On le
calomniait en le flétrissant du nom d’alchimiste, en lui jetant au nez
ce mot:—Il veut faire de l’or! Que ne disait-on pas d’éloges à propos
de ce siècle, où, comme dans tous les autres, le talent expire sous
une indifférence aussi brutale que l’était celle des temps où
moururent Dante, Cervantes, Tasse e tutti quanti. Les peuples
comprennent encore plus tardivement les créations du génie que ne
les comprenaient les Rois.
Ces opinions avaient insensiblement filtré de la haute société
douaisienne dans la bourgeoisie, et de la bourgeoisie dans le bas
peuple. Le chimiste septuagénaire excitait donc un profond
sentiment de pitié chez les gens bien élevés, une curiosité railleuse
dans le peuple, deux expressions grosses de mépris et de ce væ
victis! dont sont accablés les grands hommes par les masses quand
elles les voient misérables. Beaucoup de personnes venaient devant
la Maison Claës, se montrer la rosace du grenier où s’était consumé
tant d’or et de charbon. Quand Balthazar passait, il était indiqué du
doigt; souvent, à son aspect, un mot de raillerie ou de pitié
s’échappait des lèvres d’un homme du peuple ou d’un enfant; mais
Lemulquinier avait soin de le lui traduire comme un éloge, et pouvait
le tromper impunément. Si les yeux de Balthazar avaient conservé
cette lucidité sublime que l’habitude des grandes pensées y imprime,
le sens de l’ouïe s’était affaibli chez lui. Pour beaucoup de paysans,
de gens grossiers et superstitieux, ce vieillard était donc un sorcier.
La noble, la grande maison Claës s’appelait, dans les faubourgs et
dans les campagnes, la maison du diable. Il n’y avait pas jusqu’à la
figure de Lemulquinier qui ne prêtât aux croyances ridicules qui
s’étaient répandues sur son maître. Aussi, quand le pauvre vieux
ilote allait au marché chercher les denrées nécessaires à la
subsistance, et qu’il prenait parmi les moins chères de toutes,
n’obtenait-il rien sans recevoir quelques injures en manière de
réjouissance; heureux même, si, souvent, quelques marchandes
superstitieuses ne refusaient pas de lui vendre sa maigre pitance en
craignant de se damner par un contact avec un suppôt de l’enfer.
Les sentiments de toute cette ville étaient donc généralement
hostiles à ce grand vieillard et à son compagnon. Le désordre des
vêtements de l’un et de l’autre y prêtait encore, ils allaient vêtus
comme ces pauvres honteux qui conservent un extérieur décent et
qui hésitent à demander l’aumône. Tôt ou tard ces deux vieilles gens
pouvaient être insultés. Pierquin, sentant combien une injure
publique serait déshonorante pour la famille, envoyait toujours,
durant les promenades de son beau-père, deux ou trois de ses gens
qui l’environnaient à distance avec la mission de le protéger, car la
révolution de juillet n’avait pas contribué à rendre le peuple
respectueux.
Par une de ces fatalités qui ne s’expliquent pas, Claës et
Lemulquinier, sortis de grand matin, avaient trompé la surveillance
secrète de monsieur et madame Pierquin, et se trouvaient seuls en
ville. Au retour de leur promenade ils vinrent s’asseoir au soleil, sur
un banc de la place Saint-Jacques où passaient quelques enfants
pour aller à l’école ou au collége. En apercevant de loin ces deux
vieillards sans défense, et dont les visages s’épanouissaient au
soleil, les enfants se mirent à en causer. Ordinairement, les
causeries d’enfants arrivent bientôt à des rires; du rire, ils en vinrent
à des mystifications sans en connaître la cruauté. Sept ou huit des
premiers qui arrivèrent se tinrent à distance et se mirent à examiner
les deux vieilles figures en retenant des rires étouffés qui attirèrent
l’attention de Lemulquinier.
—Tiens, vois-tu celui-là dont la tête est comme un genou?
—Oui.
 —Hé! bien, il est savant de naissance.
—Papa dit qu’il fait de l’or, dit un autre.
—Par où? C’est-y par là ou par ici? ajouta un troisième en
montrant d’un geste goguenard cette partie d’eux-mêmes que les
écoliers se montrent si souvent en signe de mépris.
Le plus petit de la bande qui avait son panier plein de provisions,
et qui léchait une tartine beurrée, s’avança naïvement vers le banc
et dit à Lemulquinier:—C’est-y vrai, monsieur, que vous faites des
perles et des diamants?
—Oui, mon petit milicien, répondit Lemulquinier en souriant et lui
frappant sur la joue, nous t’en donnerons quand tu seras bien
savant.
—Ha! monsieur, donnez-m’en aussi, fut une exclamation
générale.
Tous les enfants accoururent comme une nuée d’oiseaux et
entourèrent les deux chimistes. Balthazar, absorbé dans une
méditation d’où il fut tiré par ces cris, fit alors un geste d’étonnement
qui causa un rire général.
—Allons, gamins, respect à un grand homme! dit Lemulquinier.
—A la chienlit! crièrent les enfants. Vous êtes des sorciers.—Oui,
sorciers, vieux sorciers! sorciers, na!
Lemulquinier se dressa sur ses pieds, et menaça de sa canne les
enfants qui s’enfuirent en ramassant de la boue et des pierres. Un
ouvrier, qui déjeunait à quelques pas de là, ayant vu Lemulquinier
levant sa canne pour faire sauver les enfants, crut qu’il les avait
frappés, et les appuya par ce mot terrible: A bas les sorciers!
Les enfants, se sentant soutenus, lancèrent leurs projectiles qui
atteignirent les deux vieillards, au moment où le comte de Solis se
montrait au bout de la place, accompagné des domestiques de
Pierquin. Ils n’arrivèrent pas assez vite pour empêcher les enfants
de couvrir de boue le grand vieillard et son valet de chambre. Le
coup était porté. Balthazar, dont les facultés avaient été jusqu’alors
conservées par la chasteté naturelle aux savants chez qui la
préoccupation d’une découverte anéantit les passions, devina, par
un phénomène d’intussusception, le secret de cette scène; son
corps décrépit ne soutint pas la réaction affreuse qu’il éprouva dans
la haute région de ses sentiments, il tomba frappé d’une attaque de
paralysie entre les bras de Lemulquinier qui le ramena chez lui sur
un brancard, entouré par ses deux gendres et par leurs gens.
Aucune puissance ne put empêcher la populace de Douai d’escorter
le vieillard jusqu’à la porte de sa maison, où se trouvaient Félicie et
ses enfants, Jean, Marguerite et Gabriel qui, prévenu par sa sœur,
était arrivé de Cambrai avec sa femme. Ce fut un spectacle affreux
que celui de l’entrée de ce vieillard qui se débattait moins contre la
mort que contre l’effroi de voir ses enfants pénétrant le secret de sa
misère. Aussitôt un lit fut dressé au milieu du parloir, les secours
furent prodigués à Balthazar dont la situation permit, vers la fin de la
journée, de concevoir quelques espérances pour sa conservation.
La paralysie, quoique habilement combattue, le laissa néanmoins
assez long-temps dans un état voisin de l’enfance. Quand la
paralysie eut cessé par degrés, elle resta sur la langue qu’elle avait
spécialement affectée, peut-être parce que la colère y avait porté
toutes les forces du vieillard au moment où il voulut apostropher les
enfants.
Cette scène avait allumé dans la ville une indignation générale.
Par une loi, jusqu’alors inconnue, qui dirige les affections des
masses, cet événement ramena tous les esprits à monsieur Claës.
En un moment il devint un grand homme, il excita l’admiration et
obtint tous les sentiments qu’on lui refusait la veille. Chacun vanta sa
patience, sa volonté, son courage, son génie. Les magistrats
voulurent sévir contre ceux qui avaient participé à cet attentat; mais
le mal était fait. La famille Claës demanda la première que cette
affaire fût assoupie. Marguerite avait ordonné de meubler le parloir,
dont les parois nues furent bientôt tendues de soie. Quand,
quelques jours après cet événement, le vieux père eut recouvré ses
facultés, et qu’il se retrouva dans une sphère élégante, environné de
tout ce qui était nécessaire à la vie heureuse, il fit entendre que sa
fille Marguerite devait être venue, au moment même où elle rentrait
au parloir; en la voyant, Balthazar rougit, ses yeux se mouillèrent
sans qu’il en sortît des larmes. Il put presser de ses doigts froids la
main de sa fille, et mit dans cette pression tous les sentiments et
toutes les idées qu’il ne pouvait plus exprimer. Ce fut quelque chose
de saint et de solennel, l’adieu du cerveau qui vivait encore, du cœur
que la reconnaissance ranimait. Épuisé par ses tentatives
infructueuses, lassé par sa lutte avec un problème gigantesque et
désespéré peut-être de l’incognito qui attendait sa mémoire, ce
géant allait bientôt cesser de vivre; tous ses enfants l’entouraient
avec un sentiment respectueux, en sorte que ses yeux purent être
récréés par les images de l’abondance, de la richesse, et par le
tableau touchant que lui présentait sa belle famille. Il fut
constamment affectueux dans ses regards, par lesquels il put
manifester ses sentiments; ses yeux contractèrent soudain une si
grande variété d’expression qu’ils eurent comme un langage de
lumière, facile à comprendre. Marguerite paya les dettes de son
père, et rendit, en quelques jours, à la maison Claës une splendeur
moderne qui devait écarter toute idée de décadence. Elle ne quitta
plus le chevet du lit de Balthazar, de qui elle s’efforçait de deviner
toutes les pensées, et d’accomplir les moindres souhaits. Quelques
mois se passèrent dans les alternatives de mal et de bien qui
signalent chez les vieillards le combat de la vie et de la mort; tous
les matins, ses enfants se rendaient près de lui, restaient pendant la
journée dans le parloir en dînant devant son lit, et ne sortaient qu’au
moment où il s’endormait. La distraction qui lui plut davantage parmi
toutes celles que l’on cherchait à lui donner, fut la lecture des
journaux que les événements politiques rendirent alors fort
intéressants. Monsieur Claës écoutait attentivement cette lecture
que monsieur de Solis faisait à voix haute et près de lui.
Vers la fin de l’année 1832, Balthazar passa une nuit
extrêmement critique pendant laquelle monsieur Pierquin le médecin
fut appelé par la garde, effrayée d’un changement subit qui se fit
chez le malade; en effet, le médecin voulut le veiller en craignant à
chaque instant qu’il n’expirât sous les efforts d’une crise intérieure
dont les effets eurent le caractère d’une agonie.
Le vieillard se livrait à des mouvements d’une force incroyable
pour secouer les liens de la paralysie; il désirait parler et remuait la
langue sans pouvoir former de sons; ses yeux flamboyants
projetaient des pensées; ses traits contractés exprimaient des
douleurs inouïes; ses doigts s’agitaient désespérément, il suait à
grosses gouttes. Le matin, les enfants vinrent embrasser leur père
avec cette affection que la crainte de sa mort prochaine leur faisait
épancher tous les jours plus ardente et plus vive; mais il ne leur
témoigna point la satisfaction que lui causaient habituellement ces
témoignages de tendresse. Emmanuel, averti par Pierquin,
s’empressa de décacheter le journal pour voir si cette lecture ferait
diversion aux crises intérieures qui travaillaient Balthazar. En
dépliant la feuille, il vit ces mots, découverte de l’absolu, qui le
frappèrent vivement, et il lut à Marguerite un article où il était parlé
d’un procès relatif à la vente qu’un célèbre mathématicien polonais
avait faite de l’Absolu. Quoique Emmanuel lût tout bas l’annonce du
fait à Marguerite qui le pria de passer l’article, Balthazar avait
entendu.
Tout à coup le moribond se dressa sur ses deux poings, jeta sur
ses enfants effrayés un regard qui les atteignit tous comme un éclair,
les cheveux qui lui garnissaient la nuque remuèrent, ses rides
tressaillirent, son visage s’anima d’un esprit de feu, un souffle passa
sur cette face et la rendit sublime, il leva une main crispée par la
rage, et cria d’une voix éclatante le fameux mot d’Archimède:
EURÊKA! (j’ai trouvé). Il retomba sur son lit en rendant le son lourd
d’un corps inerte, il mourut en poussant un gémissement affreux, et
ses yeux convulsés exprimèrent jusqu’au moment où le médecin les
ferma le regret de n’avoir pu léguer à la Science le mot d’une
énigme dont le voile s’était tardivement déchiré sous les doigts
décharnés de la Mort.

Paris, juin-septembre 1834.

FIN DU TOME QUATORZIÈME.

 TABLE DES MATIÈRES.

ÉTUDES PHILOSOPHIQUES.

La Peau de Chagrin 1
Jésus-Christ en Flandre 225
Melmoth réconcilié 241
Le Chef-d’œuvre inconnu 283
La Recherche de l’Absolu 308

FIN DE LA TABLE

PARIS.—IMP. DE PILLET FILS AINÉ, RUE DES GRANDS-AUGUSTINS, 5.

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