Influence of supports prepared with

different precipitants over catalysts for
ammonia synthesis
Edwin Andrés Álvarez Valle
Facultad de Ciencias Exactas y Naturales
Introducción a la Catálisis Heterogénea
Es igual
Al el elemento de elementos
que otros tierras rarasdel
más abundante
grupo con
del platino,
66 emplea
se ppm encomo
la corteza terrestre;
catalizador Apareceprocesos.
en distintos disperso
en diversos
Se minerales,
encuentra como la cerita,
en minerales como bastnasita
la laurita,y
monacita.y la platarsita.
anduoita

2
Introduction
  Processes such as:
Ammonia NH3
 Industrial fixation
 the Haber-Bosch process:
Plastics
(Polyurethane)
- Easy liquefaction requires high temperatures (400–500 °C) and high pressures
(20–40 Mpa).
- High hydrogen density
  Ruthenium-based catalysts with excellent activity
Synthetic textile Fertilizers
under mild conditions are most likely to replace the
fibers (nylon)
traditional iron-based catalysts in the Haber-Bosch
process.
 
Studies have shown that the high oxygen vacancy
concentration of the support could enhance the as support
absorption of Nitrogen and desorption of Hydrogen on the - Reversible transformation of
support surface, thereby affecting the ammonia synthesis - High oxygen storage capacity
performance of the catalyst. - Abundant oxygen vacancies
- Strong metal-support interactions (SMSI)
3
Introduction
•by  different
The surface oxygen vacancies of were strongly influenced
morphologies, preparation methods and
cerium precursor.

4
 Introduction
  Cerium precursors ] on the catalytic   ¡The precipitants play a crucial role in the regulating the oxygen
oxidation of by mesoporous catalysts. vacancies of support!

5
Introduction
 The effect of support prepared by different precipitants
and on the catalytic performance of catalysts for the
water-gas shift reaction.
 The results of indicate that the stronger the basicity of the
catalysts is, the lower the catalytic activity of catalyst will
be.
The basicity of the catalysts is harmful to desorption of
that is the product of the WGS reaction , which drive the
equilibrium-limited WGS reaction to the left, resulting in the
poor catalytic activities of catalysts.
The basicity of the catalysts originates from these surface
“carbonate-like” species, which have usually been believed
to be one reason for catalyst deactivation.
The stability of the as-synthesized catalysts can be also
ranked as:
6
Experimental

 
¡Scientists have not reported the relationship between the support prepared by
different precipitants and the ammonia synthesis activity of the catalyst !

 
 Three supports were prepared under hydrothermal conditions method using and as
precipitants.

 Ammonia synthesis activity was further investigated by introducing promoters into a TPAOH
catalyst.

 The physicochemical properties of catalysts were investigated by a series of

characterizations.

7
Experimental
 Chemical
Preparation of supports:
reagents:
0.87 g
Dropwised 2.8 mL
• 
• Cerium (III) nitrate hexahydrateCe(NO3)3.6 H2O aqueous solution
Dropwised
TPAOH
EDA
of
0.2 mL
0.4 g NaOH

• 97.0 % Ruthenium (III)-2, 4-pentanedionate (Ru, 97.0 %)

• Tetrapropylammonium hydroxide (TPAOH, 25%) stirred at 25° C
for 10 min
1 h, vigorous
stirring H2N
• Sodium hydroxide (NaOH, 96%)
In 35 mL Ce(NO3)3.6H2O
NH2
Aqueous solution of

• Ethylenediamine (EDA, 99%) deionized water O

O
H H Ethylenediamine
O H
H
O CeO
CeO
CeO2-TPAOH
22-NaOH
-EDA
O + O support
N
- calcined in air at
O O- H
H O- O- 500 °C for 4 h Ru O Transferred to a 50 mL
+3 stainless-steel autoclave
Ce
H H at 85 °C
Dried O O
N+ N+ for 12 h
O
O O- -O O
O O
N+
Heated at 150 °C
H H for 48 h
H H OH-
O Washed with deionized
water and ethanol
until pH=7
Cerium (III) Nitrate hexahydrate Tetrapropylammonium hydroxide
Ruthenium (III) 2,4-Pentanedionate TPAOH
8
Experimental
  Preparation of catalysts: Ruthenium (III)
-2,4-pentanedionate
Dried in a vacuum oven
  catalysts were prepared as follows, and the Ru at 120 °C for 12 h
loadings were 2.5 wt %.
syndicated for 1 h Reduced in an H2
(60 mL min-1)
Then, r.t. for
CeO2-TPAOH 16 h 450 °C, 4 h
Ru/CeO2 catalysts
CeO2 supports CeO2-EDA CeO2 supports
CeO2–NaOH

Ru/CeO2 catalysts
Metal Precursor
2.5% Ru/CeO2-TPAOH Further
2.5% Ru/CeO2-EDA
aqueous Ba(NO3)2
2.5% Ru/CeO2–NaOH nitrate solution KNO3
CsNO3
incipient impregnation
Dried at 120 °C for 12 h method

The obtained sample was 2.5% Ru/CeO2-TPAOH

reduced in H2 at 450 °C for 4 h 24 h, r.t. catalyst

9
Experimental
Measurements of catalytic activity:

•I.   catalyst was placed in a stainless-steel reactor of a high-pressure micro-reaction experimental

device.

II. Prior to the reaction, the catalyst was purged under a nitrogen atmosphere for at . The catalyst was
then activated at , , and for under atmospheric pressure, respectively.

III. Finally, the activity data of ammonia synthesis have obtained after at the experimental pressure and
the experimental temperature .

IV. The ammonia synthesis activity of catalysts in the effluent gas was obtained by chemical titration of
solution using Congo red as an indicator.

10
Experimental
Characterization of the catalysts:
 Carried out on a benchtop powder X-ray diffractometer with radiation in
  • Analysis the range of

  • Morphology of the  Examined by Scanning Electron Microscope equipped with .

supports and catalysts

 • The lattice and the dispersibility  Observed by a high resolution transmission electron microscope .
of the active metal

• Nitrogen Adsorption- Desorption  Measured from automatic surface area analyzer at .

Isotherms

• The Pore Size Distribution  Calculated according to the method.

 • X-Ray Photoelectron
 Collected on an spectrometer with as the X-ray excitation source.
Spectroscopy
•  -Temperature Programmed
Reductions  Carried out using a chemical adsorption instrument.
  • -Temperature Programmed
• Desorption 11
Thermodynamic Aspects
𝟐  .𝟓 %  𝑹𝒖+𝟒 %𝑪𝒔/𝑪𝒆
↔ 𝑶𝟐 − 𝑻𝑷𝑨𝑶𝑯
 
𝑁 2 +3 𝐻 2 500 ° 𝐶 , 200 𝑎𝑡𝑚 2 𝑁 𝐻 3

Espontaneidad del proceso

La energía libre de Gibbs y la espontaneidad de las reacciones.
Propiedades termodinámicas del estado normal a 25°C y 1ΔG
bar.= ΔH - T ΔS Energías de enlace.
Levine. Fisicoquímica Volumen 1. 5ta edición. Rayner. Descriptive Inorganic Chemistry. 5th edition.

  ΔHN H2 ΔS NH3 ΔG Espontaneidad

2
Tipo de enlace Fuerza de enlace (kJ mol-1)
<0 >0 <0 Siempre es espontánea
ΔfH°298 (kJ mol ) -1
0 0 -46,11
N≡N Espontánea a 942
<0 <0 < 0 a T baja
ΔfG°298 (kJ mol-1) 0 0 −1-16,45 −1 temperaturas bajas
∆  𝐻 ( 298 𝐾 ) = [ 2 ( − 46,11 )
>0
−((0)+3(0)) ] 𝑘𝐽 𝑚𝑜𝑙
<0
=−92,22 𝑘𝐽 𝑚𝑜𝑙
>0
H-H
Nunca es espontánea
432

∆  𝑆( 298 𝐾 )=[ 2 ( 192,45 ) −((191,61)+3(130,684 ))] 𝐽 𝑚𝑜𝑙 𝐾 =−198,762N-H𝐽 𝑚𝑜𝑙−1Espontánea

S° (J mol K ) −1 −1
𝐾 − 1=−0,1988 −1 −1
-1 -1
m, 298 191,61 130,684 192,45
a 𝑘𝐽 𝑚𝑜𝑙
386 𝐾
>0 > 0 −1 < 0 a T−alta
1
 ∆ 𝐺 temperaturas altas
( 298 𝐾 ) = [ 2 ( −16,45 ) −((0)+3(0)) ] 𝑘𝐽 𝑚𝑜𝑙 =−32,9 𝑘𝐽 𝑚𝑜𝑙
 - T
12
Mechanism of reaction

•Se  cree que el mecanismo de reacción, que involucra el catalizador heterogéneo, involucra los siguientes pasos:

La reacción 5 ocurre en tres pasos, formando y luego . La evidencia experimental señala que la reacción 2 es el paso lento y
determinante de la velocidad. Esto no es inesperado ya que el enlace roto, el triple enlace de nitrógeno, es el más fuerte de los
enlaces que deben romperse.
13
Results
Structural and morphological analysis:

 
All characteristic peaks at angles of and are
corresponding to the cubic fluorite structure and planes.

Different precipitants have little effect on the crystal

phase structure of the support.

 
The XRD spectrum of the catalysts showed that there are
no characteristic peaks of or phase in the three catalysts,
which may be due to the small amount of metal
ruthenium, uniform dispersion, or the metal in the
catalyst exists in the form of an amorphous phase.
 Fig. S1 The patterns of supports prepared by different
precipitants and the corresponding catalysts.
14
Results
Structural and morphological analysis:

15
Results
Structural and morphological analysis:

 Fig. S2 TEM images of catalysts (a) , (b) and (c) .

16
Results
Structural and morphological analysis:

 
Fig. S3 SEM and corresponding EDAX images of catalysts
(a) , (b) and (c) .

17
Results
Specific surface area and pore diameter distribution:

 The type hysteresis loops of and type hysteresis loops of the other two supports appear between and relative
pressure , indicating that the samples have mesoporous structure.
18
Results
Specific surface area and pore diameter distribution:

 
Table S1 Surface area, pore volume and pore size of the
supports prepared by different precipitants and the
corresponding catalysts.

19
Results
  temperatura-programmed reduction :

 
Table S2 data of the supports prepared by different precipitants and
the corresponding catalysts.

 The order of consumption of catalysts below was found to be

20
Results
  X-Ray Photoelectron spectroscopy :

 
The peaks near and are attributed to the species, and the other peaks appearing near and are the
characteristic peaks of species.

21
Results
  X-Ray Photoelectron spectroscopy :

 
Table S3 XPS data of catalysts corresponding to prepared by different
precipitants.

  The presence of is related to the amount of oxygen vacancies

on the surface of cerium oxide.

22
Results
  temperature-programmed desorption :

 
Table S4 data of catalysts corresponding to prepared by
different precipitants.

 The desorption peaks of the three catalysts at high

temperature are all shifted to low temperature , indicating
that the loading of the active metal promote the
formation of a large number of weak basic sites.

23
Results
Catalytic performance for ammonia synthesis:

 TThe
he catalytic activity
addition of sequence
promoter of the
to the catalysts
catalyst is: the
reduced under the same
catalytic reaction
activity, whichconditions
may be the. introduction of the
excess promoter covered the active site of the active metal .

24
Conclusions

•   synthesized three supports of different precipitants , , and and prepared catalysts by the incipient
“We
impregnation method. The ammonia synthesis activity of catalysts as follows: at

The introduction of and promoters promoted the ammonia synthesis activity of catalyst, while inhibited the
catalytic activity of . Moreover, the catalyst reached . The high activity of catalyst is attributed to the large
oxygen vacancies, the high specific surface area, the average pore size, basic site density of support and the
interaction of

In summary, the practical significance of this work is that the precipitant of synthesis is a key factor for the
catalytic ammonia synthesis performance of low pressure Ru-based catalysts”.

25
References

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 • Ma, Z., Xiong, X., Song, C., Hu, B., & Zhang, W. (2016). Electronic metal–support interactions enhance the ammonia
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doi:10.1039/c6ra10540h

 • Lin, J., Zhang, L., Wang, Z., Ni, J., Wang, R., & Wei, K. (2013). The effect of Ag as a promoter for catalysts in ammonia
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