TUGAS KINETIKA KIMIA DAN KATALIS

REVIEW JURNAL

OLEH KELOMPOK 4 KIMIA A:

NURUL QALBIYAH FADILLAH PUCE
NURDALIA ALAM
RAHMI HULOPI
AGUSTINA EKAWATI SAPUTRI HUSAIN
SRI RAHMAWATI S. GUGE

JURUSAN KIMIA
FAKULTAS MATEMATIKA DAN ILMU
PENGETAHUAN ALAM
UNIVERSITAS NEGERI GORONTALO
 REVIEW JURNAL KINETIKA KIMIA DAN KATALIS

Judul Steady state isotopic transient kinetic analysis of the

combustion Co-Mn-O catalysts.
Jurnal Catalysis Communications
Volume dan Halaman Vol. 125, Hal 32-36
Tahun 2019
Penulis Marek Rotko, Witold Zawadzki, Vladyslav Redko
Reviewer Nurul Qalbiyah Fadillah Puce
Nurdalia Alam
Rahmi Hulopi
Agustina Ekawati Saputri Husain
Sri Rahmawati S. Guge
Tanggal 26 Oktober 2020

Tujuan Penelitian Tujuan dalam penelitia ini adalah untuk menganalisis

jumlah dan aktivitas 2mmonium2 dari sisi aktif yang ada
pada permukaan system katalitik Kobalt-Mangan yang
berfungsi untuk oksidasi metana.
Subjek Penelitian Subjek penelitian ini adalah 2mmoni katalitik yang
dibuat dengan pengendapan bersama dari larutan berair
yang mengandung kobalt asetat dan mangan asetat dalam
jumlah yang sesuai. Larutan 2mmonium karbonat berair
digunakan sebagai reagen pengendapan dengan
kecepatan 5 cm3 / menit. Co-presipitasi dilakukan pada
313 K sampai dicapai pH = 8. Endapan yang diperoleh
dikondisikan pada suhu 313 K selama 2 jam, kemudian
disaring dan dicuci dengan akuades (sampai pH = 7
tercapai) dan dengan etanol anhidrat. Prekursor katalis
yang diperoleh dikeringkan pada 383 K dan dikalsinasi
pada 673 K selama 2 jam.
Metode Penelitian Metode yang digunakan pada penelitian ini adalah
metode eksperimental.
Langkah Penelitian • Karakterisasi Katalis
Adsorpsi nitrogen dilakukan pada suhu nitrogen cair
dan sampel yang diuji dibuang pada suhu 573
K.Berdasarkan adsorpsi nitrogen dan isoterm desorpsi,
ukuran pori rata-rata ditentukan dengan menggunakan
metode Barret-Joyner-Halenda, dan volume pori
diperkirakan berdasarkan isoterm desorpsi.
Komposisi fase padat katalis yang diperoleh ditentukan
dengan difraksi sinar-X (XRD). Untuk tujuan ini,
difraktometer sinar-X Empyrean resolusi tinggi
 (PANalytical) digunakan. Diantaranya, kuvet berdiri
bebas dan lampu dengan anoda Cu digunakan. Fase
kristalografi yang ada dalam katalis diidentifikasi
berdasarkan database Komite Bersama Standar Difraksi
Serbuk (JCPDS). Fraksi kuantitatif fase individu
ditentukan dengan menggunakan analisis Rietveld.
• Uji aktivitas katalitik
Uji aktivitas dilakukan dalam sistem reaksi
Mikroaktivitas (PID Eng & Tech, Spanyol) dan
spektrometer massa kuadrupol HPR-20 R&D (Hiden
Analytical, UK) digunakan untuk analisis gas. Analisis
dilakukan pada sampel katalis 50 mg yang diencerkan
dengan 450 mg pasir kuarsa. Campuran reaksi terdiri
dari 6 vol% metana, 18 vol% oksigen, 6 vol% argon
dan helium sebagai gas keseimbangan. Laju alir
campuran reaksi melalui unggun katalitik adalah 100
cm3 / menit. Temperatur sistem reaksi dinaikkan secara
linier pada kecepatan 5 K / menit.
• Percobaan SSITKA
Percobaan SSITKA dilakukan dalam modifikasi
sistem reaksi Mikroaktivitas (PID Eng & Tech,
Spanyol), dan menggunakan spektrometer massa
R & D HPR-20 (Hiden Analytical, Inggris).
Sampel katalis 50 mg diencerkan dengan 450 mg
pasir kuarsa digunakan di setiap katalis yang diuji.
Campuran reaksi terdiri dari 6 vol% metana
(12CH4 atau 13CH4), 18 vol% oksigen, 6 vol%
argon atau kripton, dan heilium sebagai gas
keseimbangan. Laju aliran campuran reaksi
melalui unggun katalitik adalah 100 cm3 / menit.
Di bawah kondisi isotermal dan isobarik, sebuah
saklar dibuat antara aliran yang mengandung
12CH4 / O2 / Ar / He dan aliran yang
mengandung 13CH4 / O2 / Kr / He. Selain itu,
sakelar isotop selalu dilakukan setelah 1 jam
reaksi kondisi-mapan pada suhu yang sesuai
dengan 10, 20, 30, 40, 50 dan 60% konversi
metana (menurut aktivitas spesifik padatan).
Tidak mungkin mencapai nilai konversi yang
lebih rendah dari 20% (rezim kinetik) dengan
jumlah katalis serendah mungkin pada suhu reaksi
yang diinginkan.
Hasil Penelitian • Sifat Fisikokimia Katalis
Katalis yang diperoleh dikarakterisasi dengan
metode XRF untuk perbedaan kandungan kobalt dan
mangan (Tabel 1). Hasil yang diperoleh menegaskan
rasio molar kobalt ke mangan (disajikan sebagai
nama katalis) yang diperkirakan pada tahap
pembuatan katalis. Katalis 0,7Co-0,3Mn dicirikan
oleh luas permukaan spesifik terbesarnya, katalis
 dengan kandungan mangan tertinggi memiliki
sedikit lebih rendah, dan SSA terkecil ditemukan
dalam kasus kandungan kobalt tertinggi (Tabel 2).
Selain itu, semakin besar luas permukaan spesifik,
semakin kecil ukuran pori rata-rata, sedangkan
dalam kasus volume pori, nilai yang sangat mirip
dicatat untuk ketiga sistem katalitik. Fase kristal dari
sistem katalitik yang dipelajari terutama terdiri dari
Co3O4, sedangkan dalam kasus sistem yang
mengandung jumlah mangan yang lebih tinggi
(0,5Co-0,5Mn dan 0,7Co-0,3Mn), fase MnCo2O4
dan Mn2CoO3 juga dicatat (Tabel 3). Ukuran kristal
primer rata-rata terkecil ditemukan untuk padatan
0.7Co-0.3Mn, sedangkan yang terbesar
satu untuk 0.9Co-0.1Mn, dengan ukuran kristal
rata-rata berada dalam kisaran 6-14 nm. Fase
kristalografi yang teridentifikasi sejalan dengan
data literatur.
• Performa Katalitik
Katalis yang mengandung jumlah mangan terkecil
(0.9Co-0.1Mn) ditandai dengan aktivitas tertinggi,
dan aktivitas terendah tercatat di atas katalis
dengan kandungan mangan tertinggi (0.5Co-
0.5Mn). Oleh karena itu, semakin kecil jumlah
manga dalam padatan (Mn-Co-O) semakin tinggi
aktivitasnya. Parameter fisika-kimiawi lain seperti:
luas permukaan spesifik dan ukuran kristal primer
rata-rata kurang penting dalam hal ini. Katalis
0,7Co-0,3Mn, yang dicirikan oleh luas permukaan
spesifik yang jauh lebih besar (94,1 m2 / g) dan
kurang dari setengah dalam ukuran kristal primer
rata-rata (ca.6,6 nm) jika dibandingkan dengan
katalis 0,9Co-0,1Mn (65,3 m2 / g dan14,1 nm,
masing-masing), menunjukkan sifat katalitik yang
lebih rendah. Hasil yang diperoleh sebanding dengan
data literatur ,yang menunjukkan bahwa aktivitas
tertinggi dalam oksidasi metana ditemukan pada
katalis ko-balt-mangan dengan kandungan mangan
terkecil.
• Hasil SSITKA
Hasil yang diperoleh SSITKA juga menunjukkan
bahwa situs aktif terdiri dari atom / atom kobalt dan
atom / atom mangan, karena perubahan komposisi
kimia katalis tidak hanya mengarah pada pergeseran
jumlah situs aktif, tetapi juga ke variasi aktivitas
intrinsik mereka. Ternyata dengan menggunakan
jumlah kobalt dan mangan yang sama, kita dapat
memperoleh katalis yang dikarakterisasi oleh situs
aktif dengan efisiensi sangat tinggi dalam proses
oksidasi metana. Namun, jumlah situs aktif yang
 lebih kecil dibandingkan dengan katalis yang
mengandung sedikit mangan, dan jumlah kobal yang
tinggi, membuat laju reaksi keseluruhan lebih rendah.
Kelebihan Penelitian Penelitian yang dilakukan memungkinkan kami untuk
menentukan nilai perkiraan dari jumlah dan efisiensi
situs aktif pada permukaan kerja oksida logam
campuran berbasis kobalt-mangan sebagai katalis
oksidasi metana.
Kekurangan Penelitian Kami hanya dapat berspekulasi bahwa jalur karbon
dari CH4 ke CO2 terdiri dari zat antara reaksi aktif
berikut: eCH3-s, eCH2-s, eCH-s, eC-s dan eCO-s,
tanpa mengecualikan keberadaan eCHxO-s. Selain
itu, yang disebut spektator atau spesies tidak aktif,
seperti karbonat dan format, juga dapat dibentuk.
SSITKA digabungkan dengan DRIFTS dapat
memberikan informasi baru tentang sifat zat antara
reaksi. Namun, studi DRIFTS yang tersedia
mengenai oksidasi metana telah menunjukkan bahwa
sulit untuk mencatat setiap zat antara reaksi aktif, di
mana hanya beberapa karbonat dan senyawa yang
teramati sebelum reaksi oksidasi metana dilakukan.
Kesimpulan Secara umum, saat suhu naik, jumlah situs aktif
meningkat (dengan sedikit penurunan jumlah situs
aktif dalam beberapa rentang suhu), sedangkan nilai
maksimum diamati untuk aktivitas situs intrinsik,
sehingga efisiensi situs aktif tertinggi dapat dicapai
dalam kisaran suhu tertentu. Jumlah situs aktif dan
aktivitasnya juga bergantung pada komposisi kimiawi
katalis. Katalis kobalt-mangan dengan kandungan
mangan sekitar 10% berat dicirikan oleh jumlah situs
aktif per gram basis tertinggi; masih dalam beberapa
kisaran temperatur, efisiensi mereka dalam proses
oksidasi metana lebih rendah atau jauh lebih rendah
dibandingkan dengan situs aktif yang ada pada
permukaan sistem katalitik lainnya. Namun
demikian, bahkan dengan aktivitas situs yang lebih
rendah, konsentrasinya yang jauh lebih besar
membuatnya menunjukkan aktivitas katalitik terbaik
per gram basa dalam oksidasi metana.
 Demikian review jurnal dari
kami untuk memenuhi tugas
mata kuliah kinetika kimia dan
katalis
 Catalysis Communications 125 (2019) 32–36

Contents lists available at ScienceDirect

Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Short communication

Steady state isotopic transient kinetic analysis of the combustion of CH4 over T
Co-Mn-O catalysts
⁎
Marek Rotko , Witold Zawadzki, Vladyslav Redko
Maria Curie-Skłodowska University, Faculty of Chemistry, Department of Chemical Technology, 3 Maria Curie-Skłodowska Square, 20-031 Lublin, Poland

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

Keywords: The main objective of the research was the analysis of the number and intrinsic activity of active sites present on
Complete methane oxidation the surface of working cobalt-manganese-based catalytic systems for complete methane oxidation. The obtained
Cobalt-manganese catalyst values of these parameters strongly depend on the reaction temperature and chemical composition of studied
SSITKA catalysts. The highest number of active sites is present on the surface of the cobalt-manganese catalyst, which
demonstrates the best catalytic activity in methane oxidation. Nevertheless, in some temperature ranges intrinsic
activity of its active sites is lower than that of the active sites present on the surface of other catalysts.

1. Introduction
Cobalt-manganese-based catalytic systems can form an alternative
to palladium and platinum-based catalysts, because replacing precious
metals with cheaper equivalent materials will foster faster and wider
development of a catalytic combustion technology. This will bring
measurable financial benefits and will have a positive impact on the
environment. That is why the replacement of the flame burning pro-
cesses with solutions based on catalytic oxidation will favour reduction
of atmospheric emissions of unburned hydrocarbons, nitrogen oxides
and carbon monoxide. In addition, the use of catalysts will enable the
use of lean fuel-air mixtures with a low concentration of combustible
components, which are currently frequently unused and emitted to the
environment. Mining and agriculture industries are among those re-
sponsible for these types of emissions.
Available literature data indicate good [1,2] or very good [3,4]
properties of cobalt-manganese-based catalytic systems for the process
of complete oxidation of methane. It was demonstrated, among others,
that the cobalt-manganese-based catalysts with a low content of man-
ganese are characterized by highest activity [3,4]. Their activity is also
affected by several physicochemical parameters, including the active
surface area, crystallite size and phase composition [1–4]. In fact, all
the aforesaid parameters affect the number of active sites present on the
surface of the catalyst and their intrinsic activity. Therefore, one of the
crucial tasks seems to be to determination of the number of active sites
and their intrinsic activity for the respective catalytic system. Most of
the efforts made towards this goal are based on spectroscopic and ad-
sorption methods which appear far from the conditions that prevail
during the actual course of the catalytic process. Practically the sole
method that allows to estimate the number of active sites in actual
working conditions of the catalytic system is the steady state isotopic
transient kinetic analysis (SSITKA) [5]. Evidently, we can also attempt
to determine the chemical nature of active intermediates and the
number of active sites present on the surface of the working catalyst
with the use of the “operando” DRIFTS technique (DRIFTS-Mass spec-
troscopy). However, the design of the measuring IR reactor cell does not
fully reflect the conditions prevailing in a flow reactor, and the presence
of very active reaction intermediates (very short residence times)
cannot always be accurately recorded. Therefore, the analysis of the
number of active sites present on the surface of a working cobalt-
manganese-based catalytic systems for complete oxidation of CH4,
performed with the SSITKA method, was the main objective of our
research. It has to be underlined that the SSITKA method provides the
number of active sites strictly related to the applied experimental
conditions (e.g. T and reactant feed concentrations), and readsorption
phenomena of products must be corrected [5,6].
2. Experimental
2.1. Catalysts preparation
The present catalytic systems were prepared by co-precipitation
from an aqueous solution containing appropriate amounts of cobalt
acetate and manganese acetate. An aqueous solution of ammonium
carbonate was used as the precipitation reagent at the rate of 5 cm3/
min. Co-precipitation was carried out at 313 K until pH = 8 was

⁎
Corresponding author.
E-mail address: marekrotko@poczta.umcs.lublin.pl (M. Rotko).

https://doi.org/10.1016/j.catcom.2019.03.019
Received 30 October 2018; Received in revised form 21 March 2019; Accepted 24 March 2019
Available online 25 March 2019
1566-7367/ © 2019 Elsevier B.V. All rights reserved.
M. Rotko, et al.
reached. The obtained precipitate was conditioned at 313 K for 2 h, and
then filtered and washed with distilled water (until pH = 7 was
reached) and with anhydrous ethanol. The obtained catalyst precursors
were dried at 383 K and calcined at 673 K for 2 h.
2.2. Catalysts characterisation
The actual composition of the catalysts produced was determined by
X-ray fluorescence (XRF) spectroscopy (Axios mAX spectrometer,
PANalytical, The Netherlands). The analysis of the results was carried
out using the Omnian and Pro-Trace programs, part of the SuperQ 5
software suite.
The specific surface area of the obtained catalysts was determined
using the Brunauer-Emmett-Teller method [7], based on the nitrogen
adsorption isotherm. The test was carried out in the ASAP 2420 MP
analytical system (Micromeritics Instrument Corporation, USA). Ni-
trogen adsorption was carried out at the temperature of liquid nitrogen
and the sample subjected to the test was degassed at 573 K. On the basis
of nitrogen adsorption and desorption isotherms, the mean pore size
was determined using the Barret-Joyner-Halenda method [8], and the
pore volume was estimated based on the desorption isotherm.
The solid phase composition of the obtained catalysts was de-
termined by means of X-ray diffraction (XRD). For this purpose, a high-
resolution Empyrean X-ray diffractometer (PANalytical) was used.
Among others, a free-standing cuvette and a lamp with a Cu anode were
used. The crystallographic phases present in the catalysts were identi-
fied based on the Joint Committee on Powder Diffraction Standards
(JCPDS) database. The quantitative fractions of individual phases were
determined using Rietveld analysis [9].
2.3. Catalytic activity measurements
Activity tests were carried out in the Microactivity reaction system
(PID Eng & Tech, Spain) and a HPR-20 R&D quadrupole mass spec-
trometer (Hiden Analytical, UK) was used for gas analysis. The analysis
was carried out on 50 mg catalyst samples diluted with 450 mg of
quartz sand. The reaction mixture consisted of 6 vol% methane, 18 vol
% oxygen, 6 vol% argon and helium as balance gas. The flow rate of the
reaction mixture through the catalytic bed was 100 cm3/min. The
temperature of the reaction system was linearly raised at the rate of
5 K/min.
2.4. SSITKA experiments
The SSITKA experiments were carried out in a modified
Microactivity reaction system (PID Eng & Tech, Spain), and using an
HPR-20 R&D mass spectrometer (Hiden Analytical, UK). A 50-mg cat-
alyst sample diluted with 450 mg of quartz sand was used in every
tested catalyst. The reaction mixture consisted of 6 vol% methane
(12CH4 or 13CH4), 18 vol% oxygen, 6 vol% argon or krypton, and he-
lium as balance gas. The flow rate of the reaction mixture through the
catalytic bed was 100 cm3/min. Under isothermal and isobaric condi-
tions, a switch was made between the stream containing 12CH4/O2/Ar/
He and the stream containing 13CH4/O2/Kr/He. Moreover, isotopic
switches were always carried out after 1 h of steady-state reaction at
temperatures corresponding to 10, 20, 30, 40, 50 and 60% of methane
conversion (according to the specific activity of the solid). It was not
possible to achieve conversion values lower than 20% (kinetic regime)
with the lowest possible amount of catalyst at the reaction temperatures
of interest.
Based on the magnitude of the delay between the signal from 12CO2
and that from Ar, the average lifetime of carbon dioxide and of active
intermediates leading to the formation of carbon dioxide were de-
termined (the appropriate equation is provided in the Electronic
Supporting Information, ESI). It should be added at this point that the
concentration of water and oxygen during the isotopic switches did not
33
Catalysis Communications 125 (2019) 32–36
change. Knowing the rate at which the reaction mixture was fed, the
catalyst mass, methane conversion and the average lifetime of carbon
dioxide and intermediates leading to the formation of carbon dioxide,
the surface concentration of reversibly adsorbed CO2 and that of the
intermediates leading to its formation were determined (the appro-
priate equations are given in ESI). Based on the magnitude of the delay
(if it is observed) between the signal from 12CH4 and the signal from Ar,
the average lifetime of methane and the concentration of reversibly
adsorbed methane can be determined (see ESI). The surface con-
centration of intermediates leading to the formation of carbon dioxide
corresponds to the number (concentration) of the active sites present on
the surface of the catalyst under given reaction conditions, whereas the
reciprocal of the average lifetime of intermediates leading to the for-
mation of carbon dioxide corresponds to the average efficiency (in-
trinsic activity) of active sites. In the subject literature, this parameter is
referred to as intrinsic centre activity [10] or TOF of particular type
(TOFITK) [5]. In this situation, the values of TOFITK are higher than the
values of turnover frequency based on the concentration of true active
sites (TOFSite). The latter refers to sites present in the catalytic cycle for
which the adsorbed reaction intermediates associated with are not
measured by SSITKA. For example, in the present work, adsorbed active
O species were not measured by the 12CH4/13CH4 SSITKA switch. In
addition, it should be mentioned that TOFITK and TOFSite and also
turnover frequency based on chemisorption (TOFchem) follow the re-
lationship: TOFchem ≤ TOFSite ≤ TOFITK [5]. More detailed information
on the mathematical processing and analysis of the results obtained by
the SSITKA method can be found in previous publications [11,12],
while the theoretical basis has been extensively elaborated in review
papers [5,6,13,14].
3. Results and discussion
3.1. Catalysts physicochemical properties
The obtained catalysts were characterized by the XRF method for
their different contents of cobalt and manganese (Table 1). The results
obtained confirm the molar ratio of cobalt to manganese (presented as
the catalyst name) estimated at the preparation stage of the catalysts.
The 0.7Co-0.3Mn catalyst is characterized by its largest specific surface
area, the catalyst with the highest manganese content has a slightly
lower one, and the smallest SSA was found in the case of the highest
cobalt content (Table 2). In addition, the larger the specific surface
area, the smaller the average pore size, while in the case of pore vo-
lume, a very similar value was recorded for all three catalytic systems.
The crystalline phase(s) of the catalytic systems studied consists
mainly of Co3O4, while in the case of systems containing higher
amounts of manganese (0.5Co-0.5Mn and 0.7Co-0.3Mn), MnCo2O4 and
Mn2CoO3 phases were also recorded (Table 3). The smallest average
primary crystal size is found for 0.7Co-0.3Mn solid, while the largest
one for 0.9Co-0.1Mn, with the average crystallite size to be in the range
of 6–14 nm. Identified crystallographic phases are in line with literature
data [2].
3.2. Catalytic performance
Fig. 1 presents a comparison of the activity of the catalytic systems
Table 1
Cobalt and manganese content in the catalysts determined by XRF.
Catalyst Metal content (wt%) Molar ratio (Co:Mn)
Co Mn
0.5Co-0.5Mn 37.2 32.5 0.52:0.48
0.7Co-0.3Mn 51.8 19.1 0.72:0.28
0.9Co-0.1Mn 68.0 6.5 0.91:0.09
M. Rotko, et al. Catalysis Communications 125 (2019) 32–36

Table 2
Total BET surface area, average pore diameter and volume of pores determined
from nitrogen adsorption/desorption measurements for the cobalt-manganese
catalysts.
Catalyst Total BET surface Average pore Volume of pores
area (m2/g) diameter (nm) (cm3/g)

0.5Co-0.5Mn 80.0 9.02 0.213

0.7Co-0.3Mn 94.1 7.66 0.222
0.9Co-0.1Mn 65.3 11.94 0.216

Table 3
Phases composition and mean size of crystallites for the cobalt-manganese
catalysts determined on the base of XRD.
Catalyst Crystallographic phases Mean size of
crystallites (nm)
Chemical Content (%) Crystallite size
formula (nm)

0.5Co-0.5Mn Mn2CoO4 22 18.3 11.4 Fig. 2. Normalised transient response curves of Ar, 12CH4 and 12CO2 obtained
MnCo2O4 21 9.1 during the SSITKA switch (12CH4/O2/Ar/He → 13CH4/O2/Kr/He).
Co3O4 57 9.5
0.7Co-0.3Mn Mn2CoO4 31 3.8 6.6
MnCo2O4 19 4.0 intermediates (e.g. CHx-s and/or CHxO-s), while the delay (Fig. 2) be-
Co3O4 50 9.3 tween the Ar and 12CO2 response curves provides information on the
0.9Co-0.1Mn Co3O4 100 14.1 14.1 reversibly adsorbed carbon dioxide and reaction intermediates that lead
to the formation of carbon dioxide from CH4 gas (tracing the C-path).
Based on the magnitude of the delay between the Ar and 12CH4, the
average lifetime of reversibly adsorbed methane molecules (Fig. S1, left
plot, ESI) were determined, while based on the magnitude of the delay
between the Ar and 12CO2, the average lifetime of carbon dioxide and
reaction intermediates leading to the formation of carbon dioxide were
determined (Fig. S2, left plot, ESI). Knowing the flow rate of the reac-
tion mixture, the catalyst mass, methane conversion (actual values
measured during the SSITKA experiments) and the average lifetime, the
surface concentration of reversibly adsorbed methane molecules (Fig.
S1, right plot, ESI) and also the surface concentration of carbon dioxide
and intermediates leading to the formation of carbon dioxide (Fig. S2,
right plot, ESI) were determined. The surface concentration of re-
versibly adsorbed methane corresponds to the concentration of ad-
sorption sites occupied by reversibly adsorbed methane molecules on
the catalyst surface at working reaction conditions (Fig. 3, left plot).
These reversibly adsorbed methane molecules are only observed at low
temperatures, when the methane conversion is small (below 30%).
Fig. 1. Activity of the cobalt-manganese catalysts as a function of reaction With increasing reaction temperature, the concentration of reversibly
temperature. adsorbed methane quickly decreases the fastest on the surface of 0.9Co-
0.1Mn and the slowest on the surface of 0.5Co-0.5Mn. These results
studied. The catalyst containing the smallest amount of manganese suggest that with increasing reaction temperature, all adsorbed me-
(0.9Co-0.1Mn) is characterized by the highest activity, and the lowest thane molecules take part in the reaction with oxygen or its surface
activity was recorded over the catalyst with the highest manganese coverage is below the detection limit. Similar results were also observed
content (0.5Co-0.5Mn). Therefore, the smaller the amount of manga- during the SSITKA analysis of the process of methane oxidation on the
nese in the solid (Mn-Co-O) the higher the activity. Other physico- palladium and platinum catalysts [11,12].
chemical parameters such as: specific surface area and mean primary The recorded values of the surface concentration of adsorbed carbon
crystallite size are found to be less important in this respect. The 0.7Co- dioxide and of the active intermediates derived from adsorbed methane
0.3Mn catalyst, which is characterized by a much larger specific surface and which eventually lead to the formation of carbon dioxide, corre-
area (94.1 m2/g) and less than half in the mean primary crystal size (ca. spond to the concentration of active sites on the surface of the working
6.6 nm) when compared to the 0.9Co-0.1Mn catalyst (65.3 m2/g and catalyst (Fig. 3, right plot). The concentration of these sites does not
14.1 nm, respectively), exhibits inferior catalytic properties. The ob- appear constant but depends on reaction conditions. In general, as the
tained results are comparable with literature data [4], which suggest temperature increases, we observe an increase in the number of active
that the highest activity in the oxidation of methane is found in co- sites available for methane oxidation reaction. This is probably due to
balt‑manganese catalysts with the smallest content of manganese. the fact that initially the process of methane oxidation takes place only
on the most active sites of the catalyst surface (these are most likely
crystallite corners and edges, defects in the crystalline structure),
3.3. SSITKA results whereas with temperature increase, new sites of the catalyst surface
become also active (e.g. crystal faces not active at lower temperatures).
The delay (Fig. 2) between the Ar and 12CH4 response curves sug- The sole exception here is the slight reduction of this parameter for the
gests that certain amount of methane molecules can be reversibly ad- 0.5Co-0.5Mn catalyst at about 700 K and for the 0.7Co-0.3Mn catalyst
sorbed on the catalyst surface and further provide active reaction

34
M. Rotko, et al.
Fig. 3. Concentration of sites occupied by reversibly adsorbed methane molecules (left plot) and concentration of active sites (right plot) present on the working
surface of cobalt-manganese catalysts.
Fig. 4. Rate of methane oxidation (left plot) and intrinsic site activity (right plot) on the working surface of the cobalt-manganese catalysts.
at about 710 K. All catalysts were calcined at 673 K, so above this
temperature, the structure of the catalyst surface can be subjected to
change (e.g. as a result of sintering), and the amount of the most active
elements of the catalyst surface can be reduced. Similar catalysts, yet
calcined at 773 K, demonstrate lower specific surface areas: 0.9Co-
0.1Mn < 13.6 m2/g; 0.7Co-0.3Mn < 10.7 m2/g and 0.5Co-0.5Mn <
25.0 m2/g. The highest concentration of active sites is observed on the
surface of 0.9Co-0.1Mn catalyst, which has the highest activity (Fig. 1),
while the lowest one appears on the surface of 0.5Co-0.5Mn catalyst.
Whereas the catalytic behaviour of the 0.7Co-0.3Mn catalyst in the
temperature range 650–700 K is interesting, as it is characterized by a
number of active sites close to that of 0.9Co-0.1Mn catalyst, yet its
methane oxidation activity is worse. This fact results from the lower
values of intrinsic site activity of active sites present in the solid (Fig. 4,
right plot). The values of intrinsic site activity in the temperature range
of 650–700 K appear much higher for the 0.9Co-0.1Mn catalyst than for
the 0.7Co-0.3Mn one. Thus, the 0.9Co-0.1Mn catalyst uses its active
sites more efficiently.
In general, the intrinsic site activity values for all tested catalytic
systems show quite similar dependence on reaction temperature. More
or less sharp maxima are observed. Thus, as the temperature rises in the
initial phase, we observe the increase in the intrinsic site activity, the
fastest one over the 0.9Co-0.1Mn surface, and the slowest over the
0.5Co-0.5Mn surface. The 0.9Co-0.1Mn catalyst consists mainly of
Co3O4, while the 0.5Co-0.5Mn catalyst is composed also with a high
amount of mixed oxides (MnCo2O4 and Mn2CoO4). After reaching the
35
Catalysis Communications 125 (2019) 32–36
maximum, the situation begins to alter slightly. The highest values of
intrinsic site activity are observed over the 0.5Co-0.5Mn surface, and
the lowest one over the 0.9Co-0.1Mn surface. This behaviour can be
caused by the different strength of oxygen binding with the surface and
the crystalline lattice of tested catalysts, but a more precise explanation
requires further research, e.g. using isotopes of oxygen.
At this point, it would be very helpful to broaden the knowledge of
the reaction mechanism. The catalytic process of oxidation on the
surface of metal oxides often proceeds according to a Mars-van
Krevelen mechanism, but unfortunately, these studies did not provide
any information on this subject. Moreover, the SSITKA-Mass spectro-
meter studies also did not provide any information on the nature of
active reaction intermediates and how this might alter with the tem-
perature increase. We can only speculate that the carbon-path from CH4
to CO2 consists of the following active reaction intermediates: eCH3-s,
eCH2-s, eCH-s, eC-s and eCO-s, without excluding the presence of
eCHxO-s. Moreover, the so-called spectator or inactive species, like
carbonates and formates, can also be formed. SSITKA coupled with
DRIFTS [15] can supply new information on the nature of reaction
intermediates. However, available DRIFTS studies [16] concerning
methane oxidation have demonstrated that it is difficult to register any
active reaction intermediates, where only some carbonates and for-
mates were observed before the reaction of methane oxidation was
initiated.
Based on the total reaction rate (calculated on the basis of methane
conversion measured during SSITKA), it can be stated that despite the
M. Rotko, et al.
lower intrinsic site activity, a much larger number of active sites makes
the 0.9Co-0.1Mn catalyst the most active in the oxidation of methane
(Fig. 4, left plot).
At this point, it should be noted that the values of the concentration
of active sites can be overestimated due to possible readsorption of
carbon dioxide. This problem was widely discussed in the literature [6].
However, the conducted tests, namely the switch between 12CO2/Ar/He
and 13CO2/Kr/He (Fig. S3, ESI) and also temperature-programmed
desorption of carbon dioxide (Fig. S4, ESI) are rather not indicative of
any readsorption of carbon dioxide at the conditions of the experiments
conducted. Moreover, the values of the concentration of active sites can
be overestimated due to mass transfer limitations, especially at the
higher methane conversion values. Nonetheless, these less precise
parameters are necessary for the better understanding of differences in
the CH4 combustion activity of cobalt-manganese-based catalysts.
The results obtained by SSITKA also suggest that the active site is
composed of both the cobalt atom/atoms and the manganese atom/
atoms, because the change in the catalyst chemical composition leads
not only to a shift in the number of active sites, but also to a variation of
their intrinsic activity. It turns out that using a similar amount of cobalt
and manganese we can obtain a catalyst characterized by active sites
with very high efficiency in the process of methane oxidation. However,
the smaller amount of these active sites compared to a catalyst con-
taining a small amount of manganese, and high amounts of cobalt,
makes the overall reaction rate lower. Thus, further research related to
the development of a highly-active catalytic system for the methane
oxidation process should focus not only on cobalt-manganese catalysts
with cobalt as the dominant element, but also on cobalt-manganese
catalysts with manganese dominating their composition.
4. Conclusions
The conducted research allowed us to determine approximate va-
lues of the number and efficiency of active sites on the surface of
working cobalt-manganese-based mixed metal oxides as methane oxi-
dation catalysts. Despite the fact that the number of active sites can be
overestimated by possible readsorption of carbon dioxide and also the
higher methane conversion due to mass transfer limitations, the ob-
tained values provide new important information about methane oxi-
dation on cobalt-manganese-based catalysts. Furthermore, for the same
reasons, the values of efficiency of active sites (intrinsic site activity)
can also be underestimated. In general, as the temperature rises, the
number of active sites increases (with a slight decrease in the number of
36
Catalysis Communications 125 (2019) 32–36
active sites in some temperature ranges), while maximum value was
observed for the intrinsic site activity, so the highest efficiency of active
sites can be achieved in a certain temperature range. The number of
active sites and their activity also depend on the chemical composition
of the catalyst. The cobalt-manganese catalyst with a manganese con-
tent of about 10 wt% is characterized by the highest number of active
sites per gram basis; still in some temperature ranges their efficiency in
methane oxidation process is lower or much lower than that of the
active sites present on the surface of other catalytic systems.
Nevertheless, even with lower site activity, their significantly larger
concentration makes them demonstrate the best catalytic activity per
gram basis in methane oxidation.
Acknowledgements
This research was funded by the National Science Centre as part of
the Miniatura 1 project no. 2017/01/X/ST4/00334.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.catcom.2019.03.019.
References
[1] X. Wang, Y. Xie, React. Kinet. Catal. Lett. 70 (2000) 43–51.
[2] W. Li, Y. Lin, Y. Zhang, Catal. Today 83 (2003) 239–245.
[3] M. Kumar, G. Rattan, J. Chem. Tech. Met. 51 (2016) 63–72.
[4] J. Li, X. Liang, S. Xu, J. Hao, Appl. Catal. B 90 (2009) 307–312.
[5] J.G. Goodwin Jr., S.Y. Kim, W.D. Rhodes, Turnover frequencies in metal catalysis:
Meanings, functionalities and relationships, in: J.J. Spivey, G. Roberts (Eds.),
Catalysis, vol. 17, The Royal Society of Chemistry, London, 2004, pp. 320–347.
[6] A.M. Efstathiou, Elucidation of mechanistic and kinetic aspects of water-gas shift
reaction on supported Pt and au catalysts via transient isotopic techniques, in:
J.J. Spivey, Y.-F. Han, K.M. Dooley (Eds.), Catalysis, vol. 28, The Royal Society of
Chemistry, Cambridge, 2016, pp. 175–236.
[7] S. Brunauer, P.H. Emmett, E. Teller, J. Am. Chem. Soc. 60 (1938) 309–319.
[8] L.G. Joyner, E.P. Barrett, R. Skold, J. Am. Chem. Soc. 73 (1951) 3155–3158.
[9] H. Rietveld, J. Appl. Crystallogr. 2 (1969) 65–71.
[10] S. Pansare, A. Sirijaruphan, J.G. Goodwin Jr., Investigation of reaction at the site
level using SSITKA, in: J.S.J. Hargreaves, S.D. Jackson, G. Webb (Eds.), Isotopes in
Heterogeneous Catalysis, Imperial College Press, London, 2006, pp. 183–211.
[11] M. Rotko, A. Machocki, G. Słowik, Appl. Catal. B 160 (161) (2014) 298–306.
[12] M. Rotko, A. Machocki, G. Słowik, Catal. Lett. 147 (2017) 1783–1791.
[13] S.L. Shannon, J.G. Goodwin Jr., Chem. Rev. 95 (1995) 677–695.
[14] C. Ledesma, J. Yang, D. Chen, A. Holmen, ACS Catal. 4 (2014) 4527–4547.
[15] P.G. Savva, A.M. Efstathiou, J. Catal. 257 (2008) 324–333.
[16] O. Demoulin, M. Navez, P. Ruiz, Appl. Catal. A 295 (2005) 59–70.