Catal Lett (2016) 146:483–492

DOI 10.1007/s10562-015-1664-7

Selective Oxidation of Methane to Methanol Over Cu- and

Fe-Exchanged Zeolites: The Effect of Si/Al Molar Ratio
Christos Kalamaras1 • David Palomas2 • Rene Bos3 • Andrew Horton3 •

Mark Crimmin2 • Klaus Hellgardt1

Received: 1 October 2015 / Accepted: 17 November 2015 / Published online: 27 January 2016
 Springer Science+Business Media New York 2016

Abstract A series of Cu-, Fe- and Fe/Cu-containing zeolite conclusions of the previous work by Hammond et al. (ACS
(ZSM-5, beta, Y) catalysts were prepared to investigate the Catal 3:689, 2013; ACS Catal 3:1835, 2013; Angew Chem Int
effect of zeolite’s physicochemical properties on the total Ed 51:5129, 2012; Chem Eur J 18:15735, 2012) over the
oxygenates production and MeOH selectivity from the partial well-studied Cu–Fe–zeolite system, providing also complete
methane oxidation using H2O2 as oxidizing agent. The material balance based on both gas and liquid reaction
NH3-TPD studies have shown that the zeolite type and Si/Al products.
molar ratio are correlated with the acid sites strength and
Graphical Abstract
concentration. The latter surface property was proved to have
a strong influence on the oxygenate productivity. In partic-
ular, a significant increase of the methanol production was
observed when lowering Si/Al ratio in the ZSM-5, Fe/ZSM-5,
Cu/ZSM-5 and Cu–Fe/ZSM-5 catalysts. This can be
explained by the increased amount of Brønsted acid sites
capable of accommodating the active catalyst (Fe species).
The Fe-only ZSM-5 catalysts exhibited the highest catalytic
activity (total oxygenated products) with HCOOH being the
major product, whereas the presence of only Cu was found to
suppress the production of MeOOH and HCOOH. On con-
trary, the deposition of both Fe3? and Cu2? results to a switch
in selectivity and the target product, MeOH, was observed in
*80 % selectivity. In the case of Cu-only ZSM-5 catalysts, a
similar activity to methanol was observed regardless the
copper source and synthesis method. The activity/selectivity
findings of the present study confirm and complement the
Keywords Partial oxidation of methane
ZSM-5 zeolite

Acidity
Methanol production
& Klaus Hellgardt
[email protected]
1
Chemical Engineering Department, Imperial College
London, South Kensington, London SW7 2AZ, UK 1 Introduction
2
Chemistry Department, Imperial College London, South
Kensington, London SW7 2AZ, UK The efficient and selective oxidation of methane to
3 methanol remains a challenging problem for catalytic sci-
Emerging Technologies, Shell Global Solutions International
B.V., P.O. Box 38000, 1030 BN Amsterdam, ence and if solved would have the potential to revolutionize
The Netherlands the petrochemical industry. The conversion of methane to

123
484 C. Kalamaras et al.

energy-dense liquid derivatives, such as methanol, could catalysts capable of very high selectivity towards methanol
lead to significant breakthroughs in the utilization of nat- [1–4, 27]. Based on EPR radical trapping studies, the
ural gas as a primary feedstock [5]. Presently, methanol authors proved that Cu ions are able to control the pro-
production is an energy-intensive two-stage process duction of hydroxyl radicals, which facilitate the over-ox-
involving the intermediate manufacture of synthesis gas idation of methanol to formic acid. It is noteworthy that the
[6]. This technology is potentially not economically viable developed catalyst was found to be over 3 orders of mag-
in remote regions where a significant fraction of the nitude more active than any previously reported system for
world’s reserves of methane are found [7].Therefore, there direct methane oxidation.
is significant interest in the valorization of methane in a In this contribution, we investigate the effect and role of
single and preferentially non-energy-intensive step to the Si/Al ratio of the ZSM-5 support on the activity and
facilitate its utilization on an industrial scale. selectivity of Cu–Fe/ZSM-5 catalysts in the partial oxida-
Despite decades of research in the field of C–H activa- tion of methane to methanol. We show that the Si/Al ratio
tion, due to the large single bond enthalpy of and in particular the resulting acidity of the support has a
438.8 kJ mol-1, low polarisability and low solubility of significant effect on catalytic activity. We propose that this
methane the problem of selective and catalytic methane to effect is due to an increase in the amount of Brønsted acid
methanol oxidation still remains unsolved [8]. Due to sites, which are capable to accommodate the active extra-
facile over-oxidation of methanol, the design of a cat- framework Fe species.
alytic system that not only activates methane, but is able
to do so under intrinsically mild reaction conditions is
required. Three main approaches have been reported,
2 Experimental
namely: (i) direct high temperature-high pressure activa-
tion of alkanes in low yield but high selectivity processes
2.1 Catalyst Synthesis
[9–11], (ii) oxidation in strong acidic media using noble
metal catalysts to produce alcohol derivatives as esters
Two common techniques were employed for the synthesis
[12–15], and (iii) activation under moderate conditions
of M/zeolite (where, M = Fe and/or Cu) type catalysts.
using micro/mesoporous catalysts containing transition
metal sites and N2O/O2 which operate without catalytic i. Catalysts were prepared by Solid State Ion Exchange
turnover [16–21]. (SSIE) technique in order to introduce Fe and/or Cu
In nature, methane monooxygebase (MMO) uses metals into various zeolite structures (i.e. ZSM-5, beta,
dioxygen from air, in combination with 2 protons and 2 Y) using different Cu(II) and Fe(III) precursors, namely
electrons, as the terminal oxidant for a highly selective, acetylacetonate (acac), chloride and nitrate. The synthesis
one-step methane oxidation that operates at room temper- procedure involved the following steps: [Fe(acac)3] was
ature and atmospheric pressure [22]. While biomimetic added to the desired amount of the ammonium form of
catalysts based upon the di-iron active site of soluble MMO ZSM-5 zeolite and ground in a pestle and mortar for
(sMMO) have been investigated extensively for alkane 30 min. The catalysts were subsequently activated prior
oxidation, the active di-copper site of particulate MMO to use, by calcination at 550 C (10 C min-1) for 3 h in
(pMMO) was only elucidated in 2010 [23–26]. Recently, a static air. This protocol was used to prepare all Cu-only,
novel low-temperature selective oxidation of methane to Fe-only and Fe–Cu bimetallic exchanged-zeolites using
oxygenated products in aqueous phase using hydrogen the appropriate amount of copper(II) and/or iron(III)
peroxide as the oxidant over Cu- and Fe-containing mor- precursors.
denite framework inverted (MFI)-type zeolites was repor- ii. The wet impregnation (WI) technique was used as an
ted [1–4, 27]. The authors demonstrated that the reaction alternative method for the preparation of Cu-only
proceeds through a methyl hydroperoxide (MeOOH) zeolite (ZSM-5, SiO2/Al2O3 = 30) catalysts in order to
intermediate, which subsequently converts to methanol probe the influence of the synthesis route on the
(MeOH) with high yield and selectivity in a closed cat- activity and selectivity of the prepared catalysts. The
alytic cycle. However, some overoxidation to formic acid Cu(II) zeolite-supported catalysts were prepared by
(HCOOH) and CO2 was also observed at various levels of impregnating the ammonium form of ZSM-5(30) with
selectivity. The active sites were attributed to trace impu- a given amount of aqueous precursor solution (i.e.
rities of iron, which is proposed to exist as extra-framework Cu(acac)2, CuCl2, Cu(NO3)2
3H2O) corresponding to
diiron–l-oxo-hydroxo complexes or oligomeric iron com- the desired 2.5 wt% Cu loading. After gradual evap-
plexes within the zeolite micropores [1–4, 27]. The addi- oration of water at 70 C for 4 h, the resulting solid
tion of Cu2? appears to militate against methanol over- was then dried at 120 C overnight and then calcined
oxidation processes, leading to binary Cu–Fe/ZSM-5 at 550 C (10 C min-1) for 3 h in static air.

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Selective Oxidation of Methane to Methanol Over Cu- and Fe-Exchanged Zeolites… 485

All the ZSM-5 (SiO2/Al2O3 = 23, 30 and 80) and beta helium from 25 to 550 C (10 C min-1). This was done to
(SiO2/Al2O3 = 25) zeolites were purchased from Zeolyst remove water and impurities. The temperature was held at
International in the ammonium form. The ammonium Y 550 C for 1 h and then cooled to 100 C under flowing
zeolite (SiO2/Al2O3 = 5) was sourced from Sigma gas (He). Then, the He flow was switched to 10 vol% NH3/
Aldrich. The number in parenthesis after each zeolite He for 30 min. Following this the reactor was purged with
indicates the nominal SiO2/Al2O3 molar ratio. He for a further 1 h to remove weakly adsorbed NH3. A
linear temperature program of 5 C min-1 was used to
2.2 Physicochemical Characterization follow the desorption of NH3 (m/z = 17) with evolved gas
detected by a quadrupole mass spectrometer (PFEIFFER
The specific surface area (SSA, m2 g-1) of the commercial Vacuum, ThermoStarTM).
zeolites was determined by applying the BET method.
N2 adsorption/desorption isotherms obtained at 77 K over 2.3 Methane to Methanol Reaction
the entire range of relative pressures on samples previously
outgassed at 300 C for 2 h (Micromeritics TriStar 3000 All catalytic tests for the oxidation of methane were car-
analyser) were used to estimate the pore volume (Vp, ried out with H2O2 over a custom-made batch apparatus
cm3 g-1) of the solids. X-ray Fluorescence (XRF) chemi- shown in Fig. 1. The stainless-steel autoclave (50 mL)
cal analysis was performed at room temperature on a reactor containing a Teflon liner and a Teflon coated
Bruker S4EXPLORER apparatus in order to determinate magnetic stirrer was charged with an aqueous solution of
the SiO2/Al2O3 molar ratio of the commercial zeolites. H2O2 (10 mL, 0.5 M) and the desired amount of catalyst
Approximately 1 g of each powder sample was placed into (27 mg). After sealing, the reactor was charged with CH4
a 40 mm sample cup mounted with 4 lm polypropylene to a fixed pressure (30.5 bar) after a series of purges (5
film and analyzed by XRF. times) to remove permanent gases. This is equivalent to
X-Ray diffraction was used for phase identification, and 36 mmol of CH4 in the gas phase. The autoclave was
to probe: (i) the presence of Fe and/or Cu X-ray active heated to the reaction temperature (50 C), and vigorously
oxides in the zeolite, and (ii) the influence of the synthesis stirred at 1500 rpm once the desired temperature was
method, SiO2/Al2O3 ratio and precursor materials on the obtained. After a reaction time of 30 min, a gas sample
morphology and crystallinity of the final catalysts. Powder loop (0.5 mL) was filled with product gas from the exit of
X-ray diffraction patterns of the prepared solids were the reactor and injected via a 6-way chromatographic
recorded in the 5–75 2h range (PANalytical X’Pert PRO valve with electrical actuator to a mass spectrometer
diffractometer using Cu Ka radiation, k = 1.5418 Å) with (European Spectrometry System II) for analysis using a
a step scan of 0.2 min-1. constant flow of carrier gas (Ar, 300 mL min-1). The
The Al, Fe, Cu and Na content of the commercial zeo- mass numbers (m/z), 15 (CH3?), 16 (CH4), 18 (H2O), 28
lites was determined by ICP-OES (Perkin–Elmer 2000 DV (CO), 31 (CH3O?), 32 (O2) and 44 (CO2) were continu-
ICP-OE spectrometer). Each zeolite was analyzed after ously monitored using Quadstar 32bit software. The purity
calcination of the commercial source (ammonium form) for of the gases used (CH4, CO2, Ar, provided by BOC gases
2 h under static air at 550 C. Approximately 0.1 g of the UK) was greater than 99.95 vol%. The amount of CO2 in
commercial zeolite was weighed accurately and digested the product gas (lmol) was calculated by multiplying the
with 0.5 mL of concentrated hydrofluoric acid (48 %) by area (ppm.s) of the CO2 molar fraction signal with the
heating at 100 C for 30 min. After evaporating the acid, carrier gas flow rate (mol s-1). The vessel was subse-
0.25 mL each of concentrated nitric acid (68 %) and con- quently cooled in an ice bath to 12 C in order to reduce
centrated hydrochloric acid (37 %) were added and volatility of any liquid products that may have formed.
digestion continued for another 30 min. This was diluted to The liquid product solution was then filtered and samples
5 mL with deionized water, and 2 mL of boric acid (2 %) were analyzed by an Agilent 6890 GC equipped with FID
and was further diluted as needed with 2 M nitric acid prior detector and 1H-NMR spectroscopy.1H NMR spectra were
to analysis (3 mL in 25 mL of total volume). measured at a frequency of 500.13 MHz using a Bruker
The acidity of the prepared M/ZSM-5(30) catalysts as AVANCE III HD 500 spectrometer operating at 298 K.
well as that of the H-form of all zeolites investigated was Solvent suppression (HOD), along with 13C decoupling to
determined by NH3-Temperature Programed Desorption remove 13C satellite signals, were achieved using the pulse
(TPD) technique. All NH3-TPD experiments were carried program wetdc [28]. All relevant parameters were selected
out in a conventional flow-through quartz reactor with automatically via execution of the Bruker AU program
helium as carrier gas (50 mL min-1). Typically, 200 mg of au_lc1d after obtaining a 1H spectrum showing the solvent
sample was pretreated by heating in a flowing stream of chemical shifts.

123
486 C. Kalamaras et al.

Fig. 1 Experimental set-up used for the aqueous-phase selective oxidation of methane to methanol by H2O2

3 Results and Discussion Na2O content. In the case of the Y-type zeolite the Na
content was equivalent to 4 wt% Na2O. Moreover, in all
3.1 Catalyst Characterization cases the SiO2/Al2O3 molar ratios reported by the manu-
facture (number in parenthesis) are in good agreement with
Table 1 lists the physical properties and chemical compo- the XRF analysis.
sition of the commercial zeolites investigated. It is clear X-ray diffraction patterns of the M/ZSM-5(30) and
that the beta zeolite exhibits the highest specific surface M/beta (where, M = Fe or Cu) solids prepared by SSIE
area and pore volume of all commercial zeolites studied. using acetylacetonate precursors, are presented in Fig. 2. It
For the ZSM-5 zeolites the specific surface area and pore is observed that both Cu- and Fe-exchanged catalysts
volume slightly increases with increasing Si/Al molar ratio. maintained the MFI and BEA framework structure of
Elemental analysis of the commercial materials was per- ZSM-5 and beta zeolite, respectively [29]. Moreover, no
formed in order to determine the role played by any shift of the main diffraction peaks of the 2.5 wt% metal
potential metal impurities within the structure. The ICP containing materials was noticed with respect to the pro-
results shown in Table 1 revealed that each sample con- tonated zeolites. The latter experiment indicates no
tained trace amounts of the transition metals Fe and Cu. In shrinkage/expansion of the crystal lattice due to introduc-
the case of the ZSM-5 series and beta zeolites trace tion of Cu2? and Fe3? into the zeolite framework. Similar
amounts of Na were also observed. The results are in line to the work of Hammond et al. [1], it is suggested that the
with relevant MSDS sheets indicating a residual 0.05 wt% framework metal cations formed by hydrothermal synthesis

Table 1 Physical properties, elemental analysis and SiO2/Al2O3 molar ratios of the commercial zeolites investigated
Zeolite SSAa (m2 g-1) Vap (cm3 g-1) Alb (ppm) Feb (ppm) Nab (ppm) Cub (ppm) SiO2/Al2Oc3

ZSM-5(23) 384 0.209 21,571 233 270 14 25.7

ZSM-5(30) 363 0.223 19,502 179 123 1 35.7
ZSM-5(80) 439 0.264 8391 204 214 4 94.0
beta(25) 601 0.687 23,102 219 156 2 27.4
Y-zeolite(5) 430 0.220 105,786 190 16,047 1 –
a
Determined by BET method
b
Determined by ICP-OES
c
Determined by XRF

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Selective Oxidation of Methane to Methanol Over Cu- and Fe-Exchanged Zeolites… 487

Fig. 2 Powder XRD patterns of the a M/ZSM-5(30) and b M/beta (where, M = Fe or Cu) catalysts in the 22–40 2h range

are able to migrate to the extra-framework during heat XRD is a bulk sensitive technique that requires crystallites
pretreatment. While for Fe-exchanged zeolites several iron of minimum dimensions near 5 nm. According to literature
oxide phases could be formed, including hematite [32], at least three types of copper species have been
(a-Fe2O3), maghemite (c-Fe2O3), lepidocrocite (c-FeO– proposed for Cu-exchanged zeolites: (i) isolated ions
OH), gohetite (a-FeO–OH), wustite (FeO) and magnetite interacting with the framework Al, either without an extra
(Fe3O4) [30], after careful analysis none of these phases framework ligand, or with an extra framework O or OH
were detected (Fig. 2). ligand, (ii) polymeric chains or multinuclear species (often
Figure 3 shows the XRD patterns of the Cu/ZSM-5(30) referred to as small copper–oxygen aggregates, for instance
solids prepared by WI and SSIE synthesis methods, derived [Cu–O–Cu]2? inside the channels, and (iii) oxide particles
from CuCl2, Cu(NO3)2
3H2O and Cu(acac)2 precursors. on the external surface of zeolite. Our data suggest that
Near identical diffraction patterns were observed for all independent of the synthesis method and precursor material
Cu-containing samples, indicative only of the MFI struc- used, Cu2? ions are well dispersed in the framework while
ture with no evidence of segregation of the CuO phase. the structure is globally maintained. This would explain the
CuO has the most intense diffraction lines at 2h values of similar methanol yield observed for these catalysts under
35.6 and 38.7. Despite these observations, CuO [31] was selective methane oxidation conditions using H2O2 (see
detected in ZSM-5-containing zeolites when the transition Sect. 3.3; Table 4).
metal content exceeded 5 %. One may argue simply that The Cu and Fe content of the final solids (M/zeolite,
metal oxide aggregates, larger than 5 nm particle size, are where M = Cu and/or Fe) after SSIE was also determined
not present in the various Cu/ZSM-5(30) catalysts, since by ICP. Elemental analysis of the resulting materials after

Fig. 3 Powder X-ray diffraction patterns of the Cu/ZSM-5(30) solids prepared by a WI and b SSIE method, derived from various Cu(II)
precursors in the 22–40 2h range

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488 C. Kalamaras et al.

calcination for 3 h under static air at 550 C was performed

in order to probe the exchange capacity of the metal (Fe
and/or Cu) into the zeolite structure. The results shown in
Table 2 revealed that in both Fe- and Cu-exchanged zeo-
lites, the materials were found to contain more than 85 %
of the nominal values of the transition metals (Fe and Cu).
In the present study the actual form of Fe and Cu metal into
the zeolites was not identified.

3.2 Acidity Studies by NH3-Temperature

Programmed Desorption (TPD)

In the TPD of ammonia, the strength of the NH3 interaction

with acid sites is reflected in the temperature profile of the
desorption rate. The area under the peaks is proportional to Fig. 4 NH3-TPD profiles obtained over ZSM-5(30), Cu/ZSM-5(30)
the total number of acid sites in the catalyst under study. and Fe/ZSM-5 catalysts prepared by SSIE method
The absolute number of acid sites was quantified by mul-
tiplying the area of the peak with the feed gas flow rate.
Table 3 Total amount of desorbed NH3 and peak maximum during
The NH3 desorption profiles during TPD for ZSM-5(30), TPD experiments
Cu/ZSM-5(30) and Fe/ZSM-5(30) catalysts are shown in
Catalyst NH3 (lmol g-1) T1max (C) T2max (C)
Fig. 4 and the total amounts of desorbed NH3 (lmol g-1)
and the peak maxima (Timax) are given in Table 3. ZSM-5(23) 894 188 411
As shown in Fig. 4, the M/ZSM-5(30) catalysts exhib- ZSM-5(30) 613 185 400
ited different profiles compared to the parent material. Two Cu/ZSM-5(30) 613 174 315
major desorption events were noted for H-ZSM-5(30) with Fe/ZSM-5(30) 452 175 403
maxima at 197 and 409 C indicating the presence of weak ZSM-5(80) 354 176 370
and strong acid sites, respectively. In particular, the peak Beta(25) 347 168 320
observed at 197 C is caused by weakly physisorbed and
coordinated NH3 on Lewis acid sites, while the peak at
about 409 C is related to NH4? ions with three hydrogen
atoms bonded to three oxygen ions of AlO4 tetrahedra (3H This explanation is also supported by previous work of
structure) on Brønsted acid sites [33–36]. The incorpora- Long et al. [34] by a separate NH3-TPD experiment over
tion of Cu and Fe metal ions into ZSM-5(30) results in a NH4-ZSM-5 where no NH3 desorption peak near 160 C
decrease of the total acidity of the zeolite as measured by a was seen, but a peak at 390 C was observed. On the other
lower amount of NH3 desorbed. In the case of Fe-ex- hand, incorporation of Cu into the ZSM-5(30) created weak
changed ZSM-5(30), the NH3 desorption peak at 409 C acid sites, as indicated by NH3 desorption below 400 C.
decreased significantly (see Fig. 4; Table 3), indicating a NH3 desorption from Cu/zeolite between the range
reduction of Brønsted acidity, which suggests that the 250–300 C was correlated to NH3 desorption occurring
Brønsted acid protons of ZSM-5 were substituted by Fe3?. from Cu–NH3 complex [37].

Table 2 Cu and Fe content of

Final catalyst SiO2/Al2O3 Cu (wt %) Fe (wt %)
the final solids after SSIE as
determined by ICP 2.5 wt% Cu/ZSM-5 30 2.23 0.02
2.5 wt% Fe/ZSM-5 0.003 2.16
1.25 wt% Cu/1.25 wt% Fe/ZSM-5 1.11 1.01
2.5 wt% Cu/ZSM-5 23 2.64 0.05
2.5 wt% Fe/ZSM-5 0.003 2.79
1.25 wt% Cu/1.25 wt% Fe/ZSM-5 1.35 1.32
2.5 wt% Cu/beta 25 2.90 0.04
2.5 wt% Fe/beta 0.0003 2.92
1.25 wt% Cu/1.25 wt% Fe/beta 1.48 1.48

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Selective Oxidation of Methane to Methanol Over Cu- and Fe-Exchanged Zeolites… 489

The total acidity of the beta and ZSM-5 zeolites with 3.3 Catalytic Activity of Zeolite Based Catalysts
different Si/Al molar ratios was also determined by the
NH3-TPD technique. Figure 5 shows the typical acid site The metal catalysts prepared were tested for the selective
distribution as obtained by NH3-TPD. Similar to Fig. 4, all oxidation of methane to methanol in an indirect process
zeolites exhibited two well resolved desorption peaks: the using H2O2 as oxidizing agent according to the experi-
low-temperature peak (LTP) at 176–188 C and the high- mental procedure described in Sect. 2.3. The catalytic
temperature peak (HTP) at 320–411 C. It was found that evaluation tests were conducted on the prepared solids as a
the HTP increased as the Si/Al ratio decreased in the case function of: (i) the synthesis method and Cu precursor
of ZSM-5 zeolites, whereas the beta zeolite showed the (Table 4), and (ii) the SiO2/Al2O3 molar ratio and zeolite
lowest NH3 desorption temperature. Figure 5 also shows type (Table 5).
that the desorption temperature of ammonia from the As shown in Table 4, the protonated and Fe-only ZSM-
strong acid sites shifted to higher temperature as the Si/Al 5(30) zeolites (entries 1 and 2, Table 4) exhibited compa-
ratio decreased, strongly suggesting the existence of alu- rable methanol yields with those reported by Hammond
minum in extra-framework positions. The total amount of et al. [3] under the same experimental conditions. On the
NH3 adsorbed onto weak and strong acid sites of beta and other hand, the Cu-only and bimetallic Fe–Cu catalysts
ZSM-5 with different molar ratio of Si/Al is shown in (entries 3–9, Table 4) were found to give lower (65–75 %)
Table 3. It is clearly seen that the total acid sites of ZSM-5 yields of methanol compared with the literature value.
decrease with increasing of Si/Al molar ratio, data which Initially it was thought that this may be due to the choice of
agree well with those reported in the literature [38, 39]. The precursor material, however, it was found that the prepa-
results show that the zeolite type and the molar ratio of Si/ ration method and the Cu precursor have only minor effects
Al have a significant effect on the physicochemical prop- on the total methanol production. Based on the physico-
erties of the final catalysts. chemical characterization of the Cu-containing catalysts, a
Costa et al. [38, 40, 41] suggested that the strength and similar structure was obtained despite different synthesis
concentration of the acid sites could be quantitatively methods and Cu precursors, while [90 % of Cu2? cations
correlated with the activity for the catalytic cracking of n- were introduced into zeolite pore (Table 2) after SSIE.
heptane and light olefins in a variety of Y and ZSM-5 The results of Table 5 indicate that the zeolite type and
zeolites. In these studies, it was verified that acid catalyzed Si/Al molar ratio have a strong influence on the methanol
reactions over zeolites could be described by Brønsted-type yield, since the Cu- and Fe-containing ZSM-5 zeolites
relations. Beyond the determinant factor of framework (SiO2/Al2O3 = 23) showed much higher activity in terms
composition of the zeolites, the spatial distribution of acid of methanol yield compared with the other catalysts
sites across the framework is also important, i.e., for a investigated. According to Hammond et al. [1, 3], the level
given composition, the structure type will modify the sur- of activity exhibited by ZSM-5 for methane activation has
face properties [42, 43]. proven so far to be unique. It was initially suggested that
the enhanced activity could be attributed to: (i) the
arrangement of molecular-sized pores and cavities found in
the zeolite framework, which allows discrimination
between molecules simply by size [44], (ii) a molecular
confinement effect within the zeolite micropores, leading
to increased interactions between confined reactants and
allowing unusual transition states to be accessed [45, 46].
Alternative zeolites (i.e., y-zeolite, silicalite) with similar
surface areas and pore structures were found to be far less
active, suggesting that the confinement effect of the MFI
framework alone does not explain the observed activity of
the ZSM-5(23) zeolite.
The other possible explanation for the superior activity
of ZSM-5 is the presence of Fe metal impurities. It was
reported that even trace Fe concentrations within the MFI
structure are capable to both activate hydrogen peroxide
[47, 48] and catalyze various selective oxidations using
H2O2 [1–4] and N2O [49–51] as oxidizing agents. Indeed,
Fig. 5 NH3-TPD profiles obtained over beta and ZSM-5 zeolites with elemental analysis of all commercial zeolites studied here
different SiO2/Al2O3 ratio demonstrated that in addition to the expected quantities of

123
490 C. Kalamaras et al.

Table 4 The effect of synthesis

Entry Catalyst Synthesis method Precursor MeOHa (lmol) Ref. [3] (lmol)
method and Cu precursor on
methanol production with ZSM- 1 ZSM-5(30) – – 9.4 15.4
5 zeolites
2 Fe/ZSM-5(30) SSIE Fe(acac)3 29.2 19.6
3 Cu–Fe/ZSM-5(30) SSIE Fe(acac)3; Cu(acac)2 52.0 188.8
4 Cu/ZSM-5(30) SSIE Cu(acac)2 20.2 65.3
5 Cu(NO3)2 29.7
6 CuCl2 21.7
7 WI Cu(acac)2 14.4
8 Cu(NO3)2 24.5
9 CuCl2 29.3
a
Reaction conditions: t = 30 min; T = 50 C; P = 30.5 bar; [H2O2]o = 0.5 M; catalyst = 27 mg;
rpm = 1500; V = 10 mL

Table 5 The effect of SiO2/Al2O3 molar ratio and zeolite type on strength and concentration as observed by NH3-TPD
methanol production studies (Table 3). It could be suggested that the high
Entry Catalyst SiO2/Al2O3 MeOH (lmol)a Ref. [3] activity of the Cu- and Fe-exchanged ZSM-5(23) for the
selective oxidation of methane is correlated to the strength
1 ZSM-5 23 16.8 15.4 and concentration of the acid sites, which are capable of
2 30 9.4 accommodating extra-framework Fe species. This strongly
3 80 4.5 suggests that the presence of Al3? in the MFI-framework is
4 beta 25 2.0 highly beneficial to the activity of the catalyst. However,
5 Y-zeolite 5 2.1 the precise role of Al3? is still the subject of much debate.
6 Fe/ZSM-5 23 47.7 19.6 For instance, Notte [52] has shown that extra-framework
7 30 29.2 iron atom(s) in close vicinity to the framework acidic
8 80 10.4 aluminum atoms constitute active catalytic centers for the
9 Fe/beta 25 2.9 one-step benzene to phenol reaction with N2O. Similarly, it
10 Fe/Y-zeolite 5 4.0 has been reported [53] that the Fe–O–Al extra framework
11 Cu/ZSM-5 23 47.4 65.3 mixed oxide formed after activation of Fe- and Al-con-
12 30 20.2 taining MFI materials could also exhibit catalytic activity
13 80 6.0 for the same reaction. Recently, Hammond et al. [2] based
14 Cu/beta 25 2.4 on catalytic measurements and spectroscopic investigations
15 Cu/Y-zeolite 5 3.1 suggested that the incorporation of non-catalytic trivalent
16 Cu–Fe/ZSM-5 23 126.3 188.8 cations (e.g., Al3? or Ga3?) into the MFI-framework leads
17 30 52.0 to an increased migration of framework Fe3? to the extra-
18 80 8.5 framework during heat pretreatment possibly stabilized by
19 Cu–Fe/beta 25 2.6 the AlO4 tetrahedra. It is important to note that, the extra-
20 Cu–Fe/Y-zeolite 5 4.9 framework Fe3? species are suggested to be the active
a catalytic components for selective aqueous-phase methane
Reaction conditions: t = 30 min; T = 50 C; P = 30.5 bar;
[H2O2]o = 0.5 M; catalyst = 27 mg; rpm = 1500; V = 10 mL oxidation [3].
Table 6 presents the full product distribution obtained
over Cu- and Fe-containing ZSM-5(23) catalysts under the
same reaction conditions presented in Tables 4 and 5, as
Al, trace (*200 ppm) levels of Fe metal were present determined by 1H-NMR spectroscopy and mass spec-
(Table 1). Thus, it is clear that the Fe content alone is not trometry for the liquid (MeOH, MeOOH, HCOOH) and gas
responsible for the significant differences in the final (CO2) products, respectively. It is obvious that the intro-
activity observed at similar catalyst compositions. duction of Fe cations into ZSM-5(23) leads to a significant
On the other hand, ZSM-5 zeolites are also well known increase in catalytic activity (total oxygenated products),
as multifunctional materials possessing both Brønsted and although HCOOH becomes the major product with selec-
Lewis acidity associated with the Al3? content and hence tivity greater than 75 %. The presence of Cu cations was
the SiO2/Al2O3 molar ratio. As discussed previously in found to suppress the production of MeOOH and HCOOH,
Sect. 3.2, the amount of Al3? is correlated to the acid site with an insignificant amount of CO2 observed. It was noted

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Selective Oxidation of Methane to Methanol Over Cu- and Fe-Exchanged Zeolites… 491

Table 6 Product distribution obtain over M/ZSM-5(23) catalysts (where, M = Fe and/or Cu)
Catalyst MeOHa (lmol) MeOOHa (lmol) HCOOHa (lmol) COb2 (lmol) Total (lmol) MeOH Selectivity (%)

ZSM-5(23) 14.0 13.7 3.8 3 34.5 40.6

Cu/ZSM-5(23) 17.1 – – 6 23.1 74.0
Fe/ZSM-5(23) 17.9 2.3 88.0 34 142.2 12.6
Cu–Fe/ZSM-5(23) 135.0 – – 38.5 173.5 77.8
a 1
Analyzed by H-NMR
b
Determined by MS

that deposition of both Fe3? and Cu2? results in a switch in extremely high. Since HCOOH is the deepest oxidation
selectivity where HCOOH is no longer produced and the product before production of CO2, the increased selectivity
target product, MeOH, is observed at *80 % selectivity. It suggests that this compound is mainly formed by the over-
is also worth noting, that in all cases, CO was not detected oxidation of MeOOH and MeOH (routes 2 and 3). More-
in the gas phase. Similar selectivity results were also over, a larger quantity of CO2 is produced via the non-
observed by Hammond et al. [3] over Cu- and Fe-ex- selective decomposition of the partial oxygenate interme-
changed ZSM-5 with a molar SiO2/Al2O3 of 30. diates (MeOOH, MeOH, HCOOH) to CO2. Nevertheless,
Based on previous studies [3, 4, 48] and the current data, the direct formation of CO2 from methane cannot be
the proposed reaction network for the oxidation of methane excluded (route 7). In contrast, the bimetallic Fe–Cu cat-
using H2O2 over ZSM-5 based catalysts is presented in alytic system was found to maintain both high activity and
Fig. 6. Broadly, methane oxidation proceeds by: (i) the MeOH selectivity. As shown in Fig. 6 (route 3), the most
catalytic activation of both hydrogen peroxide and methane preferred product, MeOH, can be oxidised towards
to produce the primary reaction product, MeOOH, (route HCOOH, under the reaction conditions employed, by fur-
1), (ii) subsequent decomposition or further reaction of ther reaction with hydroxyl radicals, which are produced
MeOOH, leading to the formation of MeOH and HCOOH from the homolytic cleavage of the HO–OH bond.
(routes 2 and 3), and (iii) production of CO2 from over- According to the recent work of Hammond and co-workers
oxidation (routes 4–7). Consequently, the results of Table 6 [1–4], the addition of Cu2? to the catalytic system can
suggest that, although the inclusion of Cu2? leads to a suppress this route entirely by its ability to minimise the
minor decrease in the total oxygenate productivity, it does production of OH radicals. It was suggested that the crucial
result in the retention of methanol as the major product at a role of Cu is either to act as a catalytic hydroxyl radical
selectivity of 74 %. In the case of the Fe-containing ZSM- scavenger, quenching or converting any x OH radicals
5(23), despite the catalyst being over four times more produced to non-participative species, or to inhibit the
active than the ZSM-5(23) alone, the HCOOH selectivity is ability of Fe3? to produce x OH radicals in the first place by
limiting the production of Fe2?.

4 Conclusions

In the present work, it has been shown that the reactivity of

commercial zeolite-based catalysts containing Fe and/or
Cu cations for the partial oxidation of methane is related to
the Si/Al molar ratio and type of zeolite, which is reflected
by the acid sites strength and concentration. It was
observed that the Cu-containing zeolites exhibited similar
methanol yield under selective methane oxidation condi-
tions, independent of synthesis method and Cu precursor
material used. This could be explained by the formation
and presence of similar CuO species. The bimetallic Cu–
Fe/ZSM-5(23) catalyst was found to be the most efficient
Fig. 6 Proposed reaction network for the oxidation of methane using
H2O2 over ZSM-5 based catalysts. Dashed lines represent direct over- and selective catalyst for the oxidation of methane to
oxidation pathways methanol using H2O2 under mild reaction conditions

123
492 C. Kalamaras et al.

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