22 2 Temperature-Programmed Techniques

and H2 O produced, while no uptake of H2 is detected. This suggests that the pre-
vailing reaction at low temperatures is the exchange of sulfur for oxygen:

MoO3 þ H2 S ! MoO2 S þ H2 O ð2-8Þ

At about 500 K, the catalyst consumes H2 in a sharp peak, while simultaneously

H2 S and some additional H2 O are produced. Arnoldy et al. [12] assigned the
uptake of hydrogen and the evolution of H2 S to the hydrogenation of excess
sulfur formed via the decomposition of the oxysulfide species in Eq. (2-8) at low
temperatures:

MoO2 S ! MoO2 þ S ð2-9Þ

S þ H2 ! H2 S ð2-10Þ

At higher temperatures, the catalyst continues to exchange oxygen for sulfur until
all molybdenum is present as MoS2 :

MoO2 þ 2H2 S ! MoS2 þ 2H2 O ð2-11Þ

Although Eqs. (2-8) to (2-11) explain the results satisfactorily, one needs to be
aware that TP studies detect only those reactions in the catalyst that are accompa-
nied by a net production or consumption of gases. Suppose, for instance, that Eq.
(2-11) is the result of two consecutive steps:

MoO2 þ 2H2 ! Mo þ 2H2 O ð2-12Þ

Mo þ 2H2 S ! MoS2 þ 2H2 ð2-13Þ

If Eq. (2-13) follows Eq. (2-12) instantaneously, the effect will not be noticeable in
the H2 signal [12]. Despite these limitations, it is concluded that TPS with mass
spectrometric detection is a highly useful technique for studying the sulfidation
of hydrotreating catalysts. We return to the sulfidation of molybdenum oxides in
Chapter 3 (photoemission), Chapter 4 (ion spectroscopy), and also in a case study
on hydrodesulfurization catalysts (Chapter 9).

2.4
Temperature-Programmed Reaction Spectroscopy

Important information on reaction mechanisms and on the influence of pro-

moters can be deduced from temperature-programmed reactions [2]. Figure 2.7
illustrates how the reactivity of adsorbed surface species on a real catalyst can be
measured with TPRS. In this figure, the reactivity of adsorbed CO towards H2 on
a reduced Rh catalyst is compared with that of CO on a vanadium-promoted Rh
catalyst [13]. The reaction sequence, in a simplified form, is thought to be as fol-
lows: