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Chapter 4 91
appear to dominate over type A. One should be aware that the possibility of formation and
distribution of various defect types is rather diverse and may not be restrict to those
mentioned here. The arrangement of the two defect types in Ru-DEMOFs (1a, 1c and 1d)
is rather diverse. Still, based on the information on XANES and UHV-IR with CO probing,
we can assume two possibilities:
i) both defects of type A and B might be generated in the Ru-DEMOFs (1a-1d) with the
incorporation of 5-OH-ip. The defects of type A are much more competitive and became
gradually dominant in case of the lower doping (samples 1a (8%) and 1c (32%)). Along
with increase of doping level (1d, 37%) of 5-OH-ip, the dominant effect of defects A is
substituted slowly by the defects B;
ii) the defects of type A are generated and becomes gradually dominant in case of
relatively low doping (samples 1a and 1c). Afterwards, defects B are created
simultaneously when the doping level reaches 37% in case of 1d. Therefore, the influence
caused by the defects A could be partly eliminated. Nevertheless, both assumptions
indicate that the defects A play a major role in Ru-DEMOFs 1c (32% of 5-OH-ip). A
comprehensive table summarizing possible defect combinations in the particular Ru-
DEMOFs (based on the performed analyses) is given in Table 4.5 and Figure 4.26.
Additional characterization and quantitative determination of the defect types requires
additional work and support by theoretical modeling.
4.2.4 CO2, CO and H2 sorption properties of Ru-DEMOFs
The previous characterizations suggest the existence of two types of defects (A and B)
being present in the samples in different absolute and relative amounts as a consequence
of the 5-X-ip framework incorporation. Both are likely to influence the gas sorption
properties of the Ru-DEMOFs. Hence, we studied the adsorption of CO2, CO and H2 at range
of samples. In general, the results obtained and discussed in the following are not very
conclusive as the observed changes in gas uptake as a function of DL incorporation are
small or even close to the error of the measurements. Nevertheless, we present the data
and provide a tentative discussion with respect to the possible counter acting effects of
the two types of defects in the samples.