10.1002/anie.201906916
Angewandte Chemie International Edition
RESEARCH ARTICLE
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based catalysts for acetylene hydrochlorination. Finally,
a
comparison to literature reported gold and ruthenium-based
catalysts evidences that the herein developed system not only
bridges the productivity gap between the two metal families, but
also rivals the performance of state-of-the art gold-based
catalysts (Figure 6d, Table S6).
[3]
Conclusions
We systematically assessed nuclearity and host effects of carbon-
supported ruthenium catalysts in acetylene hydrochlorination,
identifying surface oxidic metallic ruthenium nanoparticles of
ca. 1.5 nm hosted on polyaniline-derived N-doped carbon as the
most promising system, drawing level with the unprecedented
activity of gold-based catalysts. The origin of the superior catalytic
activity is ascribed to (i) a surface transformation into active
RuOxCly composites upon exposure to the reactants and (ii) a
promotional effect between the active metal center and graphitic
nitrogen sites. As commonly observed for metal oxychlorides,
RuOxCly is prone to redisperse under reaction conditions into
inactive single atoms. To inhibit the undesired redispersion we
developed a synthesis strategy to promote a Ru catalyzed solid-
state transformation of high-density amorphous carbon into
permeable monolayer graphene shells, encapsulating the active
sites. Directed removal of coke precursors at the metal sites, while
preserving the protective graphene layer, was achieved by
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controlled
co-feeding
of
oxygen
during
acetylene
hydrochlorination. With this integrated approach the stability could
be improved by more than 20 times, reaching comparable
performance to state-of-the-art gold-based systems at a ca. 4-fold
lower price and thereby demonstrating the great potential of
ruthenium-based catalysts for acetylene hydrochlorination in
technical scale.
Experimental Section
Details on the catalyst preparation, characterization, and evaluation, as
well as additional characterization and catalytic performance data are
provided in the Supporting Information.
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Acknowledgements
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This work was supported by ETH Research Grant ETH-40 17-1
and the Swiss National Science Foundation (project no. 200021-
169679). The Micromeritics Grant Program is thanked for the
award of the 3Flex instrument. We thank Dr. Roland Hauert, Dr.
Antonio J. Martín, Jan-Georg Rosenboom, Guido Zichittella, and
Gabriele Manzocchi for conducting XPS, SEM, GPC analysis,
Raman spectroscopy, and catalytic tests, respectively. The
Scientific Center for Optical and Electron Microscopy (ScopeM) at
ETH Zurich is acknowledged for the use of their facilities.
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Keywords: acetylene hydrochlorination • catalyst lifetime •
graphene • nanostructuring • ruthenium nanoparticle
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