A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like carbon network. The particular structure of the carbon-silica composite allows the accommodation of a broad variety of catalytically active functions, useful to attain cascade reactions, in a readily tunable pore texture. The significance of a joint action of Lewis and weak Brønsted acid sites was studied here to realize fast and selective sugar conversion. Lewis acidity is provided by grafting the silica component with Sn(IV), while weak Brønsted acidity originates from oxygen-containing functional groups in the carbon part. The weak Brønsted acid content was varied by changing the amount of carbon loading, the pyrolysis temperature, and the post-treatment procedure. As both catalytic functions can be tuned independently, their individual role and optimal balance can be searched for. It was thus demonstrated for the first time that the presence of weak Brønsted acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the first step in the reaction network from triose to lactate. Composite catalysts with well-balanced Lewis/Brønsted acidity are able to convert the trioses, glyceraldehyde and dihydroxyacetone, quantitatively into ethyl lactate in ethanol with an order of magnitude higher reaction rate when compared to the Sn grafted MCM-41 reference catalyst. Interestingly, the ability to tailor the pore architecture further allows the synthesis of a variety of amphiphilic alkyl lactates from trioses and long chain alcohols in moderate to high yields. Finally, direct lactate formation from hexoses, glucose and fructose, and disaccharides composed thereof, sucrose, was also attempted. For instance, conversion of sucrose with the bifunctional composite catalyst yields 45% methyl lactate in methanol at slightly elevated reaction temperature. The hybrid catalyst proved to be recyclable in various successive runs when used in alcohol solvent.
The lithium–sulfur (Li–S) battery is regarded as the most promising rechargeable energy storage technology for the increasing applications of clean energy transportation systems due to its remarkable high theoretical energy density of 2.6 kWh kg−1, considerably outperforming today's lithium‐ion batteries. Additionally, the use of sulfur as active cathode material has the advantages of being inexpensive, environmentally benign, and naturally abundant. However, the insulating nature of sulfur, the fast capacity fading, and the short lifespan of Li–S batteries have been hampered their commercialization. In this paper, a functional mesoporous carbon‐coated separator is presented for improving the overall performance of Li–S batteries. A straightforward coating modification of the commercial polypropylene separator allows the integration of a conductive mesoporous carbon layer which offers a physical place to localize dissolved polysulfide intermediates and retain them as active material within the cathode side. Despite the use of a simple sulfur–carbon black mixture as cathode, the Li–S cell with a mesoporous carbon‐coated separator offers outstanding performance with an initial capacity of 1378 mAh g−1 at 0.2 C, and high reversible capacity of 723 mAh g−1, and degradation rate of only 0.081% per cycle, after 500 cycles at 0.5 C.
The row of endohedral fullerenes is extended by a new type of sulfur-containing clusterfullerenes: the metal sulfide (M(2)S) has been stabilized within a fullerene cage for the first time. The new sulfur-containing clusterfullerenes M(2)S@C(82)-C(3v)(8) have been isolated for a variety of metals (M = Sc, Y, Dy, and Lu). The UV-vis-NIR, electrochemical, and FTIR spectroscopic characterization and extended DFT calculations point to a close similarity of the M(2)S@C(82) cage isomeric and electronic structure to that of the carbide clusterfullerenes M(2)C(2)@C(2n). The bonding in M(2)S@C(82) is studied in detail by molecular orbital analysis as well as with the use of quantum theory of atom-in-molecules (QTAIM) and electron localization function (ELF) approaches. The metal sulfide cluster formally transfers four electrons to the carbon cage, and metal-sulfur and metal-carbon cage bonds with a high degree of covalency are formed. Molecular dynamics simulations show that Sc(2)S cluster exhibits an almost free rotation around the C(3) axis of the carbon cage, resulting thus in a single line (45)Sc NMR spectrum.
Lewis acid Snβ-type zeolites
with varying amounts of Brønsted
acid Al in the framework were synthesized using a simple two-step
procedure comprising partial dealumination of β zeolite under
action of acid, followed by grafting with SnCl4·5H2O in dry isopropanol. Characterization of the thus-prepared
Al-containing Snβ (Sn/pDeAlβ) zeolites with ICP, (pyridine
probed) FTIR, and 27Al MAS NMR demonstrates the presence
of Brønsted acid framework AlIII. Tetrahedral Lewis
acidic SnIV is present, as ascertained by a combination
of techniques such as EPMA, 119Sn Möβbauer,
XPS, (pyridine probed) FTIR, and UV–vis. A closed SnIV configuration was implied by comparing of 119Sn solid-state
MAS NMR and deuterated acetonitrile probed FTIR spectra with literature.
The catalytic activity of the Al-containing Snβ was tested for
the conversion of 1,3-dihydroxyacetone (DHA) into ethyl lactate (ELA),
proceeding via pyruvic aldehyde (PAL). Despite the difference in synthesis
between the classic hydrothermal Snβ reference and Sn/pDeAlβ,
the activity of Sn for the Lewis acid-catalyzed hydride shift of PAL
to ELA is similar. Yet, the overall reaction rate of DHA into ELA
is faster with Sn/pDeAlβ because Brønsted acidity of the
remaining framework AlIII facilitates the rate-determining
dehydration of DHA into PAL. Materials containing moderate amounts
of Al (0.3 wt % Al) show the highest ELA productivities, leading to
a record value of 2113 g ELA·kg catalyst–1·h–1 at 363 K. The cooperative effect of Lewis SnIV and Brønsted AlIII acid sites is verified
by comparing catalytic data with physical mixtures of partially dealuminated
β zeolite and Al-free Snβ.
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