Cu
is known as one of the most promising metallic catalysts for
conversion of CO2 to hydrocarbons such as methane, ethylene,
and ethanol by electrochemical reduction. The oxide-derived Cu (OD-Cu)
moiety has been investigated as a candidate for enhancing the activity
for CO2 electrochemical reduction to C2+ products.
The reduction process is affected by catalytic grain boundary, local
pH, residual oxygen atoms, and other features of the catalysts. In
order to understand the detailed mechanism, we performed in situ attenuated
total reflection surface-enhanced infrared absorption spectroscopy
(in situ ATR-SEIRAS) measurements for CO2 reduction using
several different Cu electrodes whose oxidation states are controlled.
The spectroscopic investigations demonstrate that a copper oxide electrode
(Cu2O) has low activity against CO2 reduction
on the basis of low-level detection of CO as an intermediate of CO2 reduction. On the other hand, other Cu electrodes possessing
an OH layer on the Cu surface (Cu(OH)2/Cu) and metallic
Cu exhibit higher CO2 reduction activity with significantly
greater detection of produced CO. When the metallic Cu electrode is
used, only one peak (2060 cm–1) assignable to CO
bound to the atop site of Cu is observed. However, additional peaks
are detected in the range of 1900–2100 cm–1 when the Cu(OH)2/Cu electrode is used. To understand
these findings, the adsorption energy of CO on a Cu(OH)2/Cu electrode and the CO stretching frequency were evaluated by performing
DFT calculations. The adsorption energy is enhanced and the CO stretching
frequencies are shifted to lower energy in comparison with those using
a metallic Cu electrode. These results indicate that it is predominantly
favorable to adsorb some CO molecules near the OH moiety of the Cu(OH)2/Cu electrode and to induce interactions of CO molecules with
each other. This observation is consistent with the results of controlled
potential electrolysis (CPE), which generates C2+ products
as previously reported. When CPE is carried out in D2O
solution, residual and/or adsorbed OD– groups on
Cu are detected by ATR-SEIRAS and the surface of the Cu(OH)2/Cu electrode is confirmed to be metallic Cu, as measured by in situ
Raman and XPS. From the ATR-SEIRAS experiments when switching from
under CO2 to Ar during the electrochemical reduction, the
OH layer is suggested to prevent deactivation of the Cu electrode
via formation of the CO layer, which is detected as a bridge-bounded
form on the metallic Cu electrode. The above findings indicate that
the OH layer provides the advantage of attracting CO molecules closer
to each other while reducing them to C2+ products without
any degradation during electrolysis.
Abstract-To elucidate the role of intracellular Na ϩ kinetics during ischemia and reperfusion in postischemic contractile dysfunction, intracellular Na ϩ concentration ([Na ϩ ] i ) was measured in isolated perfused rat hearts using 23 Na nuclear magnetic resonance spectroscopy. The extension of the ischemic period from 9 minutes to 15, 21, and
Lower-energy biphasic waveform shocks were as effective as conventional higher energy monophasic waveform shocks for restoration of spontaneous circulation after 4 and 7 min of untreated VF. Significantly better postresuscitation myocardial function was observed after biphasic waveform defibrillation.
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