5 research outputs found
Redox-Mediated Reconstruction of Copper during Carbon Monoxide Oxidation
Copper has excellent initial activity
for the oxidation of CO, yet it rapidly deactivates under reaction
conditions. In an effort to obtain a full picture of the dynamic morphological
and chemical changes occurring on the surface of catalysts under CO
oxidation conditions, a complementary set of in situ ambient pressure
(AP) techniques that include scanning tunneling microscopy, infrared
reflection absorption spectroscopy (IRRAS), and X-ray photoelectron
spectroscopy were conducted. Herein, we report in situ AP CO oxidation
experiments over Cu(111) model catalysts at room temperature. Depending
on the CO:O<sub>2</sub> ratio, Cu presents different oxidation states,
leading to the coexistence of several phases. During CO oxidation,
a redox cycle is observed on the substrate’s surface, in which
Cu atoms are oxidized and pulled from terraces and step edges and
then are reduced and rejoin nearby step edges. IRRAS results confirm
the presence of under-coordinated Cu atoms during the reaction. By
using control experiments to isolate individual phases, it is shown
that the rate for CO oxidation decreases systematically as metallic
copper is fully oxidized
The Surface Structure of Cu<sub>2</sub>O(100)
Despite the industrial importance
of copper oxides, the nature
of the (100) surface of Cu<sub>2</sub>O has remained poorly understood.
The surface has previously been subject to several theoretical and
experimental studies, but has until now not been investigated by atomically
resolved microscopy or high-resolution photoelectron spectroscopy.
Here we determine the atomic structure and electronic properties of
Cu<sub>2</sub>O(100) by a combination of multiple experimental techniques
and simulations within the framework of density functional theory
(DFT). Low-energy electron diffraction (LEED) and scanning tunneling
microscopy (STM) characterized the three ordered surface structures
found. From DFT calculations, the structures are found to be energetically
ordered as (3,0;1,1), c(2 × 2), and (1 × 1) under ultrahigh
vacuum conditions. Increased oxygen pressures induce the formation
of an oxygen terminated (1 × 1) surface structure. The most common
termination of Cu<sub>2</sub>O(100) has previously been described
by a (3√2 × √2)R45° unit cell exhibiting a
LEED pattern with several missing spots. Through atomically resolved
STM, we show that this structure instead is described by the matrix
(3,0;1,1). Both simulated STM images and calculated photoemission
core level shifts compare favorably with the experimental results
<i>In Situ</i> Imaging of Cu<sub>2</sub>O under Reducing Conditions: Formation of Metallic Fronts by Mass Transfer
Active
catalytic sites have traditionally been analyzed based on
static representations of surface structures and characterization
of materials before or after reactions. We show here by a combination
of <i>in situ</i> microscopy and spectroscopy techniques
that, in the presence of reactants, an oxide catalyst’s chemical
state and morphology are dynamically modified. The reduction of Cu<sub>2</sub>O films is studied under ambient pressures (AP) of CO. The
use of complementary techniques allows us to identify intermediate
surface oxide phases and determine how reaction fronts propagate across
the surface by massive mass transfer of Cu atoms released during the
reduction of the oxide phase in the presence of CO. High resolution <i>in situ</i> imaging by AP scanning tunneling microscopy (AP-STM)
shows that the reduction of the oxide films is initiated at defects
both on step edges and the center of oxide terraces
<i>In Situ</i> Imaging of Cu<sub>2</sub>O under Reducing Conditions: Formation of Metallic Fronts by Mass Transfer
Active
catalytic sites have traditionally been analyzed based on
static representations of surface structures and characterization
of materials before or after reactions. We show here by a combination
of <i>in situ</i> microscopy and spectroscopy techniques
that, in the presence of reactants, an oxide catalyst’s chemical
state and morphology are dynamically modified. The reduction of Cu<sub>2</sub>O films is studied under ambient pressures (AP) of CO. The
use of complementary techniques allows us to identify intermediate
surface oxide phases and determine how reaction fronts propagate across
the surface by massive mass transfer of Cu atoms released during the
reduction of the oxide phase in the presence of CO. High resolution <i>in situ</i> imaging by AP scanning tunneling microscopy (AP-STM)
shows that the reduction of the oxide films is initiated at defects
both on step edges and the center of oxide terraces
<i>In Situ</i> Imaging of Cu<sub>2</sub>O under Reducing Conditions: Formation of Metallic Fronts by Mass Transfer
Active
catalytic sites have traditionally been analyzed based on
static representations of surface structures and characterization
of materials before or after reactions. We show here by a combination
of <i>in situ</i> microscopy and spectroscopy techniques
that, in the presence of reactants, an oxide catalyst’s chemical
state and morphology are dynamically modified. The reduction of Cu<sub>2</sub>O films is studied under ambient pressures (AP) of CO. The
use of complementary techniques allows us to identify intermediate
surface oxide phases and determine how reaction fronts propagate across
the surface by massive mass transfer of Cu atoms released during the
reduction of the oxide phase in the presence of CO. High resolution <i>in situ</i> imaging by AP scanning tunneling microscopy (AP-STM)
shows that the reduction of the oxide films is initiated at defects
both on step edges and the center of oxide terraces