CO adsorption studies on pure and Ni-covered Cu(111) surfaces

Kirstein, W.; Krüger, Bernd; Thieme, F.

doi:10.1016/0039-6028(86)90052-x

Cited by 125 publications

(64 citation statements)

References 37 publications

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“…Our calculated E ad = À0.48 eV for the (2 2) CO/Cu(111) system agrees very well with available experiment results of E ad = À0.46 to À0.52 eV, [52][53][54] which confirms the validity of our accuracy settings and calculation method. On the contrary, E ad = À0.62 to À0.90 eV, obtained from GGA-PBE and PW91 functionals, [50][51] are relatively lower than those from experiments [52][53][54] and the RPBE functional. [49,51] In our calculations, the magnitudes of E ad are found to be À0.51, À0.48, and À0.06 eV, respectively, when a molecule is adsorbed on the (3 3), (2 2), and (2 1) Cu(111) surfaces at coverage rates of V = 0.11, 0.25, and 0.50 monolayer (ML).…”

Section: Resultssupporting

confidence: 91%

“…To provide a comparison, available experimental [52][53][54] and other theoretical results [49][50][51][68][69] are also listed therein. Our calculated E ad = À0.48 eV for the (2 2) CO/Cu(111) system agrees very well with available experiment results of E ad = À0.46 to À0.52 eV, [52][53][54] which confirms the validity of our accuracy settings and calculation method. On the contrary, E ad = À0.62 to À0.90 eV, obtained from GGA-PBE and PW91 functionals, [50][51] are relatively lower than those from experiments [52][53][54] and the RPBE functional.…”

Section: Resultsmentioning

confidence: 99%

“…[48] For Cu(111) and Cu(211) surfaces, CO is located at the atop site according to the experimental observation. [52][53][54] The initial CÀO distance is set to 1.13 in light of available experimental data. [66] In this case, the E ad value determined is the difference of the total amount of the considered system (E t ) and the corresponding cluster (E Cu ) and free gas (E CO ), namely, that E ad = E t ÀE Cu ÀE CO .…”

Section: Calculationsmentioning

confidence: 99%

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Oxidation of CO Catalyzed by a Cu Cluster: Influence of an Electric Field

et al. 2009

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Adsorption ability and reaction rate are two essential parameters that define the efficiency of a catalyst. Herein, we implement density functional theory (DFT) and report that CO can be oxidized by a pyramidal Cu cluster with an associated reaction barrier E(b)=1.317 eV. In this case, our transition state calculations reveal that the barrier can be significantly lowered after superimposing a negative electric field. Moreover, when the field intensity corresponds to F=-0.010 au, the magnitude of E(b)=0.698 eV is equivalent to-or lower than-those of typical catalysts such as Pt, Rh, and Pd. The superimposition of a positive field is found to enhance the release of the nascent CO(2) molecule. Our study demonstrates that small Cu clusters have better adsorption ability than the corresponding flat surface while the field can be used to enhance the purification of the exhaust gas.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Section: Calculationsmentioning

confidence: 99%

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Oxidation of CO Catalyzed by a Cu Cluster: Influence of an Electric Field

et al. 2009

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“…Likewise, our raw DFT data for Rh(111) is disparate with experimental site preference [31,32] while our corrected energies are in agreement. For Cu(111) the use of the correction gives the experimental site preference [24,33], though the corrected DFT results predict small (≤ 0.1 eV) differences between the top, bridge and hollow sites. Both the raw DFT and the corrected results for Pd(111) agree with the site preference observed by experiment [23,34,35].…”

Section: Resultsmentioning

confidence: 99%

“…For each substrate, the site found to be preferred by experiment is marked with an asterisk (*). Experimental values for E chem are given in parentheses next to E corr GGA for Pt(111) [28,29,30], Rh(111) [31,32], Pd(111) [23,35], Cu(111) [24,33], Pt(100) [36,37,38], Rh(100) [39,40], Pd(100) [38,41], and Cu(100) [42,43] Site ∆Ε S-T (eV) …”

Section: Discussionmentioning

confidence: 99%

First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

2004

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We show that a simple first-principles correction based on the difference between the singlettriplet CO excitation energy values obtained by DFT and high-level quantum chemistry methods yields accurate CO adsorption properties on a variety of metal surfaces. We demonstrate a linear relationship between the CO adsorption energy and the CO singlet-triplet splitting, similar to the linear dependence of CO adsorption energy on the energy of the CO 2π* orbital found recently [Kresse et al., Physical Review B 68, 073401 (2003)]. Converged DFT calculations underestimate the CO singlet-triplet excitation energy ∆ES−T, whereas coupled-cluster and CI calculations reproduce the experimental ∆ES−T. The dependence of E chem on ∆ES−T is used to extrapolate E chem for the top, bridge and hollow sites for the (100) and (111) surfaces of Pt, Rh, Pd and Cu to the values that correspond to the coupled-cluster and CI ∆ES−T value. The correction reproduces experimental adsorption site preference for all cases and obtains E chem in excellent agreement with experimental results.

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Synthesis and Characterization of Degradation‐Resistant Cu@CuPd Nanowire Catalysts for the Efficient Production of Formate and CO from CO₂

et al. 2019

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Not only are the product selectivity and the activity of electrocatalysts important aspects for the evaluation of their overall performance, but also their stability and resistance against structural and compositional degradation during the electrocatalytic reaction. Palladium nanoparticles (Pd‐NPs) have already been identified as superior electrocatalysts for the electrochemical conversion of CO2 into formate at extremely low overpotentials and into carbon monoxide (CO) at medium overpotentials. However, these catalysts suffer from fast degradation, owing to irreversible CO poisoning of Pd reaction sites. Herein, we report on nanoparticulate bimetallic Pd45Cu55 catalysts, demonstrating a similar selectivity and activity to the pure Pd‐NPs, but showing additional superior degradation stability and resistance against CO poisoning. Pd45Cu55 catalysts were synthesized by means of a galvanic displacement reaction using copper nanowires (Cu‐NWs) as the starting material (template) for the galvanic displacement reaction, which leaves a surface‐confined alloy film and respective nanoparticles on the Cu‐NW template (denoted as Cu@CuPd‐NWs). A faradaic efficiency (FE) up to FEformate ≈80 % can be achieved at −0.3 V vs. RHE, thus clearly proving that the ‘anomalous’ CO2 reaction mechanism via the CO2 hydrogenation pathway, discussed for pure Pd‐NPs, can also be transferred to Pd‐based bimetallic systems. At medium overpotentials, the product selectivity changes from selective formate to predominant CO formation with a maximum faradaic efficiency of FECO=86 %. Extended CO2 electrolyses demonstrate, for both formate and CO production, superior degradation stability, for example, FECO remains at 85 %±5 % for the duration of 20 h. For the first time, identical location high‐angle annular dark‐field scanning transmission electron microscopy (IL‐HAADF‐STEM) in combination with energy‐dispersive X‐ray spectrometry and identical location scanning electron microscopy (IL‐SEM) were applied to demonstrate the compositional and structural stability of the bimetallic catalyst under CO2 reduction conditions.

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CO adsorption studies on pure and Ni-covered Cu(111) surfaces

Cited by 125 publications

References 37 publications

Oxidation of CO Catalyzed by a Cu Cluster: Influence of an Electric Field

Oxidation of CO Catalyzed by a Cu Cluster: Influence of an Electric Field

First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

Synthesis and Characterization of Degradation‐Resistant Cu@CuPd Nanowire Catalysts for the Efficient Production of Formate and CO from CO₂

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CO adsorption studies on pure and Ni-covered Cu(111) surfaces

Cited by 125 publications

References 37 publications

Oxidation of CO Catalyzed by a Cu Cluster: Influence of an Electric Field

Oxidation of CO Catalyzed by a Cu Cluster: Influence of an Electric Field

First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

Synthesis and Characterization of Degradation‐Resistant Cu@CuPd Nanowire Catalysts for the Efficient Production of Formate and CO from CO2

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Synthesis and Characterization of Degradation‐Resistant Cu@CuPd Nanowire Catalysts for the Efficient Production of Formate and CO from CO₂