Correlation of Electronic Structure with Catalytic Activity: H2-D2 Exchange across CuxPd1-x Composition Space

被引:21
作者
Gumuslu, G. [1 ]
Kondratyuk, P. [1 ]
Boes, J. R. [1 ]
Morreale, B. [1 ,2 ]
Miller, J. B. [1 ,2 ]
Kitchin, J. R. [1 ,2 ]
Gellman, A. J. [1 ,2 ]
机构
[1] Carnegie Mellon Univ, Dept Chem Engn, Pittsburgh, PA 15213 USA
[2] DOE Natl Energy Technol Lab, Pittsburgh, PA 15236 USA
来源
ACS CATALYSIS | 2015年 / 5卷 / 05期
基金
美国国家科学基金会;
关键词
hydrogen; palladium; alloys; electronic structure; catalysis; membranes; adsorption; HIGH-THROUGHPUT CHARACTERIZATION; PALLADIUM ALLOY SURFACES; COMPOSITION-SPREAD; CHEMICAL-PROPERTIES; PD; SEGREGATION; ADSORPTION; HYDROGEN; TERNARY; CU;
D O I
10.1021/cs501586t
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The relationship between alloy catalyst activity and valence band electronic structure has been investigated experimentally across a broad, continuous span of CuxPd1-x composition space. CuxPd1-x composition spread alloy films (CSAFs) were used as catalyst libraries with a 100 channel microreactor to measure the H-2-D-2 exchange kinetics over a temperature range of 333-593 K at 100 discrete CuxPd1-x compositions spanning the range x = 0.30-0.97. The H-2-D-2 exchange activity exhibits a monotonic decrease over the composition range x = 0.30-0.97. A steady state, microkinetic model was used to estimate the energy barriers to dissociative H-2 adsorption, Delta E-ads(double dagger), and recombinative H-2 desorption, Delta E-des(double dagger), as functions of alloy composition, x. Their values fall in the ranges Delta E-ads(double dagger)(x) = 0.15 to 0.45 eV and Delta E-des(double dagger) (x) = 0.55-0.65 eV. Spatially resolved UV photoemission spectra were obtained from the CuxPd1-x CSAF and used to estimate the average energy of the filled states of the valence band as a function of alloy composition, epsilon(v)(x). The energy of the v-band center shifted monotonically from epsilon(v) = -3.3 to -3.9 eV across the composition range x = 0.30-0.97. This monotonic shift and its magnitude were corroborated by DFT calculations. The correlation of Delta E-ads(double dagger)(x) with epsilon(v)(x) across alloy composition space yields Delta E-ads(double dagger)(epsilon(v)) which decreases as the v-band energy shifts toward the Fermi level.
引用
收藏
页码:3137 / 3147
页数:11
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