Correlation of Electronic Structure with Catalytic Activity: H2–D2 Exchange across CuxPd1–x Composition Space
Correlation of Electronic Structure with Catalytic Activity: H2–D2 Exchange across CuxPd1–x Composition Space
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电子结构与催化活性的相关性：CuxPd1-x 组成空间中的 H2-D2 交换
DOI：
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
A. Gellman
中科院分区：
文献类型：
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作者：
Gamze Gumuslu;P. Kondratyuk;Jacob R. Boes;B. Morreale;James B. Miller;J. Kitchin;A. Gellman
合金催化剂的活性和价带电子结构之间的关系进行了实验研究，在一个广泛的，连续的跨度CuxPd 1-x的组成空间。CuxPd 1-x组成扩散合金膜（CSAF）被用作催化剂库，具有100通道微反应器，以在333-593 K的温度范围内在100个离散的CuxPd 1-x组成（跨越范围x = 0.30-0.97）下测量H2-D2交换动力学。H2-D2交换活性在x = 0.30-0.97的组成范围内表现出单调下降。使用稳态微动力学模型来估算解离H2吸附的能垒Δ埃兹ε和重组H2解吸的能垒ΔEdes ε随合金成分x的变化。它们的值落在Δ埃兹ε（x）= 0.15至0.45 eV和ΔEdes ε（x）= 0.55-0.65 eV的范围内。从CuxPd 1-xCSAF获得了空间分辨的紫外光电子能谱，并用于估计作为合金成分的函数的价带填充态的平均能量。
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 H2–D2 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 H2–D2 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 H2 adsorption, ΔEads‡, and recombinative H2 desorption, ΔEdes‡, as functions of alloy composition, x. Their values fall in the ranges ΔEads‡(x) = 0.15 to 0.45 eV and ΔEdes‡(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 com...