Identification of reaction intermediates in the decomposition of formic acid on Pd

被引:6
作者
Fingerhut, Jan [1 ]
Lecroart, Loic [2 ]
Schwarzer, Michael [1 ]
Hoerandl, Stefan [1 ]
Borodin, Dmitriy [1 ,2 ,5 ]
Kandratsenka, Alexander [2 ]
Kitsopoulos, Theofanis N. [2 ,3 ]
Auerbach, Daniel J. [2 ]
Wodtke, Alec M. [1 ,2 ,4 ]
机构
[1] Georg August Univ Goettingen, Inst Phys Chem, D-37077 Gottingen, Germany
[2] Max Planck Inst Multidisciplinary Sci, Dept Dynam Surfaces, D-37077 Gottingen, Germany
[3] Univ Southern Mississippi, Sch Math & Nat Sci, Hattiesburg, MS 39406 USA
[4] Georg August Univ Goettingen, Int Ctr Adv Studies Energy Convers, D-37077 Gottingen, Germany
[5] Ctr Quantum Nanosci, Ewhayeodae Gil 52, Seoul 03760, South Korea
基金
欧洲研究理事会;
关键词
DENSITY-FUNCTIONAL THEORY; TOTAL-ENERGY CALCULATIONS; HCOOH DECOMPOSITION; HYDROGEN; SURFACE; ABSORPTION; ADSORPTION; ELECTROOXIDATION; DEHYDROGENATION; NANOPARTICLES;
D O I
10.1039/d3fd00174a
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
Uncovering the role of reaction intermediates is crucial to developing an understanding of heterogeneous catalysis because catalytic reactions often involve complex networks of elementary steps. Identifying the reaction intermediates is often difficult because their short lifetimes and low concentrations make it difficult to observe them with surface sensitive spectroscopic techniques. In this paper we report a different approach to identify intermediates for the formic acid decomposition reaction on Pd(111) and Pd(332) based on accurate measurements of isotopologue specific thermal reaction rates. At low surface temperatures (similar to 400 K) CO2 formation is the major reaction pathway. The CO2 kinetic data show this occurs via two temporally resolved reaction processes. Thus, there must be two parallel pathways which we attribute to the participation of two intermediate species in the reaction. Isotopic substitution reveals large and isotopologue specific kinetic isotope effects that allow us to identify the two key intermediates as bidentate formate and carboxyl. The decomposition of the bidentate formate is substantially slower than that of carboxyl. On Pd(332), at high surface temperatures (643 K to 693 K) we observe both CO and CO2 production. The observation of CO formation reinforces the conclusion of calculations that suggest the carboxyl intermediate plays a major role in the water-gas shift reaction, where carboxyl exhibits temperature dependent branching between CO2 and CO. We report an approach to identify intermediates for the formic acid decomposition reaction on Pd(111) and Pd(332) based on accurate measurements of isotopologue specific thermal reaction rates.
引用
收藏
页码:412 / 434
页数:23
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