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HKUST-1 as a Heterogeneous Catalyst for the Synthesis of Vanillin
Published on: July 23, 2016
Heterogeneous Fe3 single-cluster catalyst for ammonia synthesis via an associative mechanism
Jin-Cheng Liu1, Xue-Lu Ma1, Yong Li1
1Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China.
Abstract:
The current industrial ammonia synthesis relies on Haber-Bosch process that is initiated by the dissociative mechanism, in which the adsorbed N2 dissociates directly, and thus is limited by Brønsted-Evans-Polanyi (BEP) relation. Here we propose a new strategy that an anchored Fe3 cluster on the θ-Al2O3(010) surface as a heterogeneous catalyst for ammonia synthesis from first-principles theoretical study and microkinetic analysis. We have studied the whole catalytic mechanism for conversion of N2 to NH3 on Fe3/θ-Al2O3(010), and find that an associative mechanism, in which the adsorbed N2 is first hydrogenated to NNH, dominates over the dissociative mechanism, which we attribute to the large spin polarization, low oxidation state of iron, and multi-step redox capability of Fe3 cluster. The associative mechanism liberates the turnover frequency (TOF) for ammonia production from the limitation due to the BEP relation, and the calculated TOF on Fe3/θ-Al2O3(010) is comparable to Ru B5 site.
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