Journal Article

Dynamic multinuclear sites formed by mobilized copper ions in NOₓ selective catalytic reduction

Khurana, Ishant, Li, Sichi, Parekh, Atish A., Shih, Arthur J., Schneider, William F., Li, Hui, Ribeiro, Fabio H., Miller, Jeffrey T., Albarracin-Caballero, Jonatan D., Delgass, W. Nicholas, Paolucci, Christopher, Gounder, Rajamani, Di Iorio, John R., Yezerets, Aleksey

2017

Overview

Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NOₓ) with ammonia (NH₃), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O₂)–mediated CuI→CuII redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst.

• Publisher: American Association for the Advancement of Science,The American Association for the Advancement of Science,AAAS
• Subject: Absorption spectroscopy / Aluminum / Ammonia / Catalysis / Catalysts / Copper / Diesel engines / First principles / Heavy metals / Ion pairs / Ions / Low temperature / Nitrogen oxides / Oxides / Oxygen / Photochemicals / Selective catalytic reduction / Spectroscopy / Spectrum analysis / Tethering / X-ray absorption spectroscopy / X-ray spectroscopy / Zeolites