Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 19, Issue 35, Pages 23960-23970Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7cp04604a
Keywords
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Funding
- National Natural Science Foundation of China [21477007, 21407007, 91534201]
- Natural Science Foundation of Jiangsu Province of China [BK20140268]
- Fundamental Research Funds for the Central Universities [JD1719, PYVZ1701]
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HCN being a highly toxic N-containing volatile organic compound (VOCs) poses great threat to human living environment. Selective catalytic combustion of HCN (HCN-SCC) over metal modified zeolite catalysts has attracted great attention due to related high efficiency and excellent N-2 selectivity. In the present work, three types of 24T-Cu-BEA models with different active centers of single [Cu](+), double [Cu](+), and [Cu-O-Cu](2+) were constructed for HCN-SCC mechanism simulations based on density functional theory (DFT). DFT simulation results revealed that HCN-SCC followed an oxidation mechanism over double [Cu](+) through an intermediate of NCO, wherein the synergistic effects of double [Cu](+) active centers were clearly observed, resulting in a significantly lowered energy barrier (1.6 kcal mol(-1)) during HCN oxidation into NCO. However, an oxidation mechanism (HCN oxidized into NH radical and CO2 through intermediate of HNCO) combining with a hydrolysis mechanism (NH radical hydrolyses into NH3) occurred over single [Cu]+ and [Cu-O-Cu](2+), wherein the NH2 hydrolysis to NH3 step was regarded as the rate determining step with an energy barrier of 72.3 and 74.3 kcal mol(-1), respectively. Finally, Mulliken charge transfer (CT) analysis was conducted, based on which the electric properties of different active centers were well illustrated.
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