Abstract
Selective hydrogenation of halonitrobenzenes into haloanilines represents a green process to replace the environmentally unfriendly non-catalytic chemical reduction process in industry. However, this transformation often suffers from serious dehalogenation due to the easy break of carbon-halogen bonds on metal surfaces. Modulations of the electronic structure of the supported Pd nanoparticles on Lewis-basic layered double hydroxides have been demonstrated to promote catalytic activity and selectivity for hydrogenation of halonitrobenzenes into haloanilines. Mechanism studies suggest that Pd with the enhanced electron density not only improves the capability for hydrogen activation, but also generates the partially negative-charged hydrogen species to suppress the electrophilic attack on the carbon-halogen bond and avoid the dehalogenation.
Highlights
Haloanilines are important intermediates of various fine and bulk chemicals in the chemical industry, such as medicines, pesticides, dyes and pigments [1,2]
As revealed from the X-ray diffraction (XRD) patterns (Figure S2), the diffraction peaks of the CoFe-Layered double hydroxides (LDHs) are all well indexed to JPCDS No 50-0235, indicating the successful formation of CoFe-LDHs
The Pd nanoparticles with an average size of 2.33 ± 0.2 nm (Figure S3a) are observed, as shown in the transmission electron microscope (TEM) image (Figure 1a)
Summary
Haloanilines are important intermediates of various fine and bulk chemicals in the chemical industry, such as medicines, pesticides, dyes and pigments [1,2]. We demonstrate that the electronic structure of Pd nanoparticles effectively regulates the catalytic activity and selectivity for halonitrobenzenes-to-haloanilines hydrogenation.
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