Catalytic Hydrogen‐Chlorine Exchange between Chlorinated Hydrocarbons under Oxygen‐Free Conditions

Abstract

Pass the parcel: Activity experiments show that LaCl3 supported on carbon nanofibers is a highly active, selective, and stable catalyst for the H–Cl exchange reaction between CCl4 and CH2Cl2 to form CHCl3 (see scheme) in the absence of either lattice or gas‐phase oxygen. Density functional calculations suggest that the reaction proceeds through the formation of weakly adsorbed Cl and H species which can be exchanged between the reactants.

Spectroscopic observation and structure-insensitivity of hydroxyls on gold

“…Similar cluster and periodic structure models were previously successfully used to describe oxygen, H 2 O 2 and OOH adsorption on Au and other adsorbates on multiple surfaces. 9,13,15,18–28 The calculations show that on most Au surfaces hydroxyls preferentially adsorb on a bridge Au–Au site, with ν (O–H) being in a narrow range from 3683 to 3687 cm −1 (Fig. 2).…”

Scandium, yttrium, the lanthanides

“…LaCl 3 deposited onto carbon nanofibre supports proves a very active and selective catalyst for the exchange of a chlorine atom between CCl 4 and CH 2 Cl 2 , forming CHCl 3 in extremely high yield. 28 Anhydrous Nd(OAc) 3 , formed from reaction between Nd and malonic acid at 180 1C, contains eight and nine coordinate Nd. 29 The cinnamates (Sc, Y, La-Lu except Pm) have been synthesised from the metal and trans-cinnamic acid at 200 1C.…”

Mechanistic Insights into the Lanthanide-Catalyzed Oxychlorination of Methane as Revealed by Operando Spectroscopy

“…10 At moderate conversion levels (X CH 4 = 10%), S CH 3 Cl ∼80% was obtained with minor byproducts of CH 2 Cl 2 (12%) and CO (8%), essentially free of CO 2 , CHCl 3 , and CCl 4 . 31 However, the high selectivity was only obtained at low conversion levels (X CH 4 = <10%). As the conversion of CH 4 was increased (X CH 4 = ∼18%), the CO yield would surpass the CH 3 Cl yield.…”