Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework

Developing supported single-site catalysts is an important goal in heterogeneous catalysis since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based metal–organic framework (MOF), NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a MOF (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates

In situ monitoring of stirring effects on polymorphic transformations during cooling crystallization of carbamazepine

The influence of experimental conditions on polymorphic outcome and transformations during cooling crystallization of carbamazepine (CBZ) from anhydrous ethanol has been investigated. Stirring was found to be the most important controlling factor for the initial polymorphic outcome in solutions prepared using commercial CBZ powder. For quiescent conditions, a few large crystals of the metastable trigonal α form (II) initially appeared, undergoing subsequent slow transformation into the stable P-monoclinic β form (III). Under sufficiently vigorous stirring, the induction times observed were clearly defined by the onset of turbidity, which was due to formation of a large number of small form III prismatic crystals. In experiments with solutions prepared by using recrystallized CBZ, significantly shorter induction times were observed under stirring conditions: a large number of small form II needle-shaped crystals initially formed at the onset of turbidity and then relatively rapidly transformed to small crystals of form III. This indicates a possible effect of impurities in the commercial CBZ powder inhibiting rapid nucleation of form II under stirring conditions. In situ monitoring of CBZ polymorphic outcome was performed using custom-built experimental setup for simultaneous measurement of intensity of transmitted and scattered light. Distinct pathways in two-variable intensity plots were observed for formation of each respective polymorph under stirring conditions. The same monitoring technique should be readily applicable to other systems