We integrated theory with experiment to evaluate the catalytic cycle of seemingly incompatible steps enabled by nanowire array for CH4-to-CH3OH conversion, and determined the array’s efficacy in the context of microscopic compartmentalization.
The utilization of carbon dioxide in polymer synthesis is an attractive strategy for sustainable materials. Electrochemical CO 2 reduction would offer a natural starting point for producing monomers, but the conditions of electrocatalysis are often drastically different from the conditions of coordination−insertion polymerization. Reported here is a strategy for coupling electrochemical and organometallic catalysts that enables polyketone synthesis from CO 2 and ethylene in a single multicompartment reactor. Polyketone materials that are CO 2derived up to 50 wt % can be prepared in this way. Potentiostatic control over the CO-producing catalyst enables the controlled generation of low-pressure CO, which in conjunction with a palladium phosphine sulfonate organometallic catalyst enables copolymerization to nonalternating polyketones with the CO content tuned based on the applied current density.
Integrated catalysis is an emerging methodology that can streamline the multistep synthesis of complicated products in a single reaction vessel, achieving a high degree of control and reducing the waste and cost of an overall chemical process. Integrated catalysis can be defined by the use of spatial and temporal control to couple different catalytic cycles in one pot. This primer discusses commonly employed approaches and their underlying mechanisms, and elaborates on how the integration of spatially and temporally controlled catalysis in one pot can deliver the synthesis of complex products with high efficiency. We highlight recent advances, analyze current applications and limitations, and provide an outlook for the future development of integrated catalysis. surface, [28][29][30][31][32][33][34][35] or by taking advantage of microscopic concentration gradients. 18,20,36,37 By preventing incompatible species from coming into contact with each other, efficient integrated processes may be promoted. In addition to spatial control, introducing temporal control can also alleviate compatibility concerns. If two processes compete with or hinder each other's activity, deactivating one while the other is active can help avoid incompatibility. Temporal control may be achieved using a variety of external stimuli [38][39][40][41] to switch between different states of a catalyst that have orthogonal reactivity [G] toward certain substrates.
Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic...
Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic catalysis to ensure high reaction turnovers with minimal side reactions. However, a scarcity of theoretical framework towards confined organometallic chemistry impedes a broader utility for the implementation of compartmentalization. Herein, we report a general kinetic model and offer design guidance for a compartmentalized organometallic catalytic cycle. In comparison to a non-compartmentalized catalysis, compartmentalization is quantitatively shown to prevent the unwanted intermediate deactivation, boost the corresponding reaction efficiency (γ), and subsequently increase catalytic turnover frequency (TOF). The key parameter in the model is the volumetric diffusive conductance (F_V) that describes catalysts’ diffusion propensity across a compartment’s boundary. Optimal values of F_V for a specific organometallic chemistry are needed to achieve maximal values of γ and TOF. As illustrated in specific reaction examples, our model suggests that a tailored compartment design, including the use of nanomaterials, is needed to suit a specific organometallic catalytic cycle. This work provides justification and design principles for further exploration into compartmentalizing organometallics to enhance catalytic performance. The conclusions from this work are generally applicable to other catalytic systems that need proper design guidance in confinement and compartmentalization.
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