Solvent-Free Heterogeneous Catalytic Hydrogenation of Polyesters to Diols.

The utilization of carbon resources stored in plastic polymers through chemical recycling and upcycling is a promising approach for mitigating plastic waste. However, most current methods for upcycling suffer from limited selectivity towards a specific valuable product, particularly when attempting full conversion of the plastic. We present a highly selective reaction route for transforming polylactic acid (PLA) into 1,2-propanediol utilizing a Zn-modified Cu catalyst. This reaction exhibits excellent reactivity (0.65 g gcat -1 h-1 ) and selectivity (99.5 %) towards 1,2-propanediol, and most importantly, can be performed in a solvent-free mode. Significantly, the overall solvent-free reaction is an atom-economical reaction with all the atoms in reactants (PLA and H2 ) fixed into the final product (1,2-propanediol), eliminating the need for a separation process. This method provides an innovative and economically viable solution for upgrading polyesters to produce high-purity products under mild conditions with optimal atom utilization.

Catalytic Amination of Polylactic Acid to Alanine.

In comparison to the traditional petroleum-based plastics, polylactic acid, the most popular biodegradable plastic, can be decomposed into carbon dioxide and water in the environment. However, the natural degradation of polylactic acid requires a substantial period of time and, more importantly, it is a carbon-emitting process. Therefore, it is highly desirable to develop a novel transformation process that can upcycle the plastic trash into value-added products, especially with high chemical selectivity. Here we demonstrate a one-pot catalytic method to convert polylactic acid into alanine by a simple ammonia solution treatment using a Ru/TiO2 catalyst. The process has a 77% yield of alanine at 140 °C, and an overall selectivity of 94% can be reached by recycling experiments. Importantly, no added hydrogen is used in this process. It has been verified that lactamide and ammonium lactate are the initial intermediates and that the dehydrogenation of ammonium lactate initiates the amination, while Ru nanoparticles are essential for the dehydrogenation/rehydrogenation and amination steps. The process demonstrated here could expand the application of polylactic acid waste and inspire new upcycling strategies for different plastic wastes.

Atomically Dispersed Ni/α-MoC Catalyst for Hydrogen Production from Methanol/Water.

Methanol-water reforming is a promising solution for H2 production/transportation in stationary and mobile hydrogen applications. Developing inexpensive catalysts with sufficiently high activity, selectivity, and stability remains challenging. In this paper, nickel-supported over face-centered cubic (fcc) phase α-MoC has been discovered to exhibit extraordinary hydrogen production activity in the aqueous-phase methanol reforming reaction. Under optimized condition, the hydrogen production rate of 2% Ni/α-MoC is about 6 times higher than that of conventional noble metal 2% Pt/Al2O3 catalyst. We demonstrate that Ni is atomically dispersed over α-MoC via carbon bridge bonds, forming a Ni1-Cx motif on the carbide surface. Such Ni1-Cx motifs can effectively stabilize the isolated Ni1 sites over the α-MoC substrate, rendering maximized active site density and high structural stability. In addition, the synergy between Ni1-Cx motif and α-MoC produces an active interfacial structure for water dissociation, methanol activation, and successive reforming processes with compatible activity.