High‐Density Lewis Acid Sites in Porous Single‐Crystalline Monoliths to Enhance Propane Dehydrogenation at Reduced Temperatures

Abstract

The non‐oxidative dehydrogenation of propane to propylene plays an important role in the light‐olefin chemical industry. However, the conversion and selectivity remain a fundamental challenge at low temperatures. Here we create and engineer high‐density Lewis acid sites at well‐defined surfaces in porous single‐crystalline Mo2N and MoN monoliths to enhance the non‐oxidative dehydrogenation of propane to propylene. The top‐layer Mo ions with unsaturated Mo‐N1/6 and Mo‐N1/3 coordination structures provide high‐density Lewis acid sites at the surface, leading to the effective activation of C−H bonds without the overcracking of C−C bonds during the non‐oxidative dehydrogenation of propane. We demonstrate a propane conversion of ≈11 % and a propylene selectivity of ≈95 % with porous single‐crystalline Mo2N and MoN monoliths at 500 °C.

Assessment of Lewis‐Acidic Surface Sites Using Tetrahydrofuran as a Suitable and Smart Probe Molecule

“…Another research group [49] proposed that the thermal treatment and the conditions used during the preparation of MoO 3 drastically alter the population and types of acidic sites on its surface. Very recently, in a published article, high‐density Lewis acid sites were created on growing porous single‐crystalline Mo 2 N and MoN [50] …”

“…Very recently, in a published article, high-density Lewis acid sites were created on growing porous singlecrystalline Mo 2 N and MoN. [50] Results…”

Tailoring Single‐Atom Platinum for Selective and Stable Catalysts in Propane Dehydrogenation

“…Cost and element strategy considerations necessitate the use of less expensive elements, such as Fe, Ni, and Co, instead of precious Pt, which is highly demanded. Due to the low activity, selectivity, and stability of non‐precious metal‐based catalysts for PDH, development is still in progress [70–73] . Recently, some alternative alloys, such as NiMo [74] and Fe 3 Ga, [75] have been reported with the help of theoretical calculations.…”

“…Due to the low activity, selectivity, and stability of non-precious metal-based catalysts for PDH, development is still in progress. [70][71][72][73] Recently, some alternative alloys, such as NiMo [74] and Fe 3 Ga, [75] have been reported with the help of theoretical calculations. These theoretical predictions have significantly aided in the material search for non-precious metal-based catalysts.…”

Atomically precise structures of Pt2(S-Adam)4(PPh3)2 complexes and catalytic application in propane dehydrogenation

“…[37][38][39][40][41][42] Non-oxidative PDH holds more potential than oxidative dehydrogenation owing to the higher propylene selectivity. [43][44][45][46] Platinum-based catalysts are believed to be the most promising for PDH in commercial applications. [47][48][49][50][51] Owing to the relatively low selectivity for propylene and poor reaction stability of catalysts, platinum-based catalysts for PDH still need to be studied comprehensively.…”