Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation

Abstract

Finding heterogeneous catalysts that are superior to homogeneous ones for selective catalytic transformations is a major challenge in catalysis. Here, we show how micropores in metal-organic frameworks (MOFs) push homogeneous catalytic reactions into kinetic regimes inaccessible under standard conditions. Such property allows branched selectivity up to 90% in the Co-catalysed hydroformylation of olefins without directing groups, not achievable with existing catalysts. This finding has a big potential in the production of aldehydes for the fine chemical industry. Monte Carlo and density functional theory simulations combined with kinetic models show that the micropores of MOFs with UMCM-1 and MOF-74 topologies increase the olefins density beyond neat conditions while partially preventing the adsorption of syngas leading to high branched selectivity. The easy experimental protocol and the chemical and structural flexibility of MOFs will attract the interest of the fine chemical industries towards the design of heterogeneous processes with exceptional selectivity.

Engineering Nanoscale Metal‐Organic Frameworks for Heterogeneous Catalysis

“…[ 113–120 ] Upon the catalytic conversion into specific products, the size of the pores needs to match the corresponding product range, thereby improving the selectivity. [ 121–126 ] Different construction units and coordination environment endow MOFs with various types of pores. Common types refer to 0 D cage or 1D channel.…”

Reusable Catalysts for Hydroformylation‐Based Reactions

“…Ranocchiari et al [70] described the synthesis of metal-organic frameworks (MOFs) and their application as kinetic modulators in Co-catalyzed hydroformylation of olefins (Figure 9). Under optimized conditions for 1-hexene hydroformylation (100°C, 30 bar CO/H 2 , 17 h), using Co 2 (CO) 8 as catalytic precursor, these MOF materials provided conversions of up to 36 %, with an unexpected iso/n ratio up to 85 : 15.…”

“…Ranocchiari et al [70] . described the synthesis of metal‐organic frameworks (MOFs) and their application as kinetic modulators in Co‐catalyzed hydroformylation of olefins (Figure 9).…”

Cooperative Single-Atom Active Centers for Attenuating Linear Scaling Effect in Nitrogen Reduction Reaction

“…[7][8][9][10][11] Because SACs possess simple and unified active centers with well-defined composition and coordination environments, they are deemed an ideal type of catalysts model to provide mechanistic insight into heterogeneous catalysis. Particularly, the advent of high-density SACs due to the rapid advance of synthetic technologies [12][13][14][15][16][17][18] and precise control of inter-site distance [19][20][21] would facilitate the study of cooperative effects of multiple active centers. The synergetic effects between adjacent active sites on heterogeneous catalysis have drawn increasing attention in experimental work.…”

“…A single metal center coordinated with four nitrogen atoms (shorted as MN4) constitutes the essential moiety of many excellent molecular catalysts derived from metal porphyrins and metal phthalocyanines. [35][36][37] The marriage of MN4 active center and two-dimensional carbon support (shorted as MN4/C) benefits from the ease of synthesis [13][14][15][16][17][18] , which has generated quite a few promising SACs, including NRR catalysts [38][39][40][41][42][43] . As shown in Figure 1, we placed two adjacent MN4 within graphene (shorted as MN4 duo/G) as a prototype model of highdensity MN4 SACs to investigate how the cooperation of singleatom centers will impact scaling relations in NRR.…”