Intermetallic Copper‐Based Electride Catalyst with High Activity for C–H Oxidation and Cycloaddition of CO₂ into Epoxides

Abstract

Inorganic electrides have been proved to be efficient hosts for incorporating transition metals, which can effectively act as active sites giving an outstanding catalytic performance. Here, it is demonstrated that a reusable and recyclable (for more than 7 times) copper‐based intermetallic electride catalyst (LaCu0.67Si1.33), in which the Cu sites activated by anionic electrons with low‐work function are uniformly dispersed in the lattice framework, shows vast potential for the selective C–H oxidation of industrially important hydrocarbons and cycloaddition of CO2 with epoxide. This leads to the production of value‐added cyclic carbonates under mild reaction conditions. Importantly, the LaCu0.67Si1.33 catalyst enables much higher turnover frequencies for the C–H oxidation (up to 25 276 h–1) and cycloaddition of CO2 into epoxide (up to 800 000 h–1), thus exceeding most nonnoble as well as noble metal catalysts. Density functional theory investigations have revealed that the LaCu0.67Si1.33 catalyst is involved in the conversion of N‐hydroxyphthalimide (NHPI) into the phthalimido‐N‐oxyl (PINO), which then triggers selective abstraction of an H atom from ethylbenzene for the generation of a radical susceptible to further oxygenation in the presence of O2.

De novo assembly of frustrated Lewis pair bearing metal‐organic frameworks for atmospheric CO2 cycloaddition

“…As is known, the conversion of CO 2 into value-added cyclic carbonates under mild conditions is an on-going challenge. [19][20][21][22][23][24][25][26][27] The catalytic performances of different catalysts (i.e., MIL-101(Cr), IBCIL, MIL-101 (Cr)/IBCIL physically mixed system, FMOF-IBCIL 0.14 , FMOF-IBCIL 0.19 , and FMOF-IBCIL 0.30 ) in a typical reaction of CO 2 and epichlorohydrin (ECH) at 40 C and atmospheric pressure (1 bar) under same reaction temperature are presented in Figure 3A. A promising chloropropene carbonate (CPC) yield up to 95% (TON = 129.3, Table S4) can be afforded over FMOF-IBCIL 0.19 at 40 C, 1 bar and 24 h in the absence of any cocatalyst.…”

“…One can see that the assembly strategy proposed in this study enables FMOF-IBCIL to achieve high-efficiency catalytic conversion of CO 2 and ECH under the mild conditions (1 atm, 40 C) without cocatalyst, breaking through the bottleneck on the catalytic activity of traditional advanced catalysts for such reactions. [19][20][21][22][23][24][25][26][27] Meanwhile, the catalyst only requires one-step synthesis and low IL consumption, providing a feasible approach for the scale-up application of catalysts.…”

“…Up to now, it is still a bottleneck on achieving high catalytic activity for such reactions under mild especially atmospheric conditions although diverse catalysts have been developed. [19][20][21][22][23][24][25][26][27] Benefited from the cooperation of Lewis acid and Lewis base for boosting the ring opening of epoxides and CO 2 activation, the porous FLP bearing MOFs exhibit unprecedented performances for CO 2 activation and coupling reaction under atmospheric conditions.…”

Chitosan‐Derived N‐Doped Carbon for Light‐Mediated Carbon Dioxide Fixation into Epoxides

“…In this context, Covalent Organic Frameworks (COFs), [18,19] Metal Organic Frameworks (MOFs), [20,21] supported ionic liquids, [22] polyionic liquid, [23] Metal Organic Polymers, [24] supported metal complexes, [25] metal oxides, [26] etc. are found to be efficient catalysts for the reaction of CO 2 and epoxides to generate cyclic carbonates [27–29] . Despite showing good activity towards CO 2 fixation, the aforementioned catalysts required high reaction temperature or high CO 2 pressure to achieve good CO 2 conversion efficiencies.…”

“…are found to be efficient catalysts for the reaction of CO 2 and epoxides to generate cyclic carbonates. [27][28][29] Despite showing good activity towards CO 2 fixation, the aforementioned catalysts required high reaction temperature or high CO 2 pressure to achieve good CO 2 conversion efficiencies. In this context, light-active catalysts are advantageous as they require mild operating conditions like shorter reaction time, lower reaction temperature and atmospheric pressure of CO 2 .…”