Additive-free N-methylation reaction synergistically catalyzed by Pt single atoms and clusters on α-MoC using methanol as a sustainable C1 source

Shurui Fan; Mingyuan Zhang; Xiangxin Jin; Zirui Gao; Yao Xu; Maolin Wang; Chuqiao Song; Houhong Song; Xiangxiang Chen; Rulong Ma; Siyu Yao; Rui Gao; Xiaonian Li; Lili Lin

doi:10.1039/D4GC00043A

Additive-free N-methylation reaction synergistically catalyzed by Pt single atoms and clusters on α-MoC using methanol as a sustainable C1 source†

Shurui Fan,‡^ab Mingyuan Zhang,‡^c Xiangxin Jin,^ab Zirui Gao,^d Yao Xu,^d Maolin Wang,^d Chuqiao Song,^ab Houhong Song,^e Xiangxiang Chen,^ab Rulong Ma,^a Siyu Yao,

^e Rui Gao,*^c Xiaonian Li*^a and Lili Lin*^ab

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* Corresponding authors

^a Institute of Industrial Catalysis, State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China
E-mail: linll@zjut.edu.cn, xnli@zjut.edu.cn

^b Zhejiang Carbon Neutral Innovation Institute & Zhejiang International Cooperation Base for Science and Technology on Carbon Emission Reduction and Monitoring, Zhejiang University of Technology, Hangzhou 310014, China

^c College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China
E-mail: gaorui@imu.edu.cn

^d Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

^e Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

Abstract

Methanol is being actively investigated as a promising C1 reagent to replace conventional C1 reagents in organic synthesis, due to its properties of being economical, abundant, nontoxic and sustainably producible. However, because of the high enthalpy of dehydrogenation, it has not been reported frequently. Herein, we report that Pt single atoms (Pt₁) and Pt clusters (Pt_n) are cooperatively loaded on α-MoC to achieve the conversion of various of unsaturated N-containing compounds into value-added N-methylation compounds simply in methanol aqueous solution, successfully avoiding the use of external hydrogen or any additives. The synergy between coexisting Pt₁ and Pt_n on Pt_1+n/α-MoC is identified as necessary to realize the tandem conversion with superior activity and selectivity. Pt₁/α-MoC is the active site for in situ hydrogen production from aqueous phase methanol reforming, and Pt_n/α-MoC is responsible for the successive hydrogenation and methylation. The partially positive Pt_n^δ+ species are crucial for the reductive N-methylation reaction, as the strong coordination of N-containing compounds to Pt particles (Pt_n) significantly inhibits the catalytic activity. Experimental and DFT results further show that, unlike the traditional hydrogen-borrowing mechanism of methanol via the intermediate formaldehyde, formic acid is found to be a potent intermediate and agent for N-methylation.

Green Chemistry

Additive-free N-methylation reaction synergistically catalyzed by Pt single atoms and clusters on α-MoC using methanol as a sustainable C1 source†

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Additive-free N-methylation reaction synergistically catalyzed by Pt single atoms and clusters on α-MoC using methanol as a sustainable C1 source

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