Chinese team reports metal-free, ligand-free molecular sieve catalysis in Nature
In short
A team led by academician Liu Zhongmin at the Dalian Institute of Chemical Physics reported a carbonylation route in which a molecular sieve does the catalysis alone, with no metal and no ligand. It produces isobutyric acid from propylene and propionic acid from ethylene, with water taking part. The results were published online in Nature on 21 October.
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A research team led by academician Liu Zhongmin (刘中民) at the Dalian Institute of Chemical Physics (大连化学物理研究所) of the Chinese Academy of Sciences, working with partner institutions, has opened a catalytic route that needs no metal and no ligand, Xinhua reported on 21 October, citing the Chinese Academy of Sciences. In the route, a molecular sieve completes the catalysis on its own. The results were published online in Nature on 21 October, Beijing time. [ 1 , 2 , 4 ]
The team achieved two new reactions with water taking part: propylene carbonylation to isobutyric acid and ethylene carbonylation to propionic acid. It also reported a basic rule, that the position and size of the molecular sieve pores directly determine the catalytic result. China News Service said active sites near ten-membered-ring pore openings can catalyse propylene, while eight-membered-ring sites can catalyse ethylene. [ 1 , 2 ]
Carbonylation links carbon monoxide to olefin molecules to make acids, esters and alcohols, and products such as acetic acid, plasticiser alcohols, fragrances and pharmaceutical intermediates are built on it, according to Xinhua and China News Service. They said the mainstream industrial route relies on noble metals such as rhodium and iridium together with organic ligands, and is complex, cumbersome and costly, with difficult separation of catalyst and product. [ 1 , 2 ]
China News Service, citing the research team, said the confinement effect of the molecular sieve suppressed side reactions of olefin polymerisation. It added that, as a solid catalyst, the sieve separates naturally from the products, which makes recovery simpler than in liquid-phase systems. Both agencies said selectivity no longer depends on repeated trial and error with formulas and can be designed in advance through pore geometry. [ 1 , 2 ]
Liu's team had earlier applied molecular sieves to dimethyl ether carbonylation, achieving large-scale industrial production of anhydrous ethanol; China News Service dated this to 2017. Building on that path, the team worked for nearly three years on the new reactions. Xinhua said the work provides a general framework for molecular sieve carbonylation that allows new chemical processes to be predicted in reverse and rationally designed. [ 1 , 2 ]
The team's next step is to scale up the laboratory reactions and move the technology toward industry, Xinhua and Jiemian said. China News Service quoted Liu as saying the aim is to bring molecular sieve carbonylation into factories. Yicai, Jiemian and 36Kr carried short versions of the news; Jiemian and 36Kr credited CCTV News. [ 1 , 2 , 3 , 4 , 5 ]
Why it matters
The outlets say the route addresses the difficulty of separating catalyst from product in the mainstream industrial process, which relies on rhodium and iridium. The team says it will move to process scale-up, but the documents give no timeline for industrial use.
Key facts
- The team of academician Liu Zhongmin (刘中民) at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, worked with partner institutions. [ 1 , 2 , 4 ]
- The new route needs no metal and no ligand: the molecular sieve alone completes the catalysis. [ 1 , 2 , 4 ]
- Two new reactions were achieved, with water taking part: propylene carbonylation to isobutyric acid and ethylene carbonylation to propionic acid. [ 1 , 2 ]
- The team found that the position and size of the molecular sieve pores directly determine the catalytic result. [ 1 , 2 ]
- The work took nearly three years and was published online in Nature on 21 October, Beijing time. [ 1 , 2 , 4 ]
- The team's next step is to scale up the laboratory reactions toward industrial use. [ 1 , 2 , 4 ]
Confirmed by several sources
- The Liu Zhongmin team reported metal-free, ligand-free molecular sieve catalysis of olefin carbonylation, published in Nature on 21 October. [ 1 , 2 , 4 , 5 ]
- The two new reactions are propylene carbonylation to isobutyric acid and ethylene carbonylation to propionic acid. [ 1 , 2 ]
- The team plans to move on to process scale-up. [ 1 , 2 , 4 ]
Still unclear
- When, or whether, the technology will reach industrial production. The documents say only that the team will advance process scale-up; none gives a timeline or results at larger scale.
- The exact time of the Nature publication. Xinhua and Jiemian give the date as 21 October; China News Service says the night of 21 October, Beijing time.
- Details of the claimed advantages, such as suppression of olefin polymerisation side reactions and easier recovery of the solid catalyst. Only China News Service gives these details, citing the research team.
What local media are saying
Timeline, local time
- Xinhua reports, citing the Chinese Academy of Sciences, on the new catalytic route (21 October). [ 1 ]
- China News Service reports the work, saying the Nature paper went online on the night of 21 October. [ 2 ]
- Yicai publishes a short item on the result (21 October). [ 3 ]
- Jiemian publishes an item crediting CCTV News (21 October). [ 4 ]
- 36Kr publishes a summary crediting CCTV News (22 October). [ 5 ]