近日，能源催化转化全国重点实验室能源与环境小分子催化研究中心（509组群）邓德会研究员、于良研究员和黄瑞研究员团队在氮气（N2）与甲烷（CH4）直接合成高值C-N-O化合物领域取得新进展。团队设计了低温等离子体（NTP）驱动自由基级联反应系统，在室温（25 oC）、常压（0.1 MPa）的温和条件下，实现了N2、CH4与环己酮直接合成高附加值氰醇化合物，并联产氨气（NH3）。该过程避免了传统的高能耗、高碳排放及剧毒中间体问题，为短流程、绿色化、高选择性制备C-N-O化学品提供了新途径。

Recently, the team led by Researcher Deng Dehui, Researcher Yu Liang, and Researcher Huang Rui from the Energy and Environmental Small Molecule Catalytic Research Center of the National Key Laboratory of Energy Catalytic Conversion (Group 509) has made new progress in the direct synthesis of high-value C-N-O compounds from nitrogen (N2) and methane (CH4). The team designed a low-temperature plasma (NTP) driven free radical cascade reaction system, achieving the direct synthesis of high-value cyanol compounds from N2, CH4 and cyclohexanone under mild conditions of room temperature (25 °C) and normal pressure (0.1 MPa), and simultaneously producing ammonia (NH3). This process avoids the traditional problems of high energy consumption, high carbon emissions and highly toxic intermediates, providing a new approach for the short process, green and highly selective preparation of C-N-O chemicals.

氰醇是同时含有醇羟基与氰基的多官能团化合物，广泛用于合成抗抑郁、抗病毒药物，也是工程塑料的重要工业原料。传统氰醇生产工艺通常需经历复杂的多步过程： Haber-Bosch过程（450 °C、20 MPa）合成氨、Andrussow过程（>1000 °C）将氨与CH4转化成氢氰酸、氢氰酸与酮反应制得氰醇。该路线流程长、能耗高、原子经济性差，且伴随较高碳排放。在温和条件下将N2和CH4共转化并偶合酮类底物一步法直接制备氰醇，是缩短流程、降本增效并规避剧毒氢氰酸使用的可持续发展路线，但面临N2和CH4均为惰性小分子，难以在温和条件下同时高效活化和转化，以及氰基生成及其与酮的选择性偶联不易控制等难题。

Cyanohydrin is a multi-functional compound that contains both alcohol hydroxyl groups and cyanide groups. It is widely used in the synthesis of antidepressants and antiviral drugs, and is also an important industrial raw material for engineering plastics. The traditional cyanohydrin production process usually involves a complex multi-step procedure: the Haber-Bosch process (450 °C, 20 MPa) for synthesizing ammonia, the Andrussow process (>1000 °C) for converting ammonia and CH4 into hydrogen cyanide, and the reaction of hydrogen cyanide with ketones to obtain cyanohydrin. This route has a long process, high energy consumption, poor atomic economy, and accompanied by high carbon emissions. The one-step direct preparation of cyanohydrin from N2 and CH4 in a mild condition and coupling with ketone substrates is a sustainable development route that shortens the process, reduces costs, and avoids the use of highly toxic hydrogen cyanide. However, it faces difficulties such as the fact that both N2 and CH4 are inert small molecules, making it difficult to simultaneously and efficiently activate and convert them under mild conditions, as well as the difficulty in controlling the formation of the cyanide group and its selective coupling with the ketone.

邓德会团队长期致力于能源与环境小分子的催化转化研究，前期在N2和CH4等惰性小分子催化转化方面取得了系列进展（Nat. Synth.，2024；Nat. Catal.，2023；Natl. Sci. Rev.，2022；Chem，2026；J. Am. Chem. Soc.，2026；J. Am. Chem. Soc.，2025；J. Am. Chem. Soc.，2025；J. Am. Chem. Soc.，2024；Nat. Commun.，2025）。本工作针对上述挑战，提出了一条基于自由基级联反应机制的合成新路线：利用低温等离子体激发气相N2和CH4，产生N2激发态和甲基自由基（·CH3）、氢自由基（·H）等活性物种，进一步与环己酮底物直接反应，在室温常压下实现了多官能团环己酮氰醇的高效合成。

Deng Dehui's team has been dedicated to the research on catalytic conversion of energy and environmental small molecules for a long time. In the early stage, they made a series of progress in the catalytic conversion of inert small molecules such as N2 and CH4 (Nat. Synth., 2024; Nat. Catal., 2023; Natl. Sci. Rev., 2022; Chem, 2026; J. Am. Chem. Soc., 2026; J. Am. Chem. Soc., 2025; J. Am. Chem. Soc., 2025; J. Am. Chem. Soc., 2024; Nat. Commun., 2025). This work addresses the aforementioned challenges and proposes a new synthetic route based on the radical cascade reaction mechanism: using low-temperature plasma to excite gaseous N2 and CH4, generating N2 excited states and methyl radicals (·CH3), hydrogen radicals (·H), and other reactive species, and further reacting with the cyclohexanone substrate directly, achieving the efficient synthesis of multi-functional group cyclohexanone cyanol at room temperature and normal pressure.

环己酮氰醇的选择性达95.8%，收率为23.9%，生成速率为0.60 mmol h-1。研究团队结合自主搭建的等离子体耦合原位分子束质谱等监测手段与理论计算，揭示了自由基级联反应机制：等离子体激发产生的活性·H与环己酮羰基反应生成环己醇自由基，随后与·CH3发生C-C偶联；该中间体进一步脱氢形成的亚甲基自由基与激发态N2发生C-N偶联，进而被·H加氢并断裂N≡N断键，最终生成环己酮氰醇，并联产高附加值NH3。该路线可拓展至其他酮类底物，实现氰醇类化合物的定制化合成。该工作建立了一条直接利用N2和CH4一步高选择性合成氰醇类化合物的绿色反应新路径，为惰性小分子在温和条件下直接高效利用提供了新思路。

The selectivity of cyclohexanone cyanohydrin reached 95.8%, the yield was 23.9%, and the generation rate was 0.60 mmol h-1. The research team combined the monitoring methods such as plasma-coupled in situ molecular beam mass spectrometry that they independently developed with theoretical calculations to reveal the free radical cascade reaction mechanism: The reactive ·H generated by plasma excitation reacted with the carbonyl group of cyclohexanone to form a cyclohexanol radical, which then reacted with ·CH3 for C-C coupling; this intermediate further underwent dehydrogenation to form a methylene radical, which reacted with the excited-state N2 for C-N coupling, and was subsequently hydrogenated by ·H and the N≡N bond was broken, ultimately generating cyclohexanone cyanohydrin, and simultaneously producing high-value-added NH3. This route can be extended to other ketone substrates to achieve customized synthesis of cyanohydrin compounds. This work established a new green reaction path for directly and highly selectively synthesizing cyanohydrin compounds using N2 and CH4, providing a new idea for the direct and efficient utilization of inert small molecules under mild conditions.

相关研究成果以“Direct plasma synthesis of a high-value C-N-O compound with inert N2 and CH4”为题，发表在《自然—合成》（Nature Synthesis）上。上述工作得到国家自然科学基金委“空气主份转化化学”卓越研究群体项目、国家重点研发计划、我所能源催化转化全国重点实验室、我所创新基金等项目的资助。

The relevant research results were titled "Direct plasma synthesis of a high-value C-N-O compound with inert N2 and CH4" and were published in the journal "Nature Synthesis". This work was supported by the National Natural Science Foundation of China's "Air Main Component Transformation Chemistry" Outstanding Research Group Project, the National Key Research and Development Program, the National Key Laboratory of Energy Catalytic Conversion of our institute, and the Innovation Fund of our institute.