biostudies-literatureZhai STaishan Scholar Project of Shandong ProvinceNatural Science Foundation of Shandong Province (Shandong Provincial Natural Science Foundation)Ministry of Science and Technology of the People's Republic of China (Chinese Ministry of Science and Technology)National Natural Science Foundation of China (National Science Foundation of China)7876https://www.ebi.ac.uk/biostudies/studies/S-EPMC12375053biostudies-literatureUnknown16(1)Selective hydrogenation of CO2 into methanol offers an ideal route for the utilization of greenhouse gas, but it remains a great challenge to be carried out under mild conditions due to the intrinsic chemical stability of CO2. Here, we report sulfur-bridged cooperative molybdenum binuclear sites anchored on covalent triazine frameworks (denoted as Mo-S-Mo/CTF), as highly efficient active sites for CO2 hydrogenation to methanol at room temperature. Under near-ambient conditions (30 °C, 0.9 MPa), Mo-S-Mo/CTF produces methanol with 96% selectivity and a methanol synthesis rate of 21.88 μmol gMoSx-1 h-1. In-situ spectroscopic characterizations combined with theoretical calculations reveal that Mo-S-Mo/CTF favors CO2 hydrogenation into methanol via the formate pathway at room temperature instead of the CO pathway at 150 °C. The cooperation of CO2 activation on one molybdenum site and H2 splitting on the other plays a key role in high catalytic activity. Our work provides a new direction for methanol synthesis at room temperature.Nature communicationsRoom-temperature methanol synthesis via CO₂ hydrogenation catalyzed by cooperative molybdenum centres in covalent triazine frameworks.PMC123750532022YFA150310422308193ZR2020QB056tspd20230601Zhai DRen GZhai SPan YYang LYu TYang CDeng WGong XfalseRoom-temperature methanol synthesis via CO₂ hydrogenation catalyzed by cooperative molybdenum centres in covalent triazine frameworks.Selective hydrogenation of CO2 into methanol offers an ideal route for the utilization of greenhouse gas, but it remains a great challenge to be carried out under mild conditions due to the intrinsic chemical stability of CO2. Here, we report sulfur-bridged cooperative molybdenum binuclear sites anchored on covalent triazine frameworks (denoted as Mo-S-Mo/CTF), as highly efficient active sites for CO2 hydrogenation to methanol at room temperature. Under near-ambient conditions (30 °C, 0.9 MPa), Mo-S-Mo/CTF produces methanol with 96% selectivity and a methanol synthesis rate of 21.88 μmol gMoSx-1 h-1. In-situ spectroscopic characterizations combined with theoretical calculations reveal that Mo-S-Mo/CTF favors CO2 hydrogenation into methanol via the formate pathway at room temperature instead of the CO pathway at 150 °C. The cooperation of CO2 activation on one molybdenum site and H2 splitting on the other plays a key role in high catalytic activity. Our work provides a new direction for methanol synthesis at room temperature.2025-01-01T00:00:00Z2025 Aug2026-05-10T01:49:02.498Z2026-04-08T01:25:05.555ZS-EPMC123750534084949910.1038/s41467-025-63191-x