Rommens, K. T. & Saeys, M. Molecular views on Fischer–Tropsch synthesis. Chem. Rev. 123, 5798–5858 (2023).
Google Scholar
Lin, T. et al. Cobalt carbide nanocatalysts for efficient syngas conversion to value-added chemicals with high selectivity. Acc. Chem. Res. 54, 1961–1971 (2021).
Google Scholar
Pan, X., Jiao, F., Miao, D. & Bao, X. Oxide–zeolite-based composite catalyst concept that enables syngas chemistry beyond Fischer–Tropsch synthesis. Chem. Rev. 121, 6588–6609 (2021).
Google Scholar
Zhou, W. et al. New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO2 into hydrocarbon chemicals and fuels. Chem. Soc. Rev. 48, 3193–3228 (2019).
Google Scholar
Zhong, L. et al. Cobalt carbide nanoprisms for direct production of lower olefins from syngas. Nature 538, 84–87 (2016).
Google Scholar
Fang, W. et al. Physical mixing of a catalyst and a hydrophobic polymer promotes CO hydrogenation through dehydration. Science 377, 406–410 (2022).
Google Scholar
Cheng, K. et al. Direct and highly selective conversion of synthesis gas into lower olefins: design of a bifunctional catalyst combining methanol synthesis and carbon–carbon coupling. Angew. Chem. Int. Ed. 55, 4725–4728 (2016).
Google Scholar
Jiao, F. et al. Selective conversion of syngas to light olefins. Science 351, 1065–1068 (2016).
Google Scholar
Su, J. et al. Syngas to light olefins conversion with high olefin/paraffin ratio using ZnCrOx/AlPO-18 bifunctional catalysts. Nat. Commun. 10, 1297 (2019).
Google Scholar
Su, J. et al. Unveiling the anti-trap effect for bridging intermediates on ZnAlOx/AlPO-18 bifunctional catalysts to boost syngas to olefin conversion. ACS Catal. 13, 2472–2481 (2023).
Google Scholar
Ding, Y. et al. Effects of proximity-dependent metal migration on bifunctional composites catalyzed syngas to olefins. ACS Catal. 11, 9729–9737 (2021).
Google Scholar
Li, N. et al. Steering the reaction pathway of syngas-to-light olefins with coordination unsaturated sites of ZnGaOx spinel. Nat. Commun. 13, 2742 (2022).
Google Scholar
Bai, B. et al. Tuning the crystal phase to form MnGaOx-spinel for highly efficient syngas to light olefins. Angew. Chem. Int. Ed. 62, e202217701 (2023).
Google Scholar
Chen, Y. et al. Visualization of the active sites of zinc–chromium oxides and the CO/H2 activation mechanism in direct syngas conversion. J. Am. Chem. Soc. 146, 1887–1893 (2024).
Google Scholar
Liu, X. et al. Tandem catalysis for hydrogenation of CO and CO2 to lower olefins with bifunctional catalysts composed of spinel oxide and SAPO-34. ACS Catal. 10, 8303–8314 (2020).
Google Scholar
Jiao, F. et al. Disentangling the activity-selectivity trade-off in catalytic conversion of syngas to light olefins. Science 380, 727–730 (2023).
Google Scholar
Torres Galvis, H. M. et al. Supported iron nanoparticles as catalysts for sustainable production of lower olefins. Science 335, 835–838 (2012).
Google Scholar
Xu, Y. et al. A hydrophobic FeMn@Si catalyst increases olefins from syngas by suppressing C1 by-products. Science 371, 610–613 (2021).
Google Scholar
Wang, C. et al. Fischer–Tropsch synthesis to olefins boosted by MFI zeolite nanosheets. Nat. Nanotechnol. 17, 714–720 (2022).
Google Scholar
Cai, Y. et al. Trace-level halogen blocks CO2 emission in Fischer-Tropsch synthesis for olefins production. Science 390, 516–520 (2025).
Google Scholar
Gao, C. et al. Conversion of syngas into olefins with high hydrogen atom economy. Science 390, eaea0774 (2025).
Google Scholar
Wang, P. et al. Efficient conversion of syngas to linear α-olefins by phase-pure χ-Fe5C2. Nature 635, 102–107 (2024).
Google Scholar
Xie, J. et al. Promoted cobalt metal catalysts suitable for the production of lower olefins from natural gas. Nat. Commun. 10, 167 (2019).
Google Scholar
Lyu, S. et al. Cobalt clusters decorated CoxMn1−xO nanocomposites for improving the efficiency of syngas to lower olefins with lower CO2 emission. Appl. Catal. B Environ. 325, 122347 (2023).
Google Scholar
Li, X. et al. Characterization and catalytic behavior of Fischer–Tropsch catalysts derived from different cobalt precursors. Catal. Today 338, 40–51 (2019).
Google Scholar
Rahmati, M., Safdari, M.-S., Fletcher, T. H., Argyle, M. D. & Bartholomew, C. H. Chemical and thermal sintering of supported metals with emphasis on cobalt catalysts during Fischer–Tropsch synthesis. Chem. Rev. 120, 4455–4533 (2020).
Google Scholar
Wolf, M., Fischer, N. & Claeys, M. Formation of metal-support compounds in cobalt-based Fischer–Tropsch synthesis: a review. Chem. Catal. 1, 1014–1041 (2021).
Google Scholar
Liu, S. et al. The role of intermediate CoxMn1–xO (x = 0.6–0.85) nanocrystals in the formation of active species for the direct production of lower olefins from syngas. Chem. Commun. 55, 6595–6598 (2019).
Google Scholar
Ojeda, M. et al. CO activation pathways and the mechanism of Fischer–Tropsch synthesis. J. Catal. 272, 287–297 (2010).
Google Scholar
Gunasooriya, G. T. K. K., van Bavel, A. P., Kuipers, H. P. C. E. & Saeys, M. Key role of surface hydroxyl groups in C–O activation during Fischer–Tropsch synthesis. ACS Catal. 6, 3660–3664 (2016).
Google Scholar
Foppa, L., Copéret, C. & Comas-Vives, A. Increased back-bonding explains step-edge reactivity and particle size effect for CO activation on Ru nanoparticles. J. Am. Chem. Soc. 138, 16655–16668 (2016).
Google Scholar
Ge, Q. & Neurock, M. Adsorption and activation of CO over flat and stepped Co surfaces: a first principles analysis. J. Phys. Chem. B 110, 15368–15380 (2006).
Google Scholar
Li, Z. et al. Effects of sodium on the catalytic performance of CoMn catalysts for Fischer–Tropsch to olefin reactions. ACS Catal. 7, 3622–3631 (2017).
Google Scholar
Biesinger, M. C. et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf. Sci. 257, 2717–2730 (2011).
Google Scholar
Fujiwara, M., Matsushita, T. & Ikeda, S. Evaluation of Mn3s X-ray photoelectron spectroscopy for characterization of manganese complexes. J. Electron. Spectrosc. Relat. Phenom. 74, 201–206 (1995).
Google Scholar
Xu, J. et al. Multi-physics instrument: total scattering neutron time-of-flight diffractometer at China Spallation Neutron Source. Nucl. Instrum. Methods Phys. Res. A 1013, 165642 (2021).
Google Scholar
Toby, B. H. & Von Dreele, R. B. GSAS-II: the genesis of a modern open-source all purpose crystallography software package. J. Appl. Crystallogr. 46, 544–549 (2013).
Google Scholar
Feng, Z. et al. Asymmetric sites on the ZnZrOx catalyst for promoting formate formation and transformation in CO2 hydrogenation. J. Am. Chem. Soc. 145, 12663–12672 (2023).
Google Scholar
Bellamy, L. J. The Infrared Spectra of Complex Molecules Vol. 2 (Springer, 1980).
Ravel, B. & Newville, M. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).
Zhang, S. et al. Morphological modulation of Co2C by surface-adsorbed species for highly effective low-temperature CO2 reduction. ACS Catal. 12, 8544–8557 (2022).
Google Scholar
Liu, C. et al. Illustrating the fate of methyl radical in photocatalytic methane oxidation over Ag−ZnO by in situ synchrotron radiation photoionization mass spectrometry. Angew. Chem. Int. Ed. 62, e202304352 (2023).
Google Scholar
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Google Scholar
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Google Scholar
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).
Google Scholar
Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).
Google Scholar
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Google Scholar
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).
Google Scholar
Jarzynski, C. Nonequilibrium equality for free energy differences. Phys. Rev. Lett. 78, 2690–2693 (1997).
Google Scholar
Woo, T. K., Margl, P. M., Blöchl, P. E. & Ziegler, T. A combined Car−Parrinello QM/MM implementation for ab initio molecular dynamics simulations of extended systems: application to transition metal catalysis. J. Phys. Chem. B 101, 7877–7880 (1997).
Google Scholar
Sprik, M. & Ciccotti, G. Free energy from constrained molecular dynamics. J. Chem. Phys. 109, 7737–7744 (1998).
Google Scholar
Source:
www.nature.com

