Dual catalysis by homogeneous/heterogeneous ruthenium species

In this Chem issue, Han et al. devised a system relying on tandem heterogeneous and homogeneous catalysis by ruthenium species for the CO2 hydrogenation to hydrocarbons with remarkable efficiency. particular, 5-atom (or longer) chain were obtained remarkably high selectivity (71.1%). For many years, distinction between has been clear, two separated fields have mostly evolved along parallel pathways, taken forward key experts specific competences. However, such clear-cut of areas always felt somehow preposterous, because both share common ground challenges, attempting unravel steer reaction mechanisms control metal coordination and/or environment. Moreover, homo/hetero often does not find truly justification, as in catalytic reactions nature active site is uncertain. Just an example, well-known Suzuki-Miyaura C–C coupling Pd, was greatly debated past, still today there no irrefutable consensus whether catalyzed Pd complex, nanoparticles formed situ, or species.1Beletskaya I.P. Alonso F. Tyurin V. The after Nobel prize.Coord. Chem. Rev. 2019; 385: 137-173Crossref Scopus (145) Google Scholar New research trends reassessed versus approaches, incorporating concepts into development single “catalytic ensembles,” whereby cycle relies action task-specific phases.2Liu Y.-Y. Liang D. Lu L.-Q. Xiao W.-J. Practical photoredox/nickel dual C-N C-O reactions.Chem. Commun. (Camb.). 55: 4853-4856Crossref PubMed resultant synergy paves way allowing important chemical conversions higher efficiency, recent article, it chance that chose yin yang symbol graphically represent core their work, symbolizing independent (and sometimes divergent) approaches can complement each other toward ambitious processes. article targets realization one great challenges reactions, namely transformation chemicals liquid fuels.3Vogt C. Monai M. Kramer G.J. Weckhuysen B.M. renaissance Sabatier its applications Earth space.Nat. Catal. 2: 188-197Crossref (169) Here, conversion various lengths realized recurring double catalyst: RuCl3, being converted situ corresponding Ru carbonyl iodide able convert CO under mild conditions presence Li halogenides (LiCl used cocatalyst LiI promoter). Sequentially, as-formed undergoes Fischer-Tropsch CnH2n+2 products Ru(0) nanoparticles, achieving (C5+ paraffines) more than 70% yield reactor.4Cui Qian Q. Zhang J. Wang Y. Asare Bediako B.B. Liu H. B. Liquid fuel synthesis via catalysis.Chem. 2020; 7https://doi.org/10.1016/j.chempr.2020.12.005Abstract Full Text PDF (8) work ingenious making hydrocarbons, recognizing conventional hinders production hydrocarbons. To overcome limitation, examples bifunctional catalysts developed years transform MeOH, followed FT methanol-to-olefin steps (MTO). contact state functionalities pivotal activity, selectivity, even stability catalysts.5Gao P. S. Bu X. Dang Z. Zhong L. Qiu Yang Cai al.Direct fuels over catalyst.Nat. 2017; 9: 1019-1024Crossref (463) present contribution al., utilization package featuring allows operate at considerably milder improved yields, will be demonstration huge potential combining these catalysis, which hold unlock new technologies.6Cui W. Ryabchuk Junge K. Beller Bridging single-metal-site catalysts.Nat. 2018; 1: 385-397Crossref (383) raises scientific questions: what mechanism yields performance? What fate catalyst conditions? exact role Li+? More precisely, intervene both)? MeOH formation reported detrimental reaction:7Monai Melchionna Fornasiero From metal-free catalysts: Routes sustainable chemistry.in: Advances Catalysis. Volume 63. Academic Press, 2018: 1-73Google formed? While fascinating provides insights very modern process, also opens several doors further deepen our understanding process inspire combined homogeneous/heterogeneous conversion. short, run, answer some above questions may rely use operando spectroscopy techniques, are becoming ubiquitous example electrocatalysis.8Carbonio E.A. Velasco-Velez J.-J. Schlögl R. Knop-Gericke A. Perspective—outlook photoelectron absorption probe solid-liquid electrochemical Interface.J. Electrochem. Soc. 167: 054509Crossref (13) A second question how findings extended complexes/heterogeneous combinations, order replace risk metals renewable alternatives e.g., Na Ni, while retaining similar performances. Mechanistic theoretical modeling help lead way, noting frontier methodologies join experimental efforts upgrading developing existing catalysts.9Seh Z.W. Kibsgaard Dickens C.F. Chorkendorff I. Nørskov J.K. Jaramillo T.F. Combining theory experiment electrocatalysis: Insights materials design.Science. 355https://doi.org/10.1126/science.aad4998Crossref (4165) Scholar, 10Mateo Cerrillo J.L. Durini Gascon Fundamentals photo-thermal 2021; 50: 2173-2210Crossref 11Neese High-level spectroscopy, quantum chemistry, catalysis: just passing fad.Angew. Int. Ed. 56: 11003-11010Crossref (21) Hence, apart from notable results practical point view, invention based transformation, relevant powerful rational unification kept too long separated, holds solutions. We expect rapid flourishing forthcoming contemporary holistic) philosophy setting state-of-the-art catalysis. catalysisCui al.ChemDecember 30, 2020In BriefLiquid high-efficiently produced RuCl3-catalyzed RWGS Ru0-accelerated FTS reaction. proceeded lowest temperature so far reached highest C5+ date. TOF comparable Ru0-catalyzed using syngas. outstanding lie elegant components reactions. Full-Text Open Archive