Liquid fuel synthesis via CO2 hydrogenation by coupling homogeneous and heterogeneous catalysis

•CO2 hydrogenation by coupling homogeneous and heterogeneous catalysis•The reaction is conducted at low temperature with high C5+ selectivity•The activity comparable to that of the reported Ru0-catalyzed FTS CO2 a major greenhouse gas, as well cheap, nontoxic, renewable C1 resource. As clean reductant, H2 can be produced from water energy, such wind, hydro, solar energy. Production liquid fuel promising route solve ever-increasing environmental social challenges society. This usually proceeds through two consecutive reactions accelerated catalysts. Because thermodynamic limitations cascade reactions, catalysts suffer selectivity. To overcome barrier current technology, we coupled catalysis in promoting respectively, outstanding results were achieved. Synthesis (C5+ hydrocarbons) via generally involves reverse gas shift (RWGS) Fischer-Tropsch synthesis (FTS) over (above 300°C) Here, report production RuCl3 Ru0 catalysts, which proceeded lowest so far (180°C) reached highest selectivity date (71.1%). The TOF 9.5 h?1, catalyzed using syngas. Detailed study indicates synergy key for performance. Transformation into value-added chemicals great importance sustainable society.1He M. Sun Y. Han B. Green carbon science: scientific basis integrating resource processing, utilization, recycling.Angew. Chem. Int. Ed. Engl. 2013; 52: 9620-9633Crossref PubMed Scopus (558) Google Scholar, 2Artz J. Müller T.E. Thenert K. Kleinekorte Meys R. Sternberg A. Bardow Leitner W. Sustainable conversion dioxide: an integrated review life cycle assessment.Chem. Rev. 2018; 118: 434-504Crossref (882) 3Liu Q. Wu L. Jackstell Beller Using dioxide building block organic synthesis.Nat. Commun. 2015; 6: 5933Crossref (1202) 4Aresta Carbon Dioxide Chemical Feedstock. 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(C5-C28 n-paraffins) reach 71.1%, previously. turnover frequency (TOF) best level catalyst. all n-paraffins, has not before hydrogenation. know, first work combine produce Ru (Ru0) prepared simple reduction NaBH4 water. particles dispersed size about 3–5 nm (Figures S1 S2). N2 adsorption test indicated Brunauer–Emmett–Teller surface area 5.6 m2/g S3). X-ray diffraction (XRD), photoelectron spectroscopy (XPS) absorption fine structure (XAFS) data coincided S4–S6). find suitable screened different systems proceed efficiently RuCl3/Ru0 promoter solvent 180°C (entry C5-C28 confirmed GC-MS (Agilent-7890B-5977A), comparing retention times standards chromatography (GC) traces S7 S8). n-paraffins product 71.1 C-mol %, CO/H2 monometallic nanocatalyst.28Xiao C.X. Z.P. Kou Yan Aqueous-phase ruthenium nanocluster catalyst.Angew. 2008; 47: 746-749Crossref (168) Ru-based CO,28Xiao 29Li W.-Z. J.-X. Gu S.-Y. Si Su H.-Y. C.-H. 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Interestingly, totally no or other byproduct observed. hydrogenation, contained various kinds compounds, olefins, aromatics, CO, branched paraffins, naphthene, and/or oxygenates.18He chain length paraffins followed statistics, growth probability (?) 0.83, agreed fact longer chains work.Table 1Hydrogenation systemsEntryCatalystCo-catalystPromoterSolventSelectivity (C-mol %)TOFaTOF denotes moles consumption per mole hour. (h-1)COC1-4C5+CH3OH1bThe CH4 17.5 C2-4 11.4 %.RuCl3, Ru0LiClLiINMP028.971.109.52Ru0--NMP0100.0003.63Ru0LiClLiINMP0100.0004.34RuCl3--NMP0100.00025.35cThe solution after transparent clear, indicating reaction.RuCl3LiClLiINMP84.810.205.0122.86RuCl3, Ru0--NMP0100.0003.77RuCl3, Ru0LiCl-NMP091.98.107.98RuCl3, Ru0-LiINMP0100.0006.69RuBr3, Ru0LiClLiINMP043.156.906.910RuI3, Ru0LiClLiINMP076.923.106.811Ru2(CO)6Cl4, Ru0LiClLiINMP034.066.007.912Ru3(CO)12, Ru0LiClLiINMP052.847.206.413RuCl3, Ru0NaClLiINMP066.833.206.014RuCl3, Ru0KClLiINMP075.324.701.915RuCl3, Ru0AlCl3LiINMP084.016.001.316RuCl3, Ru0[Bmim]ClLiINMP58.321.020.707.517RuCl3, Ru0LiBrLiINMP042.957.108.318RuCl3, Ru0LiBF4LiINMP092.17.901.519RuCl3, Ru0LiClNaINMP047.352.707.820RuCl3, Ru0LiClKINMP062.337.706.721RuCl3, Ru0LiClLiBrNMP065.334.709.822RuCl3, Ru0LiClLiIDMI040.659.405.223RuCl3, Ru0LiClLiIToluene0100.0000.224RuCl3, Ru0LiClLiISqualane084.915.100.425RuCl3, Ru0LiClLiIH2O0100.0000.226dCO2 replaced MPa CO.Ru0--NMP-23.476.603.127cThe reaction.RuCl3LiCl-NMP61.814.6023.6110.728cThe reaction.RuCl3-LiINMP81.914.103.980.029dCO2 CO.Ru0LiCl-NMP-7.292.802.230dCO2 CO.Ru0-LiINMP-27.572.503.431dCO2 CO.Ru0LiClLiINMP-19.480.602.432cThe reaction.,dCO2 CO.RuCl3LiClLiINMP-25.0075.014.733dCO2 CO.,e50 ?L added system.Ru0LiClLiINMP-67.432.6-1.0Reaction conditions: 3 ?mol 37 (based metal), 0.75 mmol cocatalyst, 0.4 mL 5 (at room temperature), 180 oC, 12 h.a hour.b %.c reaction.d CO.e 50 system. Open table tab Reaction h. Both necessary When it only methane (entries 2, 3). situ reduced H2, sole formed 4). together RuCl3, very rate 5). suggesting reaction. photos solutions given S9. binary lithium halides required halide, detected 6). reaction, increased minor 7). acted RuCl3/Ru0. 6, 8), RuCl3/Ru0/LiCl, considerably 1, Hence target Based Ru0/LiCl/LiI, tested precursors i.e., RuBr3, RuI3, Ru2(CO)6Cl4, Ru3(CO)12. order: RuCl3> RuBr3> RuI3 9, 10). showed Cl? ligand eminent further verified control Ru2(CO)6Cl4 Ru3(CO)12, respectively 11, 12). We tried cations (Na+, K+, Al3+, [Bmim]+) anions (Br-, BF4-), most appropriate 13–18). promoters (NaI, KI, LiBr), demonstrated 19–21). cocatalysts promoters, Li+ proved cationic species. cation became larger, both decreased evidently 13–15, 19, 20). crucial 1,3-dimethyl-2-imidazolidinone (DMI), squalane, toluene, water, possess molecular structure, solubility, physico-chemical properties. For example, DMI similar NMP, squalane property products, toluene aromatic compound dissolve common proton solvent. After screening solvents, found NMP effective 22–25). weak Lewis base, stabilize absorb acidic CO2.34Gholami Azizi Peyghambarzadeh S.M. Bohloul M.R. modelling experimental diffusion coefficient N-methyl pyrolidone.Sep. Technol. 2435-2442Crossref (3) would like mention observed bases, triethylamine, dimethyl formamide (DMF), pyridine, solvents. organometallic even small modification cause large change pattern processes solution.35Gutmann Solvent effects reactivities compounds.Coord. 1976; 18: 225-255Crossref (772) cyclic amide, DMI, simultaneously facilitate C-C bond formation.36Wang Asare Efficient ethanol temperature.Green 589-596Crossref word, consisted RuCl3/Ru0/LiCl/LiI optimized system, studied impact pressure dosage At fixed ratio (1/1), elevating 4 10 1–4). less sensitive CO2/H2 affected optimal 1/1 4, did take place, took part 8, 9). results. 40 ?mol, 3/37 10–12). ratio, 13, 14). short, temperature) dosages Ru0. 3A demonstrates LiCl, produced. increase dosage, optimal. 3B). halogen ligands transition catalysis. inhibition too attributed occupation active excess I?. 3C illustrates 120°C, (> 80%), amount (about 5%) paraffin rose dramatically increasing % h?1. Beyond minor. Thus, 180°C. time course 3D. appeared rapidly beginning speed, then generated steady rate. With passing time, consumed, continuously. h, up, %. obviously, slower washed acetone dried vacuum oven 50°C directly next run. recycling revealed cycles S10). transmission electron microscopy (TEM), scanning (STEM), XRD, XPS, XAFS characterizations particle size, crystal alter obviously during S1, S2, stably catalyze gaseous sample released, determined GC. removed 70°C, reactant recharged start had obvious decrease S11). stability determining contents components (cationic Ru, Li+, Cl?, I?) presence halides, promote CO. although catalyst.28Xiao Scholar,29Li Inspired this, remarkable entry 26). These that, work, pathway 3D). scheme 4. trace began form 1 induction period comparison, time. electrospray ionization mass spectrometry (ESI-MS) immediately converted carboyl halide kept S12). Nearly operated reactors.25Su Scholar,26Dry lies elegant reactor. Synergy success work. 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