Identification of different carbenium ion intermediates in zeolites with identical chabazite topology via13C–13C through-bond NMR correlations

13C–13C through-bond NMR correlation experiments reveal the stabilization of different carbenium ion intermediates in two zeolites possessing identical CHA topology (H-SAPO-34 and H-SSZ-13) during the methanol to olefins reaction.

The production of light olens via the methanol-to-olens (MTO) reaction is an important chemical process that links non-oil resources such as coal and natural gas with olen-based petrochemicals. 1-5 The catalysts used for the MTO reaction are mainly microporous acidic zeolites amongst which H-SAPO-34, a silicoaluminophosphate zeolite with the chabazite (CHA) topology, is of particular importance due to its high selectivity to ethylene and propene, and is of commercial use. 1,3 H-SSZ-13 is a CHA silicoaluminate analogue of H-SAPO-34 which has been shown to be a potential alternative in the MTO process. 6 Despite the successful industrialization of this process with methanol conversion higher than 99%, 3 further improving of the catalyst performances in terms of selectivity has been an important scientic endeavor. For example, the selectivity to ethylene and propene has increased from 79.2% in the rst generation industrial DMTO process ("D" refers to Dalian Institute of Chemical Physics) to 85.7% in the second generation DMTO-II process in China. 3 However, there is still signicant room to improve catalysts performances which can be informed by providing a deeper understanding of the catalytic reaction intermediates and reaction mechanism.
We and others have previously investigated the MTO mechanism on H-ZSM-5, 7-10 H-SAPO-34 11-14 b zeolite 15,16 using a range of experimental and computational approaches including solidstate Nuclear Magnetic Resonance (NMR). The hydrocarbon pool (HCP) mechanism has been generally accepted for the formation of hydrocarbons from methanol 5,11,12,17,18 and suggests that for the aromatic cycle routes the organic species (mainly cyclic carbenium ions and neutral aromatic species) conned in the pores of zeolites act as co-catalysts with the inorganic framework. Based on the species observed, a sidechain and a paring reaction pathways have been proposed. While the former involves olens released through methylation of six-membered ring cations (alkylbenzenium) and elimination of the side chain groups, the later route produces the olens via expansion of alkylcyclopentenyl cations followed by contraction of the formed six-membered ring cations. 14,15,19 These cyclic carbenium ions are key nodes along the reaction routes and their identication plays an important role in determining the mechanism acting for a given zeolite.
Solid-state NMR has played a critical role in achieving this understanding 8,14,20,21 and our recent works 10,16 deploying a range of multidimensional and multinuclear NMR approaches have enabled the unequivocal structural identication of a range of veand six-membered ring cations (as well as neutral compounds) in H-ZSM-5 and b-zeolites (MFI and BEA topologies, respectively), without the need for previous knowledge or assumption of the carbenium ions structures. In particular, this approach permits to distinguish carbenium ions with closely related structures (e.g., cyclopentenyl cations with various methyl groups) and previously unidentied carbenium ions (e.g., 1,5-dimethyl-3-sec-butyl cyclopentenyl cation and methylnaphthalenium cations), all offering a complete understanding of the reaction routes.
Here, we probe the carbenium ions formed during the MTO reaction on two different CHA zeolites (H-SSZ-13 and H-SAPO-34) by utilizing the 2D 13 C-13 C refocused INADEQUATE (Incredible Natural Abundance DoublE QUAntum Transfer Experiment) 22 NMR experiment (pulse sequence in Fig. S1 in the ESI †). We experimentally identied 1,2,3,4-tetramethylcyclopentenyl(I) and 1,2,3-trimethylcyclopentenyl(II) cations as the major retained cation species on H-SSZ-13 and H-SAPO-34 CHA zeolites, respectively. Activated zeolites were prepared by owing 13 C enriched CH 3 OH on H-SSZ-13 and H-SAPO-34 catalyst beds at 275 C for 25 min and 300 C for 20 min, respectively, followed by quenching into liquid N 2 to capture the carbenium ion intermediates (full experimental details are given in the ESI †). The 13 C CP (Cross Polarisation) MAS (Magic Angle Spinning) NMR spectra of these two activated catalysts are given in Fig. 1 and show multiple signals in the 0-260 ppm region, highlighting the complexity of the retained carbon species. Three general type of species (carbenium ions, aromatics/dienes, adamantane derivatives, see ESI †) are present, the downeld signals above 150 ppm being characteristic of carbenium ions. 8,10,14,16,21 It is worth pointing out that the 13 C spectra of activated H-SSZ-13 and H-SAPO-34 are very similar in this high frequency region; the two main peaks at about 153 and 243 ppm are representative signals for polymethylcyclopentenyl cations. 8,14,20,21 These 1D NMR spectra would suggest that the same cations are retained on these two zeolites with identical CHA topology, however the more informative 2D through-bond 13 C-13 C correlation NMR experiment 22 reveals that this is not the case (see below).
The corresponding 2D 13 C-13 C refocused INADEQUATE spectra of both activated zeolites are shown in Fig. 2. These experiments are based on through-bond scalar J coupling 22 (rather than through-space dipolar-based experiments) 23,24 and the correlation maps directly yield C-C bonds information, unambiguously enabling assignment of the carbon resonances. In this experiment, two peaks resonating at the same frequency in the double quantum (vertical) dimension arise from the sum frequency of the two individual 13 C peaks in the single quantum (horizontal) dimension that correspond to chemically bonded carbons. The 2D spectra of the two activated zeolites show that the 13 C-13 C correlation maps are distinct as evidenced by correlations of the 63 and 243 ppm signals in H-SSZ-13 and of the 47 and 244 ppm peaks in H-SAPO-34 (see red and blue traces in Fig. 2), demonstrating that the main carbenium ions formed are different in both zeolites with the same CHA topology. The full maps are also shown in the 2D spectra and reveal experimental observation of the characteristic correlations C1(I) (243 ppm)-C2(I) (153 ppm) and C2(I) (153 ppm)-C3(I) (251 ppm) identifying cation I as the main retained cation species in H-SSZ-13 (Fig. 2a) and C1,3(II) (244 ppm)-C2(II) (155 ppm) and C1,3(II) (244 ppm)-C4,5(II) (47 ppm) for cation II in H-SAPO-34 ( Fig. 2b and S4-S6 † for complete set of correlations for each cation), allowing the structure of the carbenium ions and their 13 C chemical shis to be explicitly obtained ( Table 1).
Note that the tetramethyl substituted cyclopentenyl cation I has not been observed in the literature. 8,10,14,21,25,26 While trimethyl substituted cyclopentenyl II has been previously postulated in a previous study on H-SAPO-34 (ref. 27) based solely on 1D 13 C spectra, it is worth pointing out that the 2D NMR method adopted here yields C-C bonding information directly, providing straightforward structural identication not accessible using methods that require treatment of post-activated zeolites. 8,14,26,28 Additional correlations involving 13 C signals in the high frequency range (175 to 250 ppm) are also observed (maroon lines in Fig. 2 and S7 †). The correlations between signals at 30-215 ppm in H-SSZ-13 and 30-225 ppm in H-SAPO-34 are assigned to polymethylcyclohexenyl cations. 10,27,29 In H-SAPO-34, the 247 ppm resonance shows multiple correlations involving carbenium ions which are most likely other cyclopentenyl cations. 8,14,26 However, only a limited number of correlations is obtained, due to their low concentration as evidenced by their weak 1D signal intensities (Fig. 1), and challenges a complete structural determination for these cations. In H-SSZ-13, there is a unique correlation between signals at 20 and 175 ppm and is characteristic of methylnaphthalenium cations, 16 the formation of this coke precursor being ascribed to the higher acid strength of H-SSZ-13 than H-SAPO-34 (as determined by infrared spectroscopy studies 6,30 and a combination of 1 H NMR, acetone probed 13 C NMR and NH 3 -temperature programmed desorption methods). 14 The signals in the 190-203 ppm region in the 1D spectra of both zeolites (Fig. 1, S2 and S3 †) arise from polymethylbenzenium cations 14 but are absent in the 2D spectra likely due to their very low concentration too.
Whilst CP MAS-based experiments like the refocused INAD-EQUATE are inherently not quantitative, the similar natures of the carbenium ions stabilized permit some consideration regarding the main species present. It is found that I dominates the 2D spectrum in H-SSZ-13 while it is a minor retained cation species in H-SAPO-34 where II is the main cation. Note that only a few characteristic correlations corresponding to I has been detected in the later zeolite (e.g., C4(I)-C5(I) and C4(I)-C9(I), as shown in Fig. 2b and S6 †) as the others are likely beyond the detection limit of the 2D experiment. The difference in population of the main carbenium ions I and II present in these two zeolites probably arises from their different acid strengths. It is known that whether or not a carbenium ion could be persistently stabilized inside zeolites depends on its acid strength relative to that of the zeolites. 14,31-33 The distribution of carbenium ions in H-SSZ-13 vs. H-SAPO-34 may suggest that I is less stable than II and requires stronger acid sites to be stabilized.
The observation of the ve-membered ring cations I and II is also strong indication of the existence of paring route in zeolites of CHA topology. It is clear that the ve-membered ring cations are the main retained carbenium ion intermediates in both H-SSZ-13 and H-SAPO-34, while the six-membered ring cations are only present as minor species. This result is consistent with previous observation 14 showing that six-membered ring cations have higher activity and further transform and are therefore less likely to be observed than the ve-membered ring cations in the CHA zeolites.
In addition to carbenium species, neutral aromatics and dienes are present (correlated signals in the 115-150 ppm and 10-25 ppm regions, green dashed boxes and lines in Fig. 2 and S8 †) and are involved as HCP species in the catalytic cycles and precursors of carbenium ions, respectively. 27 Correlations in the 10-50 ppm region (purple dashed boxes in Fig. 2 and S8 †) are assigned to alkyl groups (in aromatics and carbenium ions) and methyladamantanes, the later being consistent with gas chromatographymass spectrometry experiments performed on CHA zeolites and suggested as coke species leading to catalyst deactivation. 34 A correlation between signals at 77 and 28 ppm (purple lines in Fig. 2 and S8 †) is also obtained on both zeolites and likely arises from hydroxy and methoxy substituted adamantanes. 35 Note that the poor resolution of the 2D spectra in these regions hinders complete assignments of the neutral species mentioned above. Finally, signals at 50 and 60 ppm do  not display 2D correlations which is consistent with their assignments to strongly adsorbed methanol and dimethyl ether, respectively. 8,10 In conclusion, we have explicitly obtained the molecular structures of the reactive carbenium ions in two zeolites with identical CHA topology using multidimensional through-bond NMR experiments. New types of polymethylcyclopentenyl cations are identied and may serve as crucial intermediates in the paring route for MTO reaction. The new cations identied here offer a more comprehensive understanding of the reaction routes and will inspire future researches on their roles in MTO processes.

Conflicts of interest
There are no conicts of interest to declare.