Nancy G.
Bush
a,
Caitlin H.
Dinh
a,
Casandrah L.
Catterton
a and
Megan E.
Fieser
*ab
aDepartment of Chemistry, University of Southern California, Los Angeles, CA 90089, USA. E-mail: fieser@usc.edu
bWrigley Institute for Environmental Studies, University of Southern California, Los Angeles, CA 90089, USA
First published on 2nd May 2023
Glycolysis is a widely studied method for chemical recycling of polyethylene terephthalate (PET). Metal-containing ionic liquids (MILs) are attractive catalysts for the glycolysis of PET, as they have been shown to have high stability and can be easily recycled. While a range of MILs have been studied with varying cations and metal containing anions, there are no conclusive trends for the different variables in MIL catalyst design and how they affect glycolysis of PET. We report the use of lanthanide MILs to identify which catalyst design variables and reaction conditions can be tuned to make the biggest difference in the deconstruction of PET. Mixtures of ionic liquids (ILs) with lanthanide metal salts were found to lead to homogeneous MIL catalysts that are active for the glycolysis of PET. These studies identified that finding a metal salt and IL combination that leads to a cooperative MIL catalyst was more important than the basicity of the IL or metal salt anion itself. Finally, the high performance of MILs with a high ratio of IL to metal salt lowers the loading of metal salts with supply risk, while maintaining the value of MIL over metal-free IL catalysts.
Sustainability spotlightIonic liquids have been identified as promising catalysts for the glycolysis of poly(ethylene terephthalate) (PET) to its monomer precursor, bis(2-hydroxyethyl)terephthalate (BHET). Metal containing ionic liquids (MILs) have shown increased stability, recyclability and activity for this process over metal-free ionic liquids. However, using these MILs requires metals with supply risk, as they typically use only one or two equivalents of ionic liquid to metal salt. We identify that lanthanide-based MILs show the highest activity for PET glycolysis with a 6![]() ![]() |
The use of a catalyst is well-known to greatly improve the rate of PET glycolysis and the yield of BHET product.8 Catalysts tested have included heterogeneous materials, metal salts, and organocatalysts.8,9 While many of these catalysts often have several benefits, catalysts rarely follow the needed qualities for commercial use, such as fast rates at mild temperatures, low loadings, high yields of BHET, stability to additives and impurities in post-consumer plastics, and recyclability of the catalyst. Recently, volatile organic bases have shown promise, as the catalysts are reasonably stable to impurities and the catalysts can be recycled through sublimation (e.g., the VolCat catalyst that has been commercialized by IBM).10 However, many of these organic bases can be highly toxic and corrosive, and complete separation of the catalyst can be challenging and energy intensive.11
Ionic liquids (ILs), or inorganic salts with low melting points, have emerged as promising catalysts for the glycolysis of PET.12–17 In general, these liquid catalysts often show a bifunctional catalytic behavior in that the cation is proposed to activate the carbonyl for nucleophilic attack, while the anion participates in hydrogen bonding to improve the nucleophilicity of the ethylene glycol, Fig. 1.15 This proposed mechanism is supported by the observation that ionic liquids with more basic anions are more active catalysts than neutral or acidic ILs.3,16 However, the high cost and intensive synthesis were noted as a flaw for long term use.18 Metal-containing ILs (MILs) showed a significant improvement, as the anionic metal fragments were proposed to improve the nucleophilicity of the ethylene glycol similar to basic ILs, with less stability challenges.19–26 Additionally, efforts using iron and cobalt-containing ILs to heterogenize the catalyst and/or use magnets allowed for efficient recovery of the catalyst for reuse.27–30 To date, studies have mostly used imidazolium cations with first row transition metal chloride or acetate salts. Studies have not thoroughly investigated the role of IL cation and the metal containing anion (including the metal ion and ligands bound to the metal ion) for the rate of PET depolymerization or BHET selectivity. Additionally, the often 1:
1 ratio of ionic liquid to metal salt to isolate these transition metal MILs leads to a high consumption of metal salts, which is not ideal with many of these metals being endangered elements.31
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Fig. 1 Proposed role for the cation [Cat+] and anion ([A]−) in the glycolysis of PET. [Cat] could be imidazolium, phosphonium, etc. |
The lanthanide series represents a unique class of metals to probe the desired trends for PET glycolysis. The ionic radius and Lewis acidity subtly change across the series,32 allowing for an understanding of how Lewis acidity and metal ion size impacts PET depolymerization. Additionally, lanthanide metals can allow a wide range of coordination environments,31 in which the ratio of IL to metal ion can be varied. While there are a few reports of lanthanide metal-containing MILs for luminescence and nuclear waste separation,33–35 none have been used for catalytic depolymerization of polymers. We hypothesized that lanthanide-containing MILs could be effective catalysts with a higher ratio of ionic liquids, lowering the endangered metal content for the catalyst without losing the added benefits of MILs over metal-free ILs. Herein we report the use of lanthanide salt/IL combinations to identify trends in PET glycolysis with MILs.
Since lanthanides can accommodate a wider range of coordination environments than transition metals, the metal salts were combined with the ILs in two different ratios (1:
2 and 1
:
6) and mixed at 180 °C. This is distinct from reported transition metal examples where only one or two equivalent of IL is mixed with the metal precursor. Mixtures that formed a homogeneous viscous liquid, indicative of the formation of a MIL, were selected for glycolysis of PET. Conditions in which the metal salt/IL mixture did not combine to homogeneous liquids were not considered further. Five initial ILs were found to effectively form homogeneous liquids at both ratios with the full range of metal ions studied, Fig. 2. For these reaction conditions, a consistent 5 wt% catalyst loading was used to determine the relevance of the metal salt/IL ratio for PET conversion and BHET selectivity. The EG
:
PET weight ratio was kept at 4
:
1, and the reaction was stirred for four hours at 180 °C, similar to conditions used for other MILs.25 Commercial PET cold drink lids, containing 25% recycled PET, from Eco-Products were used for most of the studies to gauge the practicality of the MIL catalyst system. PET conversion and BHET yields were calculated from isolated weights of PET and BHET from each reaction, as described in the ESI.† PET that does not break down fully to BHET can be found in the form of oligomers that are soluble in the ethylene glycol, which are easily separated from PET and BHET (see ESI† for characterization). Initial screening data can be seen in Fig. 3 and 4, with tabulated data present in Tables S1 and S2.†
As shown in Fig. 3, reactions with a 1:
2 ratio of LnCl3·xH2O (x = 6, 7) and IL showed that PET conversions of up to 97% could be achieved within the reaction time frame. It was noticeable that ionic liquids containing the acetate anions outperformed those with chloride anions. Phosphonium cations showed to be reasonably active, with longer alkyl substituents ([H3DP]Cl) performing better than those with shorter alkyl substituents ([B3DP]Cl). Alternatively, the imidazolium cation with the shorter substituent ([emim]OAc) performed better than the longer substituent ([bmim]OAc), which could relate to the higher basicity of [emim]OAc.37 The metals with the highest PET conversion varied depending on the ionic liquid used, with a general trend towards the bigger metals. This could be explained by the lowered Lewis acidity of the metal, causing a higher basicity of the anions bound to the metal. Alternatively, the pKa of these salts in aqueous solution, which increases as the metal ion gets bigger, could explain the observed results.38 However, the largest metal, lanthanum, often showed a drop in PET conversions, which may be a consequence of bridging or aggregate structures within the MIL caused by coordinative unsaturation.
BHET yields/selectivity most often followed the same trends as PET conversion, with imidazolium acetate ILs showing the highest BHET yields. There were some noticeable outliers, where Sm and Tm examples showed no production of BHET. The reasons for this erratic catalytic behavior are not entirely clear at the present but could be related to potentially facile variations in the active catalytic species that are primed by minor changes in the reaction conditions.
As shown in Fig. 4, reactions with a 1:
6 ratio of LnCl3·xH2O (x = 6, 7) and IL showed a significant improvement in the PET conversion for the conditions with ILs containing acetate anions, while the conditions with ILs with chloride anions showed a decrease in conversion. While the increase in conversion for acetate-containing ILs can be rationalized by the increased quantity of basic anions, it cannot explain the lower reactivity for chloride-containing ILs. We postulate that the lower conversion for the chloride containing ILs is due to a lowered metal salt content, which may be the main driver for glycolysis in this case. It was also noted that the higher IL ratio generally increased BHET yields for both acetate containing ILs, however, trends based on metal ion identity were less pronounced than in the case with the 1
:
2 ratio. Interestingly, the largest (La) and smallest (Tm) metals performed much better with the 1
:
6 ratio for PET conversion than they did with 1
:
2. In this case, Sm and Tm continued to show erratic BHET yield, depending on the ionic liquid used. The indication that a higher ratio of IL to metal salt showing more effective rates of depolymerization suggests that the metal salt content can be decreased, improving the sustainability of these MIL catalysts.
Based on these initial screenings, yttrium and gadolinium were identified to be the most promising metals to pursue further, as both showed high PET conversions with both ratios of metal salt to IL. However, yttrium is a much lighter metal than the rest of the lanthanides, which meant a higher mol% could be used for that metal. Since this could be one of the reasons for the high PET conversions, we chose to pursue further studies primarily with Gd. In some cases, lanthanum was used as an example that performed better with the high IL ratio. The imidazolium-based ILs were exclusively pursued further, as the acetate salts showed the highest impact on PET conversion and BHET yield. The next goal was to identify which reaction variables impacted the catalyst activity to optimize the MIL-catalyzed glycolysis of PET.
As shown in Fig. 5, all 1:
2 reactions with [bmim]Cl were yielded similar PET conversions for control reactions and the MIL reactions. This shows limited cooperativity between the metal chloride salts and the chloride-containing IL. We hypothesize this is due to the less basic Cl anion being less likely to associate strongly with the metal ion, dropping the potential for a cooperative MIL.
However, reactions with [bmim]OAc showed significant cooperativity. For the 1:
2 ratio of metal salt to IL, Gd and Y both showed an approximate 50% improvement in PET conversion in comparison to combined results from the metal salt and IL run individually. In this 1
:
2 case, the La-containing MIL showed no cooperativity in PET conversion. Extending to [emim]OAc showed an even larger cooperativity for Gd and Y with an approximate 100% improvement for the MIL over the controls. However, the La case showed a much lower conversion than the controls, consistent with the premise of aggregate formation that decreases acetate basicity. Alternatively, chelating coordination to an unsaturated La center could also lead to a decreased basicity of the acetate anions.
When switching to the 1:
6 ratio of metal salt to IL, cooperativity still was not observed in reactions with [bmim]Cl. However, cooperativity was increased significantly for both [bmim]OAc and [emim]OAc for all three metals, with PET conversion increases reaching an approximate 300% increase in comparison to the controls. In this case, we hypothesize the demonstration of cooperativity for La is probably due to coordinative saturation that facilitates stronger metal interactions with the anions from the IL, leading to similar behavior to that of Gd and Y. No significant metal preference is identified for this condition, therefore the use of Gd was maintained. As mentioned previously, this cooperativity demonstrates the benefit of MIL catalysts over metal-free IL catalysts. However, these results also indicate the benefit of the metal can also be maintained with a much higher IL to metal salt ratio than previously described in the literature.
To identify the cause of the lowered reactivity of the all-acetate examples, cooperativity studies were also conducted for Ln(OAc)3·xH2O (Ln = Y, Gd and La) with [bmim]Cl, [bmim]OAc, and [emim]OAc combinations, analogous to those done about for the chloride metal salts (Fig. S4 and S5†). Interestingly, these studies showed no strong evidence for cooperativity between the metal acetate salts and the IL for both PET conversion and BHET selectivity. These results could be explained by the lowered Lewis acidity for the metal ions with acetate anions, leading to less interaction of the IL anions with the metal. These results suggest at a polydisperse catalyst speciation in solution that may be contingent on identity, quantity and source of basic anions, which can convolute observations of anticipated trends. In this regard, efforts to more deeply characterize the structures and speciation of the MILs studied herein are currently underway, using guidance from prior literature on lanthanide acetate species.39,40
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Fig. 8 PET conversion and BHET yield for GdCl3·6H2O/[emim]OAc (1![]() ![]() ![]() ![]() ![]() ![]() |
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Fig. 9 PET conversion and BHET yield for GdCl3·6H2O/[emim]OAc (1![]() ![]() ![]() ![]() |
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Fig. 10 PET conversion and BHET yield for GdCl3·6H2O/[emim]OAc (1![]() ![]() |
Interestingly, the Gd-containing MIL did not reach the performance of the reported literature examples when used at their optimized conditions. At its optimized condition however, this catalyst achieves comparable PET conversions and BHET yields to prior catalysts. While the goal of this work was not necessarily to find the best catalyst, it is clear that optimization of conditions for each catalyst dictates the obtained measures of catalytic activity and selectivity. That is, optimized conditions for one catalyst may only show slow catalysis for another. For example, the Gd-containing MIL did not perform as well at the higher catalyst loadings above 5 wt%. However, exhibiting higher performance at lower catalyst loadings would be considered valuable and potentially more sustainable. Therefore, relevant comparisons of catalyst activity should consider both optimized conditions for individual catalysts and conditions reported in the literature.
With several variables at play in this reaction, identifying those most critical for optimization will ultimately be necessary to inform catalyst design principles for PET glycolysis using MILs. In this regard, life cycle assessment and techno-economic assessment would be valuable to guide the establishment of appropriate priorities in route to MIL catalyst optimization. In doing so, attributes of each reaction variable can be weighed against overarching outcomes that define practicality and economic feasibility.
Results above also identify lanthanum as a promising metal ion, specifically when high ratios of IL are used. Since La and Ce represent the most abundant and inexpensive lanthanides, also with the lowest supply risks of the series, identification for their catalytic activity is warranted. Additionally, since La and Ce are difficult to separate, a MCl3·6H2O mixture with La and Ce, donated by a lanthanide metal processing company, that were not separated as oxide precursors was also pursued for PET glycolysis. As shown in Fig. 12, La, Ce and La/Ce mix (estimating a 1:
1 ratio of La
:
Ce) MILs with a 1
:
6 ratio of metal salt to [emim]OAc were tested for glycolysis of all five PET materials tested in Fig. 11. In this case, a reaction temperature of 190 °C was used, as it showed higher BHET selectivity for Gd, with all other conditions matching that of the Gd reaction shown in Fig. 8.
In general, the La MIL showed the highest conversion of PET for all materials tested, except the used plastic bottle which showed the highest PET conversion with Ce. However, BHET yields were very low for most of the materials with the La MIL, with the exception of the recycled flake. Ce MILs showed rather low PET conversions, in comparison to La, but had elevated BHET selectivity for some of the materials. Finally, the La/Ce mix showed lower conversions of PET than La, but showed the best BHET yields of the metals studied. This suggests that lanthanide metal salt mixtures, obtained without separation, could be promising alternatives to any one lanthanide metal in particular. While these results identify lanthanide metal mixtures in the MIL catalyst could lead to another improvement on catalyst sustainability, efforts to identify what mixtures are most effective and how conditions can be optimized for these MILs are currently underway.
With an optimized MIL, further tuning reaction conditions revealed that reasonable conversions were achieved above 170 °C, with PET conversion and BHET yield generally increasing with temperature. PET conversion and BHET yield did not change much as EG amount was increased, suggesting any increase in rate from higher EG concentrations is countered by dilution of the MIL catalyst. Reactivity is reasonably maintained with different PET materials, including postconsumer recycled products that contain dyes and other additives. However, harsher conditions and longer reaction times are expected to be required for PET materials with low surface area and high density. Comparisons to optimized literature conditions emphasize that optimized conditions for one catalyst won't necessarily match that of another. Finally, La/Ce mixture-based MILs were found to have high BHET yields, encouraging the use of nonseparated or application-recovered lanthanide metal salts for this catalysis. These results show progress in improving the sustainability of MIL catalysts for the glycolysis of PET.
Efforts to optimize these catalysts and address the recycling of the MILs, as well as studies to understand the examples with high cooperativity, are currently underway. Additionally, identifying how MIL cooperativity changes with metal and IL choice will also be important for advances in MIL catalyst design for catalysis in general.
Footnote |
† Electronic supplementary information (ESI) available: General considerations, glycolysis reaction conditions, and detailed reaction data. See DOI: https://doi.org/10.1039/d3su00090g |
This journal is © The Royal Society of Chemistry 2023 |