Biomimetic supported catalyst inspired by stalked crinoid

Biomimetic supported catalyst inspired by stalked crinoid | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Biomimetic supported catalyst inspired by stalked crinoid Xianhong Wang, Can Liao, Shunjie Liu, Kuang Qingxian, Zhang Ruoyu, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7193791/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Supported catalysis is considered as an ideal catalytic mode as it combines the advantages of homogeneous catalysis (activity and selectivity) and heterogeneous catalysis (separation and recyclability). However, its application is greatly limited by the loss of catalytic performance after immobilization of molecular catalyst on solid supports. Inspired by the upright feeding posture of stalked crinoids—characterized by outstretched arms with ordered pinnules extending away from the substrate—we have addressed this issue by immobilizing of a linear polymer catalyst decorated with aluminum porphyrin on silica. Our catalyst demonstrates remarkable productivity (62.4 kg polyols/g Al porphyrin), polymer selectivity (99%) and proton tolerance (320,000 equiv. to [Al]) under highly dilute conditions (0.000125 mol [Al]%, 17.8 ppm) for bulk telomerization of CO 2 and epoxides, which is greatly improved compared to traditional systems. Furthermore, our catalyst exhibits stability and maintains its catalytic performance after three recycling cycles. This strategy provides a rational approach to designing highly efficient supported catalysts. Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Physical sciences/Chemistry/Polymer chemistry/Polymer synthesis Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Main text Heterogeneous catalysis is the cornerstone of industrial process technology, as over 90% of all chemical products are synthesized by heterogeneous catalysts 1, 2 . An efficient catalyst produces the desired products at high rates while enabling recovery and reuse of the catalyst 3 . Supported catalysts, which are molecular organometallic complexes immobilized on solid supports, are gaining an increasing attention because they combine the advantages of homogeneous catalysis (activity and selectivity) with those of heterogeneous catalysis (separation and recyclability) 3-8 . The method of fabricating supported catalysts is critical for enhancing catalyst performance in terms of activity, selectivity, and cost. Significant breakthroughs in the molecular-level design and synthesis of supported catalysts have been reported, including direct coordination of metal complex to supports and covalent attachment of metal complexes or cocatalysts to the support by linkers (Supplementary Scheme 1) 4, 5, 9-11 . However, many of these catalysts exhibit inferior catalytic performance compared to their homogeneous counterparts 12, 13 , largely due to the unavoidable complex interactions between the support surface and catalyst, as well as issues related to confined diffusion and steric hindrance. Thus, designing high-performance supported catalysts to meet the demands of practical applications remains a true “grand challenge”. Stalked crinoids are deep-sea, lily-like suspension feeders that grow on hard seafloors 14, 15 . They utilize a robust stalk to elevate their crown above the substrate, enhancing foraging efficiency compared to a flat-lying posture. Meanwhile, their outstretched arms, adorned with ordered pinnules, create a virtually continuous filtration fan that improves filtration efficiency (Fig. 1a) 16 . This feeding posture exemplifies the concept of diverting collaborative functional parts away from the support surface to maximize their capabilities. Herein, we propose a stalked crinoid-inspired strategy for the covalent immobilization of linear polymer (stalk and arm) decorated with organometallic complexes (pinnule) onto a solid support via a linker (Fig. 1b) to dramatically improve catalytic performance for the telomerization of CO 2 and epoxide. Ingeniously, triggered by a proton chain transfer agent (CTA), the resulting supported polymeric catalyst adopts an upright posture with active centers extending into the reaction medium and swaying like stalked crinoids in the current, due to the desorption of metal complex from the support surface. As a proof-of-concept, SiO 2 nanosphere-supported bifunctional polymeric catalysts, which consist of aluminum porphyrin (Lewis acid) and tertiary amine (Lewis base), demonstrated impressive productivity (62.4 kg polyols/g Al porphyrin) and selectivity (>99%) even under extremely dilute conditions (0.000125 mol [Al]%) for the synthesis of ultralow molecular weight CO 2 -polyols (600 g/mol), benefited from the extraordinary proton tolerance (320,000 equiv. to [Al]). A mechanistic study indicates that protons of CTA/chain end coordinated at Al center activate the epoxy group, facilitating the rapid ring-opening of epoxides. Furthermore, the catalyst can be reused efficiently at least three times without any loss of performance, and no metal leaching was detected. Learning from nature, our work provides a viable strategy for designing robust and effective supported catalysts. Results and discussion Design and Characterization Mimicking the upright feeding posture of stalked crinoids represents an efficient strategy for diverting functional complexes away from the support surface and into the bulk fluid phase. To achieve this goal, chemists have developed methods for grafting metal complexes with flexible long chains onto the support surface 17 . However, the reduced synergy between the separated active sites hinders applications in the field of catalysis, such as ring-opening polymerization. Additionally, surface inhomogeneity caused by the randomly distributed active sites complicates precise catalyst design 10 , 18 . We envision that the preorganization of single molecular catalysts into polymer chains prior to immobilization will facilitate the fabrication of supported polymeric catalysts that extend multiple active centers into the liquid phase. Recently, we demonstrated that pendulously connected homogeneous polymeric aluminum porphyrins, in conjunction with equimolar sterically hindered ammonium cocatalyst, showcased significantly enhanced activity compared to their monomeric analogs for the copolymerization of CO 2 and epoxides 19 – 21 , owing to the enhanced synergistic effects 22 . Furthermore, it is preferable to incorporate sterically hindered organic bases as cocatalysts into the polymer side chains to construct bifunctional polymeric catalyst 23 – 26 . On this premise, we posit that the design of supported bifunctional polymeric catalyst ( sBFPC , Fig. 2 a) containing pendant Al porphyrin (Lewis acid) and tertiary amine (Lewis base) will enable heterogeneous catalysis to rival that of their homogeneous counterparts ( BFPC ). To embody the advantages of our stalked crinoid-inspired strategy, we also designed control catalysts (Fig. 2 b,c,d), including the supported single molecular Al porphyrin catalyst ( sSC ), supported polymeric Al porphyrin catalyst without tertiary amine ( sPC ), and the supported bifunctional polymeric catalyst adhering to surface ( sBFPC’ ). The precise synthesis method ensures the homogeneity of supported polymeric catalysts. Controlled radical polymerization allows for the adjustment of ratios of catalyst and cocatalyst along the polymer backbone 27 , while azide-alkyne click chemistry facilitates the efficient attachment of polymeric catalysts to supports 28 (Supplementary Schemes 2–6). Due to the steric hindrance effect of acrylate porphyrin, methyl methacrylate (MMA) was introduced to regulate the composition of the polymeric catalyst controlled by an alkyne-substituted trithiocarbonate agent. Hence, the corresponding homogeneous polymeric catalysts were fabricated as BFPC , PC , and BFPC’ (Fig. 2 ) with molar ratios of Al porphyrin/tertiary amine/MMA (n/m/p) of 6/14.4/11.4 (9.2 kg/mol), 9/0/25.2 (12.1 kg/mol), and 6/12/12.6 (9.2 kg/mol), respectively, maintaining a Lewis acid/Lewis base ratio close to 1/2 for optimized catalytic performance 21 . For the supported single-site catalyst precursor, alkyne-substituted porphyrins with varied alkyl chain lengths were obtained (Supplementary Scheme 3d). Alternatively, in selecting a support, the well-known porous silica was likely to restrict the growth and dissociation of polymer chains. In fact, highly active supported catalysts have remained largely unexplored, with limited success in olefin polymerization focusing on product morphology control 6 . Therefore, we constructed the supported polymeric catalyst by tethering the polymeric catalyst to the solid-core silica surface. Collectively, the click chemistry between azide-functionalized silica ( SiO 2 -N 3 , diameter ~ 15 nm) and alkyne-substituted polymer catalysts yielded the designed supported polymeric catalysts. Detailed characterizations of the precursors are provided in Supplementary Figs. 1–43. Multiple characterization technologies demonstrate the attachment of polymeric catalysts through the comparison of characteristic signals (Supplementary Figs. 44–62). ATR-FTIR analysis indicated the presence of C = N stretching vibrations at 1480 and 1400 cm − 1 , associated with the porphyrin macrocycle in the supported polymeric catalysts (Supplementary Figs. 44–47). The solid-state 13 C NMR spectra (Supplementary Figs. 48–51) and X-ray photoelectron spectroscopy (XPS) (Supplementary Fig. 52) revealed signals corresponding to the aromatic carbon atoms of porphyrin (120–150 ppm) and Al complex (Al 2p and Br 3d ), respectively. Interestingly, SEM and multi-point BET results (Supplementary Figs. 53–60) showed no obvious differences among the four supported catalysts, which may be attributed to the adsorption of Al porphyrin on silica in powdered form. UV-vis absorption spectra reflect the H-aggregation of Al porphyrin along the polymer backbone in the dispersion (Supplementary Figs. 61–62), resembling the ordered pinnules on the arms of stalked crinoids. Collectively, these results confirm the successful immobilization of the homogeneous catalysts on the support surface. A long-standing challenge in supported catalyst is the difficulty in quantifying active species 29 . Commonly used analytical methods, such as inductively coupled plasma-optical emission spectroscopy (ICP-OES) and thermogravimetric analysis (TGA), often suffer from high measurement error or low sensitivity. Given the high molar absorption coefficient (10 5 ) of porphyrin in the Soret band (400 to 500 nm), we utilized UV-vis spectroscopy to quantitatively determine the loading of Al porphyrin. This was achieved by calibrating pure complexes through the basic hydrolysis of the ester group and silica in supported catalysts, taking advantage of the high stability of Al porphyrin complexes (Supplementary Fig. 63). Accordingly, the loading of the primary catalyst, sBFPC-1 , and control catalysts, sSC-1 , sPC-1 and sBFPC’-1 were calculated to be 13.0, 12.3, 15.1 and 17.2 µmol Al/g respectively (Supplementary Scheme 7, Supplementary Tables 1–2). These values are closely aligned, facilitating performance comparison. Evidence of stretching state The polymer chains in supported polymeric catalysts tend to move away from the surface under polar conditions. As shown in Fig. 3 a,b, sBFPC-1 sedimented rapidly ( 10 min), indicating the extended state of the polymer chains. These results suggest that the weak interaction between the residual surface silanol and Al porphyrin can be disrupted under polar conditions. The adsorption and desorption processes were further monitored through 1 H NMR analysis of the monomeric Al porphyrin ( M-TPPAl ) and silica ( SiO 2 -N 3 ) mixture (Supplementary Fig. 64). A decrease and blurring of proton signals of M-TPPAl were observed by addition of SiO 2 -N 3 in CDCl 3 , while these signals recovered upon the addition of a drop of CD 3 OD. These findings indicate that polar conditions drive the metal complex away from the support surface. The chain extension of supported polymeric catalysts was directly visualized under polar conditions using cryo-transmission electron microscope (cryo-TEM) (Fig. 3 c,d,e,f). By rapidly freezing supported catalyst suspensions (2 mg/mL in DMSO) with high thermal conductivity liquid ethane (m.p. -183°C) to preserve their conformation in the liquid state 30 , the cryo-TEM analysis revealed various spherical morphologies. By counting > 100 nanoparticles, the supported polymeric catalysts sBFPC-1 (37.6 nm) and sPC-1 (35.1 nm) exhibited larger average diameters than sSC-1 (19.3 nm) and sBFPC’-1 (20.8 nm). These dates further confirm that extended polymeric chains spatially separate the molecular complex from the surface, while shorter linkers confine them to the surface. The influence of the support on the metal complex is significantly reduced in the stretched state. We ingeniously utilized a lyophilization process to preserve stretched state of suspensions in DMSO as much as possible for XPS testing. Unlike the nearly identical Al 2 p binding energies of the homogeneous precursors SC (74.74 eV), PC (74.71 eV), BFPC (74.62 eV), and BFPC’ (74.66 eV), all supported catalysts exhibited Al 2 p peaks that shifted to lower binding energies (Fig. 3 g,h,I,j), suggesting the presence of residual silanol coordination to Al center. However, sBFPC-1 and sPC-1 showed smaller shifts (0.19 and 0.42 eV, respectively) compared to sBFPC’-1 and sSC-1 (0.55 eV and 0.60 eV, respectively). These results confirm that the stalked crinoid-inspired strategy minimizes the detrimental effects of the support on the molecular metal complex. The dynamic behavior of surface solvents is critically influenced by the conformational states—collapsing or stretching—of supported polymeric catalysts 31 . Solvent relaxation NMR has proven to be a valuable technique for investigating these interactions 32 , with detailed principles outlined in Supplementary Scheme 8. Using a single-exponential decay model, the spin-spin relaxation time ( T 2 ) was measured to calculate the average relaxation rate ( R av = 1/ T 2 ). A useful parameter is the specific relaxation rate, R sp , which is defined as R av / R f -1, where R f represents the relaxation rate of the free solvent (blank control) 33 . A smaller R sp indicates faster overall solvent mobility. As shown in Fig. 3 k, for catalyst dispersions (10 mg/mL in ethanol), the results revealed distinct orders of R sp : sSC-1 (1.07) > sBFPC’-1 (0.33) > sBFPC-1 (0.22) ≈ sPC-1 (0.21). These findings suggest that solvent movement is severely restricted near sSC-1 surface and moderate for sBFPC’-1 , and demonstrates the fastest mobility for sBFPC-1 and sPC-1 (Fig. 3 l). The terminal anchor groups in sBFPC-1 and sPC-1 maximize the freedom of the molecular complexes 34 , facilitating less hindered solvent movement through extended chain conformations. Telomerization of CO and epoxides To validate our catalyst design strategy, we conducted the telomerization of PO and CO 2 to produce CO 2 -polyols using protic CTAs such as acids and alcohols (Fig. 4 a). The resulting CO 2 -polyols, which feature a tunable carbonate/ether coexisting structure (Supplementary Scheme 9), represent an excellent option for potential large-scale utilization of CO 2 35 . This approach not only reduces greenhouse gas emission and conserves fossil resources 36 , but it can also provide high-quality polyurethanes by reacting with isocyanates 37 , 38 . Generally, previous studies have shown that catalytic performance declines significantly at high CTA loadings as carefully summarized in Supplementary Schemes 10-11 39−42 , primarily due to the poisoning effect of CTAs on the metal center 43 . Therefore, the development of highly efficient and reusable catalysts is desirable for large-scale applications. Through prescreening the polymerization conditions (Supplementary Table 3), the optimized telomerization of PO/CO 2 using supported catalysts was performed at a ratio of [Al]/CTA/PO = 1/2,000/200,000 under 70°C and 3 MPa of CO 2 pressure for 36 h using sebacic acid (SA) as a modal CTA (entries 1–6, Supplementary Table 4). Notably the porphyrin unit in the four supported catalysts displayed tight H-aggregation in the dispersion even at 90°C (Supplementary Fig. 61), indicating strong molecular interactions 44 . We were pleased to find that sBFPC-1 achieved a high activity of 7.2 kg polyols/g [Al] (Al porphyrin) (corresponding to TOF of 2500 h − 1 ) with a polymer selectivity of 97% and a carbonate unit content of 35% (Fig. 4 b, Supplementary Fig. 65). This performance surpassed that of previously reported homogeneous catalysts (Supplementary Scheme 11), demonstrating the effectiveness of the stalked crinoid-inspired strategy. Importantly, in the absence of CTA, sBFPC-1 afforded lower productivity (5.4 kg polyols/g [Al]) and polymer selectivity (91%) (entry 6, Supplementary Table 3), attributed to insufficient stretching of the polymeric catalyst chain without polar stimulation. Under cocatalyst-free conditions, the activity of sSC-1 , sPC-1 and sBFPC’-1 was relatively low, showing values of 0.3, 3.0 and 3.5 kg polyols/g [Al] respectively, while still maintaining high polymer selectivity. The addition of equimolar bis(triphenylphosphine)iminium chloride (PPNCl) as cocatalyst based on Al porphyrin enhanced the activity of sSC-1 and sPC-1 to 1.3 and 5.8 kg polyols/g [Al], respectively (entries 5–6, Supplementary Table 4), although this improvement came at the cost of approximately 10% polymer selectivity for sPC-1 . The external cocatalyst increased activity but also facilitated the back-biting of the growing chain, leading to the formation of the byproduct cyclic propylene carbonate (cPC) 45 . Furthermore, recycling the external cocatalyst is challenging, which may impact the utility of downstream products and elevate separation costs. These results underscore the advantages of supported bifunctional polymeric catalysts for the preparation and separation of CO 2 -polyols. Unlike conventional heterogeneous catalysts, sBFPC-1 demonstrated exceptional control over product structure. The polymer dispersity index ( Đ ) of CO 2 -polyols was precisely regulated at 1.06 with a molecular weight comparable to the theoretical value (2.7 vs. 3.4 kg/mol) (Supplementary Table 4). In contrary, sSC-1 and sBFPC’-1 produced polyols with broad dispersity ( Đ >1.2) (Supplementary Fig. 66), similar to the behavior of traditional heterogeneous catalyst double metal cyanide (DMC) complexes 46 . Additionally, sPC-1 required the addition of cocatalyst to achieve a narrow Đ of 1.05. These results can be elucidated by solvent relaxation NMR, which indicates that the extended conformation of catalysts sBFPC-1 and sPC-1 facilitated a more rapid exchange between active and dormant polymer chains compared to catalysts in a more compact position, due to enhanced mass transfer efficiency. To further illustrate the advantages of supported polymeric catalysts, control supported single-site catalysts with varying loadings (12.3–95.5 µmol Al/g) and different lengths of alkyl linkers ( sSC-y , where y = 2 , 3 , 4 , 5 , 6 ) were synthesized (Supplementary Table 5). To ensure sufficient monomer conversion, the telomerization conditions were adjusted to [Al]/SA/PO = 1/100/10,000. However, the catalytic performance of these supported single-site catalysts was minimally affected, exhibiting comparable productivity (0.26–0.40 kg polyols/g [Al]) and a broad Đ (1.4–2.5). This again highlights the challenges of systematic tunability of supported single-site catalysts due to the random distribution of active sites. The loading density of polymeric catalyst has a significant effect on catalytic performance (Fig. 4 c, Supplementary Table 4). Compared to sBFPC-1 (13.0 µmol Al/g, moderate loading), both sBFPC-2 (2.1 µmol Al/g, low loading) and sBFPC-3 (38.0 µmol Al/g, high loading) exhibited inferior performance, yielding 2.7 and 5.4 kg polyols/g [Al] with polymer selectivity of 87% and 92%, respectively. The analysis of the UV-vis spectrum of porphyrin units serves as a powerful tool for studying the interactions of polymeric catalysts in a suspended state (Supplementary Fig. 62). The decreased shoulder peak (405 nm) for sBFPC-2 suggests weak interpolymeric chain synergy 47 , 48 , while the red-shifted Soret band (422 nm) for sBFPC-3 indicates the formation of less-active J aggregates 44 . The moderate loading of sBFPC-1 enables optimized synergies and reduced steric hindrance for the porphyrin active sites 49 . Our strategy enables sBFPC-1 to achieve performance levels comparable to those of the homogeneous analogue (Fig. 4 d, Supplementary Table 6). Notably, sBFPC-1 displayed exceptional proton-enhanced activity, achieving an unprecedented productivity of 62.4 kg polyols/g [Al] under a molar ratio of [Al]/SA/PO = 1/160,000/800,000 for 144 h (Fig. 4 d). This performance benefits from the ultrahigh proton tolerance (320,000 protons) and resistance to dilution effects (0.000125 mol [Al]%), significantly surpassing previous reports (Fig. 4 e) 7 , 39 , 41 , 50 , 51 . Additionally, the molecular weight was well-controlled to ultralow values (0.6 kg/mol) with a narrow Đ (< 1.1) and an adjusted carbonate unit (30–60%) (Supplementary Fig. 67), inheriting the merits of the parental catalysts (Fig. 4 f, Supplementary Table 7). Furthermore, sBFPC-1 is broadly applicable to various CTA (Supplementary Table 8) and epoxides (Supplementary Table 9) with different architectures, where stronger acidity correlates with higher activity (Supplementary Figs. 68–69), further demonstrating its excellent proton tolerance. All these CO 2 -polyols were characterized using MALDI-TOF-MS spectra (Supplementary Figs. 70–77). The reusability of sBFPC-1 was evaluated by a 5 L autoclave at the ratio of [Al]/SA/PO = 1/40,000/200,000 at 70°C and 3 MPa of CO 2 for 36 h, utilizing 10 g supported catalyst, 2 L PO and 1.16 kg SA (Fig. 4 g, Supplementary Table 10). The process achieved 67% PO conversion and > 99% polymer selectivity, yielding a productivity of 19.5 kg polyols/g [Al]. Due to the absence of by-product (cPC), the catalyst was facilely recovered from CO 2 -polyols through centrifugation and evaporation of low-boiling point PO (32°C), giving a light-green catalyst and a nearly colorless oily product. Notably, the product contained negligible Al content (~ 0.2 ppm), demonstrating the high stability of the supported polymeric catalysts. The catalyst can be reused at least 3 times without compromising product architecture ( Đ < 1.1), polymer selectivity (~ 99%) and productivity (18.2 kg polyols/g [Al]) (Fig. 4 h), deriving from the integrity of the spherical morphology (Supplementary Fig. 78). Possible mechanism for proton-enhanced polymerization The proton-enhanced catalytic performance of sBFPC-1 , which differs from conventional systems (proton-deactivated polymerization), prompts us to explore the underlying mechanisms. Owing to the heterogeneous nature of supported catalysts, homogeneous analogues were utilized to elucidate the catalytic process. Additionally, trifluoroacetic acid (TFA) was strategically selected as CTA, as it can be further verified by 19 F NMR. Interestingly, when a mixture of M-TPPAl /TFA/PO (1/2/5) was combined in CDCl 3 , obvious signal shifts of TFA (trifluoromethyl, Fig. 5 a) and PO (epoxy group, Fig. 5 b) were observed. These shifts were attributed to the shielding effect of Al porphyrin (Supplementary Fig. 79), which only occurred in the presence of CTA (Supplementary Fig. 80) during NMR titration experiments of TFA with M-TPPAl /PO (1/5). Variable temperature 19 F NMR further demonstrated two distinct types of TFA signals (approximately 1:1) at low temperatures (213 K) (Fig. 5 c), which experienced different shielding effects, possibly due to varying distances from the porphyrin plane. The resulting species was likely a hexa-coordinated 52 dicarboxylate aluminum complex, accompanied by hydrogen-bonding activated PO, where the Soret band showed a redshift from 420 nm (without TFA) to 422 nm (with TFA) (Fig. 5 d). This coordination pattern was also suitable for other CTAs (Supplementary Figs. 81–82), with stronger acidity leading to higher activation of PO (Supplementary Fig. 83) and greater binding affinity to Al porphyrin (Supplementary Fig. 84). The hexa-coordinated dicarboxylate Al complex was also observed in the presence of sterically hindered organic bases (Supplementary Figs. 85–89), which acted as hydrogen bond receptors to enhance the nucleophilicity of residual CTA/chain end 53 . In addition to the new monomer activation pattern, the high local concentration of active sites is crucial for achieving impressive catalytic performance. Reducing the distance between Al porphyrin is a top priority, as homogeneous monomolecular Al porphyrin exhibits minimal activity in the presence of substantial CTA (Supplementary Table 11). The increased local concentration, originating from the confinement of polymer chains and moderate immobilization, facilitates both interchain and intrachain synergies within the supported polymeric catalyst (Fig. 5 e) 54 . The covalently linked organic base sustains the local activation of the CTA/chain end, further enhancing catalytic performance. The simultaneous activation of both the monomer and CTA/chain end in proximity combines the advantages of optimal perfromance 55 , 56 . Conclusion We have successfully addressed the long-standing challenge of preparing highly active supported catalysts. Unlike traditional methods that immobilize molecular metal complex/cocatalyst onto a support via a short linker, we developed a biomimetic approach in which polymeric catalysts with active sites decorated on pendants are grafted to the surface. Notably, when triggered by proton CTA, our supported polymeric catalyst adopted an upright posture, with active centers extending into the reaction medium and swaying like stalked crinoids in the current, greatly mitigating the detrimental effects of support surface on the metal center. In the telomerization of CO 2 and epoxides, the optimal sBFPC-1 exhibits impressive productivity (62.4 kg polyols/g Al porphyrin) and selectivity (99%) under extremely dilute conditions (0.000125 mol [Al]%, 17.8 ppm), which can be reused at least three times. Mechanistic studies indicate that the extraordinary proton tolerance (320,000 equiv. to [Al]) results from an activation pattern of epoxy by the protons of coordinated CTA/chain end. Beyond this proof-of-concept work, our research highlights a robust and feasible strategy for enhancing various supported catalysts, which are essential for practical applications. Methods General procedure for homogeneous polymeric Al porphyrin The polymeric porphyrin ligand was prepared through RAFT polymerization. Generally, monomeric porphyrin ligand ( M-TPP ) (1 g, 1.07 mmol), MMA (0.214 g, 2.14 mmol), 2-(dimethylamino)-ethyl methacrylate (DMAEMA) (0.336 g, 2.14 mmol), RAFT agent (46 mg, 0.107 mmol), AIBN (9 mg, 0.05 mmol) were dissolved in THF (20 mL). After degassed, the mixture was heated to 65 °C for 48 h. After cooling to room temperature, the mixture was centrifuged in cold diethyl ether and washed by cold diethyl ether for 3 times. The ligand was dried under vacuum at 80 °C. Then in the glove box, the ligand was dissolved in CH 2 Cl 2 and metallized with AlEt 2 Cl. After completion of metallization, the solvent was removed in vacuo to give BFPC . PC and BFPC’ were prepared by similar processes. General procedure for supported catalysts The homogeneous Al porphyrin was supported through azide-alkyne click chemistry. Generally, SiO 2 -N 3 (0.5 g), homogeneous catalyst (0.05 g), CuBr (0.01 g, 0.07 mmol), PMDETA (0.025 g, 0.14 mmol) were added into a round-bottom flask. Then 10 mL DMF (10 mL) was injected under nitrogen. The mixture was dispersed by sonication and stirred for 24 h. The Immobilized catalyst was separated by centrifugation and washed by CH 2 Cl 2 /CH 3 OH (V/V, 10/1) and then dried under vacuum at 80 °C. General procedure for telomerization of CO 2 and epoxide Generally, in a glove box, the desired supported catalyst, CTA and PO (4.0 mL) was added into a pre-dried 10 mL autoclave with a magnetic stir. Then the autoclave was taken out of the glove box followed by pressurized with CO 2 and the mixture was stirred at the desired temperature for a necessary time. After cooling to room temperature, release CO 2 and a small aliquot of the mixture were taken out for 1 H NMR and GPC analysis. For the viscous crude mixtures, dilution was carried out by adding CH 2 Cl 2 , followed by centrifugation to separate the supported catalysts. Small amount of cyclic propylene carbonate (cPC, byproduct) was removed by aqueous washing. Low-boiling point PO and/or CH 2 Cl 2 were removed under vacuum. The recycled supported catalysts were washed by CH 3 CN/CH 3 CO 2 H (V/V, 50/1) three times and dried at 70 °C under vacuum and then reused. 50 mL and 75 mL autoclaves were used when the telomerizations were performed at dilution effects (Supplementary Table 6). 5 L autoclave was used for reaction amplification. Declarations Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant Nos. 51988102). We thank W.F. at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, for the cryo-TEM tests. Author contributions C.L., S.L., and X.W. conceived the idea. C.L. and S.L. designed the experiments. C.L. conducted experiments. 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Supplementary Files SupplementaryInformationBiomimeticsupportedcatalystinspiredbystalkedcrinoid.pdf Supplementary Information TableofContents.png Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-7193791","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":504212716,"identity":"8df3f606-eab0-4397-9a7d-32352a2d9fb0","order_by":0,"name":"Xianhong 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Sciences","correspondingAuthor":false,"prefix":"","firstName":"Xuesi","middleName":"","lastName":"Chen","suffix":""}],"badges":[],"createdAt":"2025-07-23 08:15:09","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7193791/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7193791/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":91609743,"identity":"3ee60861-1641-4a53-82fa-8529ea19d7ad","added_by":"auto","created_at":"2025-09-18 09:43:56","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":192147,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eBiomimetic design of supported catalyst.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e, Schematic illustration of the upright feeding posture (lifting outstretched arms with ordered pinnules away from substrate) of a stalked crinoid mediated by a potent stalk. \u003cstrong\u003eb\u003c/strong\u003e, Schematic of bioinspired design of supported catalysts.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/c0ca49f56873e7606d415724.png"},{"id":91609750,"identity":"a561bd52-1caf-4b41-9d13-48e10d2db2c9","added_by":"auto","created_at":"2025-09-18 09:43:57","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":348543,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSchematic of various Al porphyrins in this work.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e, Cartoon model of the designed route for synthesis of \u003cstrong\u003esBFPC-1\u003c/strong\u003e and its real picture. \u003cstrong\u003eb\u003c/strong\u003e,\u003cstrong\u003ec\u003c/strong\u003e,\u003cstrong\u003ed\u003c/strong\u003e, Cartoon models and pictures of three control catalysts: \u003cstrong\u003esSC-1\u003c/strong\u003e (\u003cstrong\u003eb\u003c/strong\u003e), \u003cstrong\u003esPC-1\u003c/strong\u003e (\u003cstrong\u003ec\u003c/strong\u003e), \u003cstrong\u003esBFPC’-1\u003c/strong\u003e (\u003cstrong\u003ed\u003c/strong\u003e). \u003cstrong\u003ee\u003c/strong\u003e, The homogeneous counterparts of three control catalysts.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/1bf0c99ad3544ee053d7f1af.png"},{"id":91609746,"identity":"967020f1-14b0-4c89-a733-7bb9d9937511","added_by":"auto","created_at":"2025-09-18 09:43:56","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":327038,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEvidence of stretching state.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e,\u003cstrong\u003eb\u003c/strong\u003e, Pictures and schematic of \u003cstrong\u003esBFPC-1\u003c/strong\u003e in CHCl\u003csub\u003e3\u003c/sub\u003e (non-polar solvent, 10 mg/mL) (\u003cstrong\u003ea\u003c/strong\u003e) and CH\u003csub\u003e3\u003c/sub\u003eOH (polar solvent, 10 mg/mL) (\u003cstrong\u003eb\u003c/strong\u003e). \u003cstrong\u003ec\u003c/strong\u003e,\u003cstrong\u003ed\u003c/strong\u003e,\u003cstrong\u003ee\u003c/strong\u003e,\u003cstrong\u003ef\u003c/strong\u003e, Cryo-TEM images and cartoon models of \u003cstrong\u003esBFPC-1\u003c/strong\u003e (\u003cstrong\u003ec\u003c/strong\u003e), \u003cstrong\u003esBFPC’-1\u003c/strong\u003e (\u003cstrong\u003ed\u003c/strong\u003e), \u003cstrong\u003esSC-1\u003c/strong\u003e (\u003cstrong\u003ee\u003c/strong\u003e), \u003cstrong\u003esPC-1\u003c/strong\u003e (\u003cstrong\u003ef\u003c/strong\u003e). \u003cstrong\u003eg\u003c/strong\u003e,\u003cstrong\u003eh\u003c/strong\u003e,\u003cstrong\u003ei\u003c/strong\u003e,\u003cstrong\u003ej\u003c/strong\u003e, XPS spectra of Al \u003cem\u003e2p\u003c/em\u003e of \u003cstrong\u003esBFPC-1\u003c/strong\u003e and \u003cstrong\u003eBFPC\u003c/strong\u003e (\u003cstrong\u003eg\u003c/strong\u003e), \u003cstrong\u003esBFPC’-1\u003c/strong\u003e and \u003cstrong\u003eBFPC’\u003c/strong\u003e (\u003cstrong\u003eh\u003c/strong\u003e), \u003cstrong\u003esSC-1\u003c/strong\u003e and \u003cstrong\u003eSC\u003c/strong\u003e (\u003cstrong\u003ei\u003c/strong\u003e), \u003cstrong\u003esPC-1\u003c/strong\u003e and \u003cstrong\u003ePC\u003c/strong\u003e (\u003cstrong\u003ej\u003c/strong\u003e). The supported catalysts were suspended in DMSO first and then obtained by lyophilization process. \u003cstrong\u003ek\u003c/strong\u003e, Solvent relaxation NMR of four supported catalysts in ethanol (10 mg/mL). Inset: \u003cem\u003eR\u003c/em\u003e\u003csub\u003esp\u003c/sub\u003e of four suspensions of supported catalysts. \u003cstrong\u003el\u003c/strong\u003e, Schematic illustration of the different mobility of surface solvent in four suspensions.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/a7ba553b6f3b201ff44b70f6.png"},{"id":91609745,"identity":"02061cf5-e67a-4802-a877-3ab7896a24f5","added_by":"auto","created_at":"2025-09-18 09:43:56","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":206779,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eResults of telomerization of CO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e and PO by supported catalysts.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e, Scheme showing telomerization of CO\u003csub\u003e2\u003c/sub\u003e and PO for CO\u003csub\u003e2\u003c/sub\u003e-polyols. \u003cstrong\u003eb\u003c/strong\u003e, A direct comparison of catalytic performance among main catalysts and control catalysts at the ratio of [Al]/SA/PO = 1/2,000/200,000 at 70 °C and 3 MPa of CO\u003csub\u003e2\u003c/sub\u003e pressure for 36 h (entries 1-4, Supplementary Table 4). \u003cstrong\u003ec\u003c/strong\u003e, Cartoon models and comparison of catalytic performance (entries 1, 7-8, Supplementary Table 4) of \u003cstrong\u003esBFPC-1\u003c/strong\u003e, \u003cstrong\u003esBFPC-2\u003c/strong\u003e and \u003cstrong\u003esBFPC-3\u003c/strong\u003e. \u003cstrong\u003ed\u003c/strong\u003e, The effect of CTA dosage on catalyst performance \u003cstrong\u003esBFPC-1\u003c/strong\u003e and \u003cstrong\u003eBFPC\u003c/strong\u003e. (entries 1-10, Supplementary Table 6). \u003cstrong\u003ee\u003c/strong\u003e, Comparison of proton tolerance and resistance to dilution effects of \u003cstrong\u003esBFPC-1\u003c/strong\u003e with previous catalysts (Supplementary Scheme 11). \u003cstrong\u003ef\u003c/strong\u003e, Comparison of catalytic performance of \u003cstrong\u003esBFPC-1\u003c/strong\u003e and \u003cstrong\u003eBFPC\u003c/strong\u003e (entries 1-8, Supplementary Table 7). \u003cstrong\u003eg\u003c/strong\u003e, The demonstration of \u003cstrong\u003esBFPC-1 \u003c/strong\u003ereusability using 5 L autoclave. The polymerization was performed at the ratio of [Al]/SA/PO = 1/40,000/200,000 at 70 °C and 3 MPa of CO\u003csub\u003e2\u003c/sub\u003e pressure for 36 h, where 2 L PO and 1.16 kg SA were used. \u003cstrong\u003eh\u003c/strong\u003e, Recycle tests of \u003cstrong\u003esBFPC-1\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/c719061963ebcd9db733b797.png"},{"id":91610334,"identity":"8f76c3e2-85bd-44c7-91fc-3f01d73663f9","added_by":"auto","created_at":"2025-09-18 09:51:56","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":109617,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eInsight into proton-enhanced polymerization.\u003c/strong\u003e \u003cstrong\u003ea\u003c/strong\u003e,\u003csup\u003e 19\u003c/sup\u003eF NMR spectra of 1) TFA, 2) TFA/PO (2/5) and 3) \u003cstrong\u003eM-TPPAl\u003c/strong\u003e/TFA/PO (1/2/5) at 293K in CDCl\u003csub\u003e3\u003c/sub\u003e. Referenced to fluorobenzene internal standard (-113.1 ppm). \u003cstrong\u003eb\u003c/strong\u003e, Portion of \u003csup\u003e1\u003c/sup\u003eH NMR spectral changes (2.4-3.0 ppm from PO) of 1) PO, 2) TFA/PO (2/5) and 3) \u003cstrong\u003eM-TPPAl\u003c/strong\u003e/TFA/PO (1/2/5) at 293K in CDCl\u003csub\u003e3\u003c/sub\u003e. \u003cstrong\u003ec\u003c/strong\u003e, Variable temperature \u003csup\u003e19\u003c/sup\u003eF NMR spectra of \u003cstrong\u003eM-TPPAl\u003c/strong\u003e/TFA/PO (1/2/5) from 213 K to 273 K in CDCl\u003csub\u003e3\u003c/sub\u003e. \u003cstrong\u003ed\u003c/strong\u003e, Comparison of UV-vis spectra (in CHCl\u003csub\u003e3\u003c/sub\u003e at 293 K) of \u003cstrong\u003eM-TPPAl\u003c/strong\u003e/PO (1/5) in the absence and presence of TFA. \u003cstrong\u003ee\u003c/strong\u003e, The possible multiple synergies existed in \u003cstrong\u003esBFPC-1\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/765af6083ea966e26f6c18ec.png"},{"id":91611686,"identity":"7262ad4b-0136-4d50-8dd7-f20248607324","added_by":"auto","created_at":"2025-09-18 09:59:56","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2127448,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/70eeb7aa-7659-40ca-8b58-98ff812aaf38.pdf"},{"id":91609747,"identity":"ce4b5b99-20bf-49f5-a521-7c097122f406","added_by":"auto","created_at":"2025-09-18 09:43:56","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4291071,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"SupplementaryInformationBiomimeticsupportedcatalystinspiredbystalkedcrinoid.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/ecd223d7d0b8ddbbe41a3691.pdf"},{"id":91609744,"identity":"084c92f4-ed1e-4718-a5f8-e5afb60148c6","added_by":"auto","created_at":"2025-09-18 09:43:56","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":71436,"visible":true,"origin":"","legend":"","description":"","filename":"TableofContents.png","url":"https://assets-eu.researchsquare.com/files/rs-7193791/v1/47b6c9a7e9bb32c20721b528.png"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Biomimetic supported catalyst inspired by stalked crinoid","fulltext":[{"header":"Main text","content":"\u003cp\u003eHeterogeneous catalysis is the cornerstone of industrial process technology, as over 90% of all chemical products are synthesized by heterogeneous catalysts\u003csup\u003e1, 2\u003c/sup\u003e. An efficient catalyst produces the desired products at high rates while enabling recovery and reuse of the catalyst\u003csup\u003e3\u003c/sup\u003e. Supported catalysts, which are molecular organometallic complexes immobilized on solid supports, are gaining an increasing attention because they combine the advantages of homogeneous catalysis (activity and selectivity) with those of heterogeneous catalysis (separation and recyclability)\u003csup\u003e\u0026nbsp;3-8\u003c/sup\u003e. The method of fabricating supported catalysts is critical for enhancing catalyst performance in terms of activity, selectivity, and cost. Significant breakthroughs in the molecular-level design and synthesis of supported catalysts have been reported, including direct coordination of metal complex to supports and covalent attachment of metal complexes or cocatalysts to the support by linkers (Supplementary Scheme 1)\u003csup\u003e\u0026nbsp;4, 5, 9-11\u003c/sup\u003e. However, many of these catalysts exhibit inferior catalytic performance compared to their homogeneous counterparts\u003csup\u003e12, 13\u003c/sup\u003e, largely due to the unavoidable complex interactions between the support surface and catalyst, as well as issues related to confined diffusion and steric hindrance. Thus, designing high-performance supported catalysts to meet the demands of practical applications remains a true “grand challenge”.\u003c/p\u003e\n\u003cp\u003eStalked crinoids are deep-sea, lily-like suspension feeders that grow on hard seafloors\u003csup\u003e14, 15\u003c/sup\u003e. They utilize a robust stalk to elevate their crown above the substrate, enhancing foraging efficiency compared to a flat-lying posture. Meanwhile, their outstretched arms, adorned with ordered pinnules, create a virtually continuous filtration fan that improves filtration efficiency (Fig. 1a)\u003csup\u003e\u0026nbsp;16\u003c/sup\u003e. This feeding posture exemplifies the concept of diverting collaborative functional parts away from the support surface to maximize their capabilities.\u003c/p\u003e\n\u003cp\u003eHerein, we propose a stalked crinoid-inspired strategy for the covalent immobilization of linear polymer (stalk and arm) decorated with organometallic complexes (pinnule) onto a solid support via a linker (Fig. 1b) to dramatically improve catalytic performance for the telomerization of CO\u003csub\u003e2\u003c/sub\u003e and epoxide. Ingeniously, triggered by a proton chain transfer agent (CTA), the resulting supported polymeric catalyst adopts an upright posture with active centers extending into the reaction medium and swaying like stalked crinoids in the current, due to the desorption of metal complex from the support surface. As a proof-of-concept, SiO\u003csub\u003e2\u003c/sub\u003e nanosphere-supported bifunctional polymeric catalysts, which consist of aluminum porphyrin (Lewis acid) and tertiary amine (Lewis base), demonstrated impressive productivity (62.4 kg polyols/g Al porphyrin) and selectivity (\u0026gt;99%) even under extremely dilute conditions (0.000125 mol [Al]%) for the synthesis of ultralow molecular weight CO\u003csub\u003e2\u003c/sub\u003e-polyols (600 g/mol), benefited from the extraordinary proton tolerance (320,000 equiv. to [Al]). A mechanistic study indicates that protons of CTA/chain end coordinated at Al center activate the epoxy group, facilitating the rapid ring-opening of epoxides. Furthermore, the catalyst can be reused efficiently at least three times without any loss of performance, and no metal leaching was detected. Learning from nature, our work provides a viable strategy for designing robust and effective supported catalysts.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003eDesign and Characterization\u003c/h2\u003e\u003cp\u003eMimicking the upright feeding posture of stalked crinoids represents an efficient strategy for diverting functional complexes away from the support surface and into the bulk fluid phase. To achieve this goal, chemists have developed methods for grafting metal complexes with flexible long chains onto the support surface\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e. However, the reduced synergy between the separated active sites hinders applications in the field of catalysis, such as ring-opening polymerization. Additionally, surface inhomogeneity caused by the randomly distributed active sites complicates precise catalyst design\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e. We envision that the preorganization of single molecular catalysts into polymer chains prior to immobilization will facilitate the fabrication of supported polymeric catalysts that extend multiple active centers into the liquid phase. Recently, we demonstrated that pendulously connected homogeneous polymeric aluminum porphyrins, in conjunction with equimolar sterically hindered ammonium cocatalyst, showcased significantly enhanced activity compared to their monomeric analogs for the copolymerization of CO\u003csub\u003e2\u003c/sub\u003e and epoxides\u003csup\u003e\u003cspan additionalcitationids=\"CR20\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e, owing to the enhanced synergistic effects\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. Furthermore, it is preferable to incorporate sterically hindered organic bases as cocatalysts into the polymer side chains to construct bifunctional polymeric catalyst\u003csup\u003e\u003cspan additionalcitationids=\"CR24 CR25\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. On this premise, we posit that the design of supported bifunctional polymeric catalyst (\u003cb\u003esBFPC\u003c/b\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea) containing pendant Al porphyrin (Lewis acid) and tertiary amine (Lewis base) will enable heterogeneous catalysis to rival that of their homogeneous counterparts (\u003cb\u003eBFPC\u003c/b\u003e). To embody the advantages of our stalked crinoid-inspired strategy, we also designed control catalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb,c,d), including the supported single molecular Al porphyrin catalyst (\u003cb\u003esSC\u003c/b\u003e), supported polymeric Al porphyrin catalyst without tertiary amine (\u003cb\u003esPC\u003c/b\u003e), and the supported bifunctional polymeric catalyst adhering to surface (\u003cb\u003esBFPC\u0026rsquo;\u003c/b\u003e).\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe precise synthesis method ensures the homogeneity of supported polymeric catalysts. Controlled radical polymerization allows for the adjustment of ratios of catalyst and cocatalyst along the polymer backbone\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e, while azide-alkyne click chemistry facilitates the efficient attachment of polymeric catalysts to supports\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e (Supplementary Schemes 2\u0026ndash;6). Due to the steric hindrance effect of acrylate porphyrin, methyl methacrylate (MMA) was introduced to regulate the composition of the polymeric catalyst controlled by an alkyne-substituted trithiocarbonate agent. Hence, the corresponding homogeneous polymeric catalysts were fabricated as \u003cb\u003eBFPC\u003c/b\u003e, \u003cb\u003ePC\u003c/b\u003e, and \u003cb\u003eBFPC\u0026rsquo;\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e) with molar ratios of Al porphyrin/tertiary amine/MMA (n/m/p) of 6/14.4/11.4 (9.2 kg/mol), 9/0/25.2 (12.1 kg/mol), and 6/12/12.6 (9.2 kg/mol), respectively, maintaining a Lewis acid/Lewis base ratio close to 1/2 for optimized catalytic performance\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e. For the supported single-site catalyst precursor, alkyne-substituted porphyrins with varied alkyl chain lengths were obtained (Supplementary Scheme 3d). Alternatively, in selecting a support, the well-known porous silica was likely to restrict the growth and dissociation of polymer chains. In fact, highly active supported catalysts have remained largely unexplored, with limited success in olefin polymerization focusing on product morphology control\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e. Therefore, we constructed the supported polymeric catalyst by tethering the polymeric catalyst to the solid-core silica surface. Collectively, the click chemistry between azide-functionalized silica (\u003cb\u003eSiO\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e-N\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e, diameter\u0026thinsp;~\u0026thinsp;15 nm) and alkyne-substituted polymer catalysts yielded the designed supported polymeric catalysts. Detailed characterizations of the precursors are provided in Supplementary Figs.\u0026nbsp;1\u0026ndash;43.\u003c/p\u003e\u003cp\u003eMultiple characterization technologies demonstrate the attachment of polymeric catalysts through the comparison of characteristic signals (Supplementary Figs.\u0026nbsp;44\u0026ndash;62). ATR-FTIR analysis indicated the presence of C\u0026thinsp;=\u0026thinsp;N stretching vibrations at 1480 and 1400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, associated with the porphyrin macrocycle in the supported polymeric catalysts (Supplementary Figs.\u0026nbsp;44\u0026ndash;47). The solid-state \u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003eC NMR spectra (Supplementary Figs.\u0026nbsp;48\u0026ndash;51) and X-ray photoelectron spectroscopy (XPS) (Supplementary Fig.\u0026nbsp;52) revealed signals corresponding to the aromatic carbon atoms of porphyrin (120\u0026ndash;150 ppm) and Al complex (Al \u003cem\u003e2p\u003c/em\u003e and Br \u003cem\u003e3d\u003c/em\u003e), respectively. Interestingly, SEM and multi-point BET results (Supplementary Figs.\u0026nbsp;53\u0026ndash;60) showed no obvious differences among the four supported catalysts, which may be attributed to the adsorption of Al porphyrin on silica in powdered form. UV-vis absorption spectra reflect the H-aggregation of Al porphyrin along the polymer backbone in the dispersion (Supplementary Figs.\u0026nbsp;61\u0026ndash;62), resembling the ordered pinnules on the arms of stalked crinoids. Collectively, these results confirm the successful immobilization of the homogeneous catalysts on the support surface.\u003c/p\u003e\u003cp\u003eA long-standing challenge in supported catalyst is the difficulty in quantifying active species\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e. Commonly used analytical methods, such as inductively coupled plasma-optical emission spectroscopy (ICP-OES) and thermogravimetric analysis (TGA), often suffer from high measurement error or low sensitivity. Given the high molar absorption coefficient (10\u003csup\u003e5\u003c/sup\u003e) of porphyrin in the Soret band (400 to 500 nm), we utilized UV-vis spectroscopy to quantitatively determine the loading of Al porphyrin. This was achieved by calibrating pure complexes through the basic hydrolysis of the ester group and silica in supported catalysts, taking advantage of the high stability of Al porphyrin complexes (Supplementary Fig.\u0026nbsp;63). Accordingly, the loading of the primary catalyst, \u003cb\u003esBFPC-1\u003c/b\u003e, and control catalysts, \u003cb\u003esSC-1\u003c/b\u003e, \u003cb\u003esPC-1\u003c/b\u003e and \u003cb\u003esBFPC\u0026rsquo;-1\u003c/b\u003e were calculated to be 13.0, 12.3, 15.1 and 17.2 \u0026micro;mol Al/g respectively (Supplementary Scheme 7, Supplementary Tables\u0026nbsp;1\u0026ndash;2). These values are closely aligned, facilitating performance comparison.\u003c/p\u003e\u003c/div\u003e\n\u003ch3\u003eEvidence of stretching state\u003c/h3\u003e\n\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe polymer chains in supported polymeric catalysts tend to move away from the surface under polar conditions. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea,b, \u003cb\u003esBFPC-1\u003c/b\u003e sedimented rapidly (\u0026lt;\u0026thinsp;1min) when dispersed in non-polar solvent CHCl\u003csub\u003e3\u003c/sub\u003e, while the suspension remained stable in polar solvent CH\u003csub\u003e3\u003c/sub\u003eOH (\u0026gt;\u0026thinsp;10 min), indicating the extended state of the polymer chains. These results suggest that the weak interaction between the residual surface silanol and Al porphyrin can be disrupted under polar conditions. The adsorption and desorption processes were further monitored through \u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003eH NMR analysis of the monomeric Al porphyrin (\u003cb\u003eM-TPPAl\u003c/b\u003e) and silica (\u003cb\u003eSiO\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e-N\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e) mixture (Supplementary Fig.\u0026nbsp;64). A decrease and blurring of proton signals of \u003cb\u003eM-TPPAl\u003c/b\u003e were observed by addition of \u003cb\u003eSiO\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003e-N\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e in CDCl\u003csub\u003e3\u003c/sub\u003e, while these signals recovered upon the addition of a drop of CD\u003csub\u003e3\u003c/sub\u003eOD. These findings indicate that polar conditions drive the metal complex away from the support surface.\u003c/p\u003e\u003cp\u003eThe chain extension of supported polymeric catalysts was directly visualized under polar conditions using cryo-transmission electron microscope (cryo-TEM) (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec,d,e,f). By rapidly freezing supported catalyst suspensions (2 mg/mL in DMSO) with high thermal conductivity liquid ethane (m.p. -183\u0026deg;C) to preserve their conformation in the liquid state\u003csup\u003e\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u003c/sup\u003e, the cryo-TEM analysis revealed various spherical morphologies. By counting\u0026thinsp;\u0026gt;\u0026thinsp;100 nanoparticles, the supported polymeric catalysts \u003cb\u003esBFPC-1\u003c/b\u003e (37.6 nm) and \u003cb\u003esPC-1\u003c/b\u003e (35.1 nm) exhibited larger average diameters than \u003cb\u003esSC-1\u003c/b\u003e (19.3 nm) and \u003cb\u003esBFPC\u0026rsquo;-1\u003c/b\u003e(20.8 nm). These dates further confirm that extended polymeric chains spatially separate the molecular complex from the surface, while shorter linkers confine them to the surface.\u003c/p\u003e\u003cp\u003eThe influence of the support on the metal complex is significantly reduced in the stretched state. We ingeniously utilized a lyophilization process to preserve stretched state of suspensions in DMSO as much as possible for XPS testing. Unlike the nearly identical Al 2\u003cem\u003ep\u003c/em\u003e binding energies of the homogeneous precursors \u003cb\u003eSC\u003c/b\u003e (74.74 eV), \u003cb\u003ePC\u003c/b\u003e (74.71 eV), \u003cb\u003eBFPC\u003c/b\u003e (74.62 eV), and \u003cb\u003eBFPC\u0026rsquo;\u003c/b\u003e (74.66 eV), all supported catalysts exhibited Al 2\u003cem\u003ep\u003c/em\u003e peaks that shifted to lower binding energies (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eg,h,I,j), suggesting the presence of residual silanol coordination to Al center. However, \u003cb\u003esBFPC-1\u003c/b\u003e and \u003cb\u003esPC-1\u003c/b\u003e showed smaller shifts (0.19 and 0.42 eV, respectively) compared to \u003cb\u003esBFPC\u0026rsquo;-1\u003c/b\u003e and \u003cb\u003esSC-1\u003c/b\u003e (0.55 eV and 0.60 eV, respectively). These results confirm that the stalked crinoid-inspired strategy minimizes the detrimental effects of the support on the molecular metal complex.\u003c/p\u003e\u003cp\u003eThe dynamic behavior of surface solvents is critically influenced by the conformational states\u0026mdash;collapsing or stretching\u0026mdash;of supported polymeric catalysts\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e. Solvent relaxation NMR has proven to be a valuable technique for investigating these interactions\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e, with detailed principles outlined in Supplementary Scheme 8. Using a single-exponential decay model, the spin-spin relaxation time (\u003cem\u003eT\u003c/em\u003e\u003csub\u003e2\u003c/sub\u003e) was measured to calculate the average relaxation rate (\u003cem\u003eR\u003c/em\u003e\u003csub\u003eav\u003c/sub\u003e = 1/\u003cem\u003eT\u003c/em\u003e\u003csub\u003e2\u003c/sub\u003e). A useful parameter is the specific relaxation rate, \u003cem\u003eR\u003c/em\u003e\u003csub\u003esp\u003c/sub\u003e, which is defined as \u003cem\u003eR\u003c/em\u003e\u003csub\u003eav\u003c/sub\u003e/\u003cem\u003eR\u003c/em\u003e\u003csub\u003ef\u003c/sub\u003e-1, where \u003cem\u003eR\u003c/em\u003e\u003csub\u003ef\u003c/sub\u003e represents the relaxation rate of the free solvent (blank control) \u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e. A smaller \u003cem\u003eR\u003c/em\u003e\u003csub\u003esp\u003c/sub\u003e indicates faster overall solvent mobility. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ek, for catalyst dispersions (10 mg/mL in ethanol), the results revealed distinct orders of \u003cem\u003eR\u003c/em\u003e\u003csub\u003esp\u003c/sub\u003e: \u003cb\u003esSC-1\u003c/b\u003e (1.07)\u0026thinsp;\u0026gt;\u0026thinsp;\u003cb\u003esBFPC\u0026rsquo;-1\u003c/b\u003e (0.33)\u0026thinsp;\u0026gt;\u0026thinsp;\u003cb\u003esBFPC-1\u003c/b\u003e (0.22)\u0026thinsp;\u0026asymp;\u0026thinsp;\u003cb\u003esPC-1\u003c/b\u003e (0.21). These findings suggest that solvent movement is severely restricted near \u003cb\u003esSC-1\u003c/b\u003e surface and moderate for \u003cb\u003esBFPC\u0026rsquo;-1\u003c/b\u003e, and demonstrates the fastest mobility for \u003cb\u003esBFPC-1\u003c/b\u003e and \u003cb\u003esPC-1\u003c/b\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003el). The terminal anchor groups in \u003cb\u003esBFPC-1\u003c/b\u003e and \u003cb\u003esPC-1\u003c/b\u003e maximize the freedom of the molecular complexes\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e, facilitating less hindered solvent movement through extended chain conformations.\u003c/p\u003e\n\u003ch3\u003eTelomerization of CO and epoxides\u003c/h3\u003e\n\u003cp\u003eTo validate our catalyst design strategy, we conducted the telomerization of PO and CO\u003csub\u003e2\u003c/sub\u003e to produce CO\u003csub\u003e2\u003c/sub\u003e-polyols using protic CTAs such as acids and alcohols (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea). The resulting CO\u003csub\u003e2\u003c/sub\u003e-polyols, which feature a tunable carbonate/ether coexisting structure (Supplementary Scheme 9), represent an excellent option for potential large-scale utilization of CO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e35\u003c/sup\u003e. This approach not only reduces greenhouse gas emission and conserves fossil resources\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e, but it can also provide high-quality polyurethanes by reacting with isocyanates\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e, \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. Generally, previous studies have shown that catalytic performance declines significantly at high CTA loadings as carefully summarized in Supplementary Schemes 10-11\u003csup\u003e39\u0026minus;42\u003c/sup\u003e, primarily due to the poisoning effect of CTAs on the metal center\u003csup\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. Therefore, the development of highly efficient and reusable catalysts is desirable for large-scale applications.\u003c/p\u003e\u003cp\u003eThrough prescreening the polymerization conditions (Supplementary Table\u0026nbsp;3), the optimized telomerization of PO/CO\u003csub\u003e2\u003c/sub\u003e using supported catalysts was performed at a ratio of [Al]/CTA/PO\u0026thinsp;=\u0026thinsp;1/2,000/200,000 under 70\u0026deg;C and 3 MPa of CO\u003csub\u003e2\u003c/sub\u003e pressure for 36 h using sebacic acid (SA) as a modal CTA (entries 1\u0026ndash;6, Supplementary Table\u0026nbsp;4). Notably the porphyrin unit in the four supported catalysts displayed tight H-aggregation in the dispersion even at 90\u0026deg;C (Supplementary Fig.\u0026nbsp;61), indicating strong molecular interactions\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e. We were pleased to find that \u003cb\u003esBFPC-1\u003c/b\u003e achieved a high activity of 7.2 kg polyols/g [Al] (Al porphyrin) (corresponding to TOF of 2500 h\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) with a polymer selectivity of 97% and a carbonate unit content of 35% (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb, Supplementary Fig.\u0026nbsp;65). This performance surpassed that of previously reported homogeneous catalysts (Supplementary Scheme 11), demonstrating the effectiveness of the stalked crinoid-inspired strategy. Importantly, in the absence of CTA, \u003cb\u003esBFPC-1\u003c/b\u003e afforded lower productivity (5.4 kg polyols/g [Al]) and polymer selectivity (91%) (entry 6, Supplementary Table\u0026nbsp;3), attributed to insufficient stretching of the polymeric catalyst chain without polar stimulation.\u003c/p\u003e\u003cp\u003eUnder cocatalyst-free conditions, the activity of \u003cb\u003esSC-1\u003c/b\u003e, \u003cb\u003esPC-1\u003c/b\u003e and \u003cb\u003esBFPC\u0026rsquo;-1\u003c/b\u003e was relatively low, showing values of 0.3, 3.0 and 3.5 kg polyols/g [Al] respectively, while still maintaining high polymer selectivity. The addition of equimolar bis(triphenylphosphine)iminium chloride (PPNCl) as cocatalyst based on Al porphyrin enhanced the activity of \u003cb\u003esSC-1\u003c/b\u003e and \u003cb\u003esPC-1\u003c/b\u003e to 1.3 and 5.8 kg polyols/g [Al], respectively (entries 5\u0026ndash;6, Supplementary Table\u0026nbsp;4), although this improvement came at the cost of approximately 10% polymer selectivity for \u003cb\u003esPC-1\u003c/b\u003e. The external cocatalyst increased activity but also facilitated the back-biting of the growing chain, leading to the formation of the byproduct cyclic propylene carbonate (cPC) \u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e. Furthermore, recycling the external cocatalyst is challenging, which may impact the utility of downstream products and elevate separation costs. These results underscore the advantages of supported bifunctional polymeric catalysts for the preparation and separation of CO\u003csub\u003e2\u003c/sub\u003e-polyols.\u003c/p\u003e\u003cp\u003eUnlike conventional heterogeneous catalysts, \u003cb\u003esBFPC-1\u003c/b\u003e demonstrated exceptional control over product structure. The polymer dispersity index (\u003cem\u003eĐ\u003c/em\u003e) of CO\u003csub\u003e2\u003c/sub\u003e-polyols was precisely regulated at 1.06 with a molecular weight comparable to the theoretical value (2.7 vs. 3.4 kg/mol) (Supplementary Table\u0026nbsp;4). In contrary, \u003cb\u003esSC-1\u003c/b\u003e and \u003cb\u003esBFPC\u0026rsquo;-1\u003c/b\u003e produced polyols with broad dispersity (\u003cem\u003eĐ\u003c/em\u003e \u0026gt;1.2) (Supplementary Fig.\u0026nbsp;66), similar to the behavior of traditional heterogeneous catalyst double metal cyanide (DMC) complexes\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e. Additionally, \u003cb\u003esPC-1\u003c/b\u003e required the addition of cocatalyst to achieve a narrow \u003cem\u003eĐ\u003c/em\u003e of 1.05. These results can be elucidated by solvent relaxation NMR, which indicates that the extended conformation of catalysts \u003cb\u003esBFPC-1\u003c/b\u003e and \u003cb\u003esPC-1\u003c/b\u003e facilitated a more rapid exchange between active and dormant polymer chains compared to catalysts in a more compact position, due to enhanced mass transfer efficiency.\u003c/p\u003e\u003cp\u003eTo further illustrate the advantages of supported polymeric catalysts, control supported single-site catalysts with varying loadings (12.3\u0026ndash;95.5 \u0026micro;mol Al/g) and different lengths of alkyl linkers (\u003cb\u003esSC-y\u003c/b\u003e, where \u003cb\u003ey\u003c/b\u003e\u0026thinsp;=\u0026thinsp;\u003cb\u003e2\u003c/b\u003e, \u003cb\u003e3\u003c/b\u003e, \u003cb\u003e4\u003c/b\u003e, \u003cb\u003e5\u003c/b\u003e, \u003cb\u003e6\u003c/b\u003e) were synthesized (Supplementary Table\u0026nbsp;5). To ensure sufficient monomer conversion, the telomerization conditions were adjusted to [Al]/SA/PO\u0026thinsp;=\u0026thinsp;1/100/10,000. However, the catalytic performance of these supported single-site catalysts was minimally affected, exhibiting comparable productivity (0.26\u0026ndash;0.40 kg polyols/g [Al]) and a broad \u003cem\u003eĐ\u003c/em\u003e (1.4\u0026ndash;2.5). This again highlights the challenges of systematic tunability of supported single-site catalysts due to the random distribution of active sites.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThe loading density of polymeric catalyst has a significant effect on catalytic performance (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec, Supplementary Table\u0026nbsp;4). Compared to \u003cb\u003esBFPC-1\u003c/b\u003e (13.0 \u0026micro;mol Al/g, moderate loading), both \u003cb\u003esBFPC-2\u003c/b\u003e (2.1 \u0026micro;mol Al/g, low loading) and \u003cb\u003esBFPC-3\u003c/b\u003e (38.0 \u0026micro;mol Al/g, high loading) exhibited inferior performance, yielding 2.7 and 5.4 kg polyols/g [Al] with polymer selectivity of 87% and 92%, respectively. The analysis of the UV-vis spectrum of porphyrin units serves as a powerful tool for studying the interactions of polymeric catalysts in a suspended state (Supplementary Fig.\u0026nbsp;62). The decreased shoulder peak (405 nm) for \u003cb\u003esBFPC-2\u003c/b\u003e suggests weak interpolymeric chain synergy\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e, \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e, while the red-shifted Soret band (422 nm) for \u003cb\u003esBFPC-3\u003c/b\u003e indicates the formation of less-active J aggregates\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e. The moderate loading of \u003cb\u003esBFPC-1\u003c/b\u003e enables optimized synergies and reduced steric hindrance for the porphyrin active sites\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003eOur strategy enables \u003cb\u003esBFPC-1\u003c/b\u003e to achieve performance levels comparable to those of the homogeneous analogue (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed, Supplementary Table\u0026nbsp;6). Notably, \u003cb\u003esBFPC-1\u003c/b\u003e displayed exceptional proton-enhanced activity, achieving an unprecedented productivity of 62.4 kg polyols/g [Al] under a molar ratio of [Al]/SA/PO\u0026thinsp;=\u0026thinsp;1/160,000/800,000 for 144 h (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed). This performance benefits from the ultrahigh proton tolerance (320,000 protons) and resistance to dilution effects (0.000125 mol [Al]%), significantly surpassing previous reports (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ee) \u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e, \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e, \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e. Additionally, the molecular weight was well-controlled to ultralow values (0.6 kg/mol) with a narrow \u003cem\u003eĐ\u003c/em\u003e (\u0026lt;\u0026thinsp;1.1) and an adjusted carbonate unit (30\u0026ndash;60%) (Supplementary Fig.\u0026nbsp;67), inheriting the merits of the parental catalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ef, Supplementary Table\u0026nbsp;7). Furthermore, \u003cb\u003esBFPC-1\u003c/b\u003e is broadly applicable to various CTA (Supplementary Table\u0026nbsp;8) and epoxides (Supplementary Table\u0026nbsp;9) with different architectures, where stronger acidity correlates with higher activity (Supplementary Figs.\u0026nbsp;68\u0026ndash;69), further demonstrating its excellent proton tolerance. All these CO\u003csub\u003e2\u003c/sub\u003e-polyols were characterized using MALDI-TOF-MS spectra (Supplementary Figs.\u0026nbsp;70\u0026ndash;77).\u003c/p\u003e\u003cp\u003eThe reusability of \u003cb\u003esBFPC-1\u003c/b\u003e was evaluated by a 5 L autoclave at the ratio of [Al]/SA/PO\u0026thinsp;=\u0026thinsp;1/40,000/200,000 at 70\u0026deg;C and 3 MPa of CO\u003csub\u003e2\u003c/sub\u003e for 36 h, utilizing 10 g supported catalyst, 2 L PO and 1.16 kg SA (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eg, Supplementary Table\u0026nbsp;10). The process achieved 67% PO conversion and \u0026gt;\u0026thinsp;99% polymer selectivity, yielding a productivity of 19.5 kg polyols/g [Al]. Due to the absence of by-product (cPC), the catalyst was facilely recovered from CO\u003csub\u003e2\u003c/sub\u003e-polyols through centrifugation and evaporation of low-boiling point PO (32\u0026deg;C), giving a light-green catalyst and a nearly colorless oily product. Notably, the product contained negligible Al content (~\u0026thinsp;0.2 ppm), demonstrating the high stability of the supported polymeric catalysts. The catalyst can be reused at least 3 times without compromising product architecture (\u003cem\u003eĐ\u003c/em\u003e \u0026lt; 1.1), polymer selectivity (~\u0026thinsp;99%) and productivity (18.2 kg polyols/g [Al]) (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eh), deriving from the integrity of the spherical morphology (Supplementary Fig.\u0026nbsp;78).\u003c/p\u003e\n\u003ch3\u003ePossible mechanism for proton-enhanced polymerization\u003c/h3\u003e\n\u003cp\u003eThe proton-enhanced catalytic performance of \u003cb\u003esBFPC-1\u003c/b\u003e, which differs from conventional systems (proton-deactivated polymerization), prompts us to explore the underlying mechanisms. Owing to the heterogeneous nature of supported catalysts, homogeneous analogues were utilized to elucidate the catalytic process. Additionally, trifluoroacetic acid (TFA) was strategically selected as CTA, as it can be further verified by \u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003eF NMR.\u003c/p\u003e\u003cp\u003eInterestingly, when a mixture of \u003cb\u003eM-TPPAl\u003c/b\u003e/TFA/PO (1/2/5) was combined in CDCl\u003csub\u003e3\u003c/sub\u003e, obvious signal shifts of TFA (trifluoromethyl, Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea) and PO (epoxy group, Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb) were observed. These shifts were attributed to the shielding effect of Al porphyrin (Supplementary Fig.\u0026nbsp;79), which only occurred in the presence of CTA (Supplementary Fig.\u0026nbsp;80) during NMR titration experiments of TFA with \u003cb\u003eM-TPPAl\u003c/b\u003e/PO (1/5). Variable temperature \u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003eF NMR further demonstrated two distinct types of TFA signals (approximately 1:1) at low temperatures (213 K) (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec), which experienced different shielding effects, possibly due to varying distances from the porphyrin plane. The resulting species was likely a hexa-coordinated\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e dicarboxylate aluminum complex, accompanied by hydrogen-bonding activated PO, where the Soret band showed a redshift from 420 nm (without TFA) to 422 nm (with TFA) (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). This coordination pattern was also suitable for other CTAs (Supplementary Figs.\u0026nbsp;81\u0026ndash;82), with stronger acidity leading to higher activation of PO (Supplementary Fig.\u0026nbsp;83) and greater binding affinity to Al porphyrin (Supplementary Fig.\u0026nbsp;84). The hexa-coordinated dicarboxylate Al complex was also observed in the presence of sterically hindered organic bases (Supplementary Figs.\u0026nbsp;85\u0026ndash;89), which acted as hydrogen bond receptors to enhance the nucleophilicity of residual CTA/chain end\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eIn addition to the new monomer activation pattern, the high local concentration of active sites is crucial for achieving impressive catalytic performance. Reducing the distance between Al porphyrin is a top priority, as homogeneous monomolecular Al porphyrin exhibits minimal activity in the presence of substantial CTA (Supplementary Table\u0026nbsp;11). The increased local concentration, originating from the confinement of polymer chains and moderate immobilization, facilitates both interchain and intrachain synergies within the supported polymeric catalyst (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ee)\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e. The covalently linked organic base sustains the local activation of the CTA/chain end, further enhancing catalytic performance. The simultaneous activation of both the monomer and CTA/chain end in proximity combines the advantages of optimal perfromance\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e, \u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eWe have successfully addressed the long-standing challenge of preparing highly active supported catalysts. Unlike traditional methods that immobilize molecular metal complex/cocatalyst onto a support via a short linker, we developed a biomimetic approach in which polymeric catalysts with active sites decorated on pendants are grafted to the surface. Notably, when triggered by proton CTA, our supported polymeric catalyst adopted an upright posture, with active centers extending into the reaction medium and swaying like stalked crinoids in the current, greatly mitigating the detrimental effects of support surface on the metal center. In the telomerization of CO\u003csub\u003e2\u003c/sub\u003e and epoxides, the optimal \u003cb\u003esBFPC-1\u003c/b\u003e exhibits impressive productivity (62.4 kg polyols/g Al porphyrin) and selectivity (99%) under extremely dilute conditions (0.000125 mol [Al]%, 17.8 ppm), which can be reused at least three times. Mechanistic studies indicate that the extraordinary proton tolerance (320,000 equiv. to [Al]) results from an activation pattern of epoxy by the protons of coordinated CTA/chain end. Beyond this proof-of-concept work, our research highlights a robust and feasible strategy for enhancing various supported catalysts, which are essential for practical applications.\u003c/p\u003e"},{"header":"Methods","content":"\u003cp\u003e\u003cstrong\u003eGeneral procedure for homogeneous polymeric Al porphyrin\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe polymeric porphyrin ligand was prepared through RAFT polymerization. Generally, monomeric porphyrin ligand\u0026nbsp;(\u003cstrong\u003eM-TPP\u003c/strong\u003e) (1 g, 1.07 mmol), MMA (0.214 g, 2.14 mmol), 2-(dimethylamino)-ethyl methacrylate (DMAEMA) (0.336 g, 2.14 mmol), RAFT agent (46 mg, 0.107 mmol), AIBN (9 mg, 0.05 mmol) were dissolved in THF (20 mL). After degassed, the mixture was heated to 65 °C for 48 h. After cooling to room temperature, the mixture was centrifuged in cold diethyl ether and washed by cold diethyl ether for 3 times. The ligand was dried under vacuum at 80 °C. Then in the glove box, the ligand was dissolved in CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e and metallized with AlEt\u003csub\u003e2\u003c/sub\u003eCl. After completion of metallization, the solvent was removed in vacuo to give \u003cstrong\u003eBFPC\u003c/strong\u003e. \u003cstrong\u003ePC\u003c/strong\u003e and \u003cstrong\u003eBFPC’\u003c/strong\u003e were prepared by similar processes.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eGeneral procedure for supported catalysts\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe homogeneous Al porphyrin was supported through azide-alkyne click chemistry. Generally, \u003cstrong\u003eSiO\u003csub\u003e2\u003c/sub\u003e-N\u003csub\u003e3\u003c/sub\u003e\u003c/strong\u003e (0.5 g), homogeneous catalyst (0.05 g), CuBr (0.01 g, 0.07 mmol), PMDETA (0.025 g, 0.14 mmol) were added into a round-bottom flask. Then 10 mL DMF (10 mL) was injected under nitrogen. The mixture was dispersed by sonication and stirred for 24 h. The Immobilized catalyst was separated by centrifugation and washed by CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e/CH\u003csub\u003e3\u003c/sub\u003eOH (V/V, 10/1) and then dried under vacuum at 80 °C.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eGeneral procedure for telomerization of CO\u003csub\u003e2\u003c/sub\u003e and epoxide\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eGenerally, in a glove box, the desired supported catalyst, CTA and PO (4.0 mL) was added into a pre-dried 10 mL autoclave with a magnetic stir. Then the autoclave was taken out of the glove box followed by pressurized with CO\u003csub\u003e2\u003c/sub\u003e and the mixture was stirred at the desired temperature for a necessary time. After cooling to room temperature, release CO\u003csub\u003e2\u003c/sub\u003e and a small aliquot of the mixture were taken out for \u003csup\u003e1\u003c/sup\u003eH NMR and GPC analysis. For the viscous crude mixtures, dilution was carried out by adding CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e, followed by centrifugation to separate the supported catalysts. Small amount of cyclic propylene carbonate (cPC, byproduct) was removed by aqueous washing. Low-boiling point PO and/or CH\u003csub\u003e2\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003e were removed under vacuum. The recycled supported catalysts were washed by CH\u003csub\u003e3\u003c/sub\u003eCN/CH\u003csub\u003e3\u003c/sub\u003eCO\u003csub\u003e2\u003c/sub\u003eH (V/V, 50/1) three times and dried at 70 °C under vacuum and then reused.\u003c/p\u003e\n\u003cp\u003e50 mL and 75 mL autoclaves were used when the telomerizations were performed at dilution effects (Supplementary Table 6). 5 L autoclave was used for reaction amplification.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the National Natural Science Foundation of China (Grant Nos. 51988102). We thank W.F. at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, for the cryo-TEM tests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eC.L., S.L., and X.W. conceived the idea. C.L. and S.L. designed the experiments. 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Soc.\u003c/em\u003e \u003cstrong\u003e146\u003c/strong\u003e. 25852-25859 (2024).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7193791/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7193791/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSupported catalysis is considered as an ideal catalytic mode as it combines the advantages of homogeneous catalysis (activity and selectivity) and heterogeneous catalysis (separation and recyclability). However, its application is greatly limited by the loss of catalytic performance after immobilization of molecular catalyst on solid supports. Inspired by the upright feeding posture of stalked crinoids\u0026mdash;characterized by outstretched arms with ordered pinnules extending away from the substrate\u0026mdash;we have addressed this issue by immobilizing of a linear polymer catalyst decorated with aluminum porphyrin on silica. Our catalyst demonstrates remarkable productivity (62.4 kg polyols/g Al porphyrin), polymer selectivity (99%) and proton tolerance (320,000 equiv. to [Al]) under highly dilute conditions (0.000125 mol [Al]%, 17.8 ppm) for bulk telomerization of CO\u003csub\u003e2\u003c/sub\u003e and epoxides, which is greatly improved compared to traditional systems. Furthermore, our catalyst exhibits stability and maintains its catalytic performance after three recycling cycles. This strategy provides a rational approach to designing highly efficient supported catalysts.\u003c/p\u003e","manuscriptTitle":"Biomimetic supported catalyst inspired by stalked crinoid","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-09-18 09:43:51","doi":"10.21203/rs.3.rs-7193791/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"b220f7c6-d0c6-421d-b58a-5e7029bf0fad","owner":[],"postedDate":"September 18th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[{"id":53572169,"name":"Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis"},{"id":53572170,"name":"Physical sciences/Chemistry/Polymer chemistry/Polymer synthesis"}],"tags":[],"updatedAt":"2025-09-18T09:43:51+00:00","versionOfRecord":[],"versionCreatedAt":"2025-09-18 09:43:51","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7193791","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7193791","identity":"rs-7193791","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}