Low-temperature photocatalytic dry reforming of methane over porous cylindrical, gyroidal, and asymmetric catalyst structures

Low-temperature photocatalytic dry reforming of methane over porous cylindrical, gyroidal, and asymmetric catalyst structures | 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 Low-temperature photocatalytic dry reforming of methane over porous cylindrical, gyroidal, and asymmetric catalyst structures William Moore, Shusaku Shoji, Lieihn Tsaur, Fei Yu, R. Paxton Thedford, and 9 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3830664/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Recent advances in the photocatalytic activation of dry reforming of methane (DRM: CO 2 + CH 4 → 2CO + 2H 2 ) at low temperature and ambient pressure have generated considerable interest as a promising route to convert greenhouse gases into valuable synthetic gas (syngas). While detailed studies have revealed the mechanisms involved in photocatalytic DRM at metal-semiconductor interfaces, less attention has been devoted to how high surface area semiconductor supports may enhance such conversions. Here we structure triblock terpolymer self-assembly directed sol-gel derived transition metal oxide (Ta 2 O 5 or TiO 2 ) supports of Rh-decorated photocatalysts into various equilibrium and non-equilibrium derived porous morphologies and show how they modulate single-pass conversion, total production rate, and material efficiency. Supported by in-depth materials characterization and flow simulations rationalizing observed trends, results reveal record catalyst performance. Our work suggests that asymmetric pore structures simultaneously optimizing mass transport and surface area may be well-suited to maximize photocatalyst performance. Physical sciences/Materials science/Materials for energy and catalysis/Photocatalysis Physical sciences/Materials science/Soft materials/Polymers Physical sciences/Materials science/Materials for energy and catalysis/Porous materials Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction The drastic increase in atmospheric greenhouse gases such as carbon dioxide (CO 2 ) and methane (CH 4 ) is a primary driver of climate change. Dry reforming of methane (DRM: CO 2 + CH 4 → 2CO + 2H 4 ) has been attracting attention as one of the most promising ways to convert CO 2 and CH 4 into a valuable synthesis gas (syngas) consisting of carbon monoxide (CO) and hydrogen (H 2 ) [ 1 , 2 ]. This technology can potentially reduce environmental harms associated with emissions from the extraction and utilization of natural gas, shale gas, biogas, methane hydrates, and other natural resources, while providing a pathway to creating feedstocks for organic chemistry precursors [ 3 – 6 ]. DRM is a highly endothermic reaction (Δ H = + 247 kJ/mol) that traditionally requires temperatures of 800°C or higher to proceed efficiently. Due to these high reaction temperatures, DRM catalysts suffer from deactivation by thermal aggregation of co-catalysts and carbon deposition, limiting their practical use. Recent advances have been made toward photocatalytic, rather than thermally activated, DRM. These systems use metals supported by oxide semiconductors such as Ga 2 O₃, SrTiO 3 , TiO 2 , or CeO 2 , or metal localized surface plasmon resonances in reactant activation [ 7 – 13 ]. Very recently, it has been reported that rhodium nanoparticle-loaded strontium titanate (Rh/SrTiO 3 ) and rhodium intertwined with cerium oxide (Rh#CeO 2 ) considerably exceeded the theoretical thermal catalyst thermodynamic limit by utilizing light rather than heat [ 14 , 15 ]. Mechanistic investigations via isotope studies of the photocatalytic DRM system identified that lattice oxygen in the oxide mediates oxidation, while charge density in the supported metal mediates the reduction of CO 2 , suggesting that the metal-semiconductor interface is key to the photocatalytic reaction. In particular, the Rh#CeO 2 photocatalyst with many exposed nanoscopic metal-semiconductor interfaces exhibited a methane conversion rate exceeding 60% due to the efficient charge separation of photoexcited electron-hole pairs and diffusion of lattice oxygen. The photocatalysts described above were used in the form of non-porous solids, however, thus limiting the accessible surface area per unit volume. Furthermore, despite relatively high reactant conversions, these studies were performed at very low flow rates of dilute reactants, achieving impractically low production rates of CO and H 2 . Here photocatalysts for DRM were developed from porous semiconducting oxides decorated with rhodium metal nanoparticles. To that end, block copolymer self-assembly (BCP SA) directed periodically ordered mesoporous TiO 2 and Ta 2 O 5 supports with hexagonally-packed cylinders (Hex), co-continuous double gyroid (G D ), or alternating gyroid (G A ) morphologies and homogeneous 15–30 nm diameter pores were synthesized from evaporation induced SA (EISA): a (close to) equilibrium process. For comparison, TiO 2 film supports combining asymmetric, hierarchical pore structures across the film normal with well-defined mesoporosity throughout the material were derived from a non-equilibrium BCP SA approach referred to as SNIPS ( s elf-assembly plus n on-solvent i nduced p hase s eparation). Rhodium metal nanoparticles were generated on supports by reduction of rhodium chloride hydrate to rhodium metal. Photocatalytic DRM conversions were studied under light irradiation without external heating, achieving up to 75% (Rh/Ta 2 O 5 -G D ), 78% (Rh/TiO 2 -Film) and 82% (Rh/Ta 2 O 5 -G A ) CO 2 and CH 4 conversion at low flow rates. In concentrated gas at high flow rates, CO/H 2 production rates up to 28,500 mmol / (hr·g) at 9.7% CO 2 /CH 4 conversion were achieved (Rh/TiO 2 -Film). This mass-normalized production rate is more than 400 times higher than that of previous state-of-the-art ambient-temperature photocatalysts. All mesoporous catalysts outperformed commercial non-mesoporous Ta 2 O 5 and TiO 2 powder based catalysts. Furthermore, only moderate performance degradation was observed over a 72-hour long test run for Ta 2 O 5 -G A supports, yielding a turnover frequency of 38,300/hr. Especially at high flow rates, G A and asymmetric film supports demonstrated enhanced single-pass conversions as well as production rates on the bases of mass and surface area over hexagonal and G D supports. With respect to the latter two performance metrics, the asymmetric thin film catalyst substantially outperformed all other samples across all flow rates tested. Results demonstrate the importance of asymmetric hierarchical pore structures that optimize both mass transport and surface area, thereby allowing substantial improvements in DRM photocatalytic reactivity. Results and Discussion Synthesis and characterization of porous supports and metal decorated photocatalysts Seven porous catalyst supports were synthesized for this study from two materials and with four morphologies: mesoporous TiO 2 and Ta 2 O 5 supports with alternating gyroid (G A ), double-gyroid (G D ), and hexagonal-cylindrical (Hex) structures, as well as a porous TiO 2 thin film combining asymmetric, hierarchical pore structures across the film normal with well-defined mesoporosity throughout the material (Figure 1, Materials and Methods) [16]. Gyroidal and hexagonal supports were fabricated via BCP SA with one of two poly(isoprene- block -styrene- block -ethylene oxide) (PI- b -PS- b -PEO or ISO) terpolymers (ISO-1 and ISO-2, Supplementary Table 1), depending on the desired mesostructure: G A from ISO-1; G D and Hex from ISO-2. Structure formation for gyroidal and hexagonal structures occurred overnight via evaporation-induced self-assembly (EISA) at 40°C. The TiO 2 thin film was fabricated via SNIPS using a poly(isoprene- block -styrene- block­- 4-vinyl-pyridine) (PI- b -PS- b -P4VP or ISV) terpolymer (ISV-1, Supplementary Table 1). Hybrid polymer/oxide materials were subsequently heat treated at 130°C for 5 hours in vacuum, followed by calcination in air to remove the ISO or ISV terpolymer and crystallize the oxide phase. TiO 2 and Ta 2 O 5 materials were calcined at 550°C and 700°C, respectively. After calcination, porous supports were characterized via a combination of small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and nitrogen sorption to establish sample structure and porosity (Materials and Methods). The corresponding scattering patterns for the six periodically ordered materials are shown in Figure 2a. The asymmetric SNIPS derived TiO 2 -Film sample lacking mesoscale periodic order was not included in the SAXS analysis. The low signal intensity for all support materials due to the strongly absorbing nature of these crystalline oxides, together with the relatively broad observed peaks, makes assignments to underlying lattices challenging. Tentative indexing of the observed peaks is shown in the figure. The four peaks assigned to samples TiO 2 -G A and Ta 2 O­ 5 -G A are consistent with an alternating gyroid (G A ) lattice with cubic unit cell lattice parameters of 52.3 nm and 44.8 nm, respectively. For sample TiO 2 -G D , the first two indexed peaks of the pattern have been tentatively assigned to a double gyroid lattice with cubic lattice parameter of a = 135.8 nm. For sample Ta 2 O 5 -G D , three of the observed peaks have been tentatively assigned to a double gyroid lattice with cubic lattice parameter a = 94.0 nm. SAXS results for samples TiO 2 -Hex and Ta 2 O 5 -Hex both show a very broad first order peak and one additional higher order reflection tentatively assigned to hexagonal lattices. Associated (10) lattice dimensions, d 10 , were 47.6 nm and 39.8 nm, respectively. Interestingly, although TiO 2 and Ta 2 O 5 samples were synthesized from the same terpolymers, all TiO 2 structures showed patterns shifted to smaller values of q, i.e., larger mesostructure unit cell sizes than Ta 2 O 5 counterparts. This shift is likely due to the higher density of Ta 2 O 5 , resulting in higher degrees of shrinkage during calcination. To corroborate lattice interpretations from SAXS (Table 1), sample mesostructure was further investigated via SEM (Figure 2b-i). Supports were imaged after calcination (to increase contrast), but prior to rhodium deposition. SEM images for G A and G D samples clearly show continuous network morphologies, while those of TiO 2 -Hex and Ta 2 O 5 -Hex both show cylinders, consistent with gyroidal and hexagonally-packed cylinder lattice assignments from SAXS, respectively. In the G A morphology, the d 100 distance can be measured as the distance between the wall of a pore, and the center of the neighboring pore. From the visible [111] projection of the G A samples in Figure 2b, f lattice parameters of d 100 = 51 ± 2 nm for TiO 2 -G A and d 100 = 45 ± 3 nm for Ta 2 O 5 -G A were obtained. These are similar to the respective d 100 values obtained from SAXS (52.3 nm and 44.8 nm). Along the G D structure [211] projection, the width of each row of coils is approximately 80% of the d 100 length, which was determined as d 100 = 132 ±5 nm for TiO 2 and d 100 = 88 ± 6 nm for Ta 2 O 5 from suitably orientated grains in Figure 2c, g [17]. This is again similar to the values for TiO 2 (d 100 = 135.8 nm) and Ta 2 O 5 (d 100 = 94.0 nm) derived from SAXS. SEM images of the respective gyroid structures in Figure 2b, c, f, g have visible features in agreement with simulated projections of these structures (see insets) corroborating the lattice assignments. SEM analysis of the (10) spacing for the hexagonal structures (Figure 2d, h), the distance between rows of pores, yields 48 ± 2 nm and 42 ± 3 nm for the TiO 2 -Hex and Ta 2 O 5 -Hex structures, respectively, consistent with values of 47.6 nm and 39.8 nm from SAXS results. SEM images of the asymmetric TiO 2 film (Figure 2e, i) show a finger-like asymmetric cross-section with mesoporous walls and a mesoporous top surface. In the context of photocatalysis applications, these images collectively suggest that pore accessibility should increase in the following order: hexagonally packed cylinder < networked gyroidal < asymmetric structures. Finally, all seven supports were characterized by quantitative sorption/desorption analyses (Supplementary Discussion, Supplementary Figure 1). Results summarized in Table 1 show systematic decreases in surface area for both TiO 2 - and Ta 2 O 5 -supports across morphologies (G A > G D > Hex) and higher values for TiO 2 as compared to Ta 2 O 5 . Table 1: Summary of structural characterization results for oxide catalyst supports and rhodium particles. BJH pore statistics do not include pores larger than 300 nm, thus the TiO 2 film values marked with asterisks (BET surface area, average pore width, pore volume, and overall porosity) are likely slight underestimations. The seven catalyst supports were decorated with Rh metal nanoparticles via hydrothermal infiltration of Rh and subsequent photoreduction under illumination during catalytic evaluation (Materials and Methods). Resulting metal photocatalysts were characterized by X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS) (Supplementary Figure 2), with quantitative XPS results summarized in Supplementary Table 2. All materials measured were phase-pure and fully crystalline, indicated by the lack of broad amorphous background scattering, with metallic Rh detected on all samples. Ta 2 O 5 supports could be matched to the orthorhombic tantalum oxide lattice structure. TiO 2 supports exclusively showed an anatase titania lattice structure. XPS results confirmed no chemical discrepancies between different structures of each material (Supplementary Figure 2b, d). Corroboratory UV-vis measurements (Supplementary Figure 3) confirmed all oxides have approximately 3 eV band gaps. Samples were not intentionally doped but may have lower than expected band gaps due to either unintentional impurities or the higher surface-to-bulk ratio resulting from the 10-30 nm diameter strut networks. Rhodium particles were fully reduced to the metallic phase, without remnant rhodium chloride precursor detected in XRD, although some remnant Cl was detected in XPS as a low-intensity peak around 200 eV. Oxide crystallite sizes and rhodium particle sizes were calculated via Scherrer analysis from XRD patterns (Supplementary Figure 2a, c). XRD-based structural information for oxide supports and rhodium particles is summarized in Table 1. Oxide crystallite sizes can be compared to oxide domain dimensions as reflected by SEM results (Figure 2b-i). From SEM, the TiO 2 -G A and Ta 2 O 5 -G A structures have ~12 nm thick struts, slightly smaller than the XRD derived crystallite sizes of 14 nm and 18 nm. TiO 2 -G D and Ta 2 O 5 -G D oxide strut dimensions were ~25 nm, larger than the TiO 2 -G D 9 nm crystallite size and close to the ~27-28 nm Ta 2 O 5 XRD crystallite size. SEM derived oxide domain dimensions for both hexagonal supports were also ~25 nm, larger than the XRD based crystallite sizes of ~9 nm and ~18 nm for TiO 2 -Hex and Ta 2 O 5 -Hex, respectively. Oxide crystallite sizes for most samples were therefore either close to (for G D structures) or smaller (for hexagonal structures) than the associated oxide domain dimensions. Slightly larger domain sizes in G A structures without loss of mesostructure may suggest elongation of crystallites along the sample strut direction. All this is consistent with periodic mesoscale structure retention after high temperature thermal processing, as substantial crystalline overgrowth beyond the confinement of BCP SA directed nanoscale domains is typically associated with loss of mesoscale structure. TEM micrographs were collected for the three most active catalyst supports (TiO 2 -Film and G A catalysts, vide infra ) to confirm the presence of metallic rhodium. Figure 3a-c show open pore networks for all structures, including the TiO­ 2 -Film (Figure 3c) which is likely a fragment from the more-ordered top surface layer. The micrograph of the TiO 2 -G A structure (Figure 3b) suggests slightly improved periodic order relative to the Ta 2 O 5 -G A material (Figure 3a), consistent with the slightly improved peak definition observed in its SAXS pattern (Figure 2a). Figure 3d-f depicts high-magnification images of the same structures revealing lattice spacings (see insets) that can be indexed to Rh metal (200) and various oxide lattice planes. Results agree with earlier XRD and XPS datasets suggesting the presence of metallic Rh in catalyst samples. Photocatalytic DRM Photocatalysts were evaluated in a flow-through setup (Materials and Methods). Feed gas streams of either 1%/1%/98% or 10%/10%/80% CH₄/CO₂/Ar were delivered to the photocatalysts at flow rates of 0.2-2.1 mmol / hr for the 1% feed gas and 2.5-25 mmol / hr for the 10% feed gas. A large range of flow rates was used to enable a more comprehensive investigation of catalyst behavior relative to singe flow rate studies. The gyroidal and hexagonal catalyst materials were held in a quartz glass reactor (Supplementary Figure 4a), while the TiO 2 film was held in a top-loading brass reactor designed to accept samples in a film geometry (Supplementary Figure 4b and 5). Both reactors were illuminated by a 300W Xe lamp (Supplementary Figure 6) and oriented to make the reactant gas incident to the top illuminated surface. For a performance comparison of both reactors, please see Materials and Methods section. Products were measured with a gas chromatograph (Supplementary Figure 7). Volumetric flow rates ranged from 10-100 mL / min for each gas concentration. Conversion (%) is defined as the amount of products generated relative to the complete conversion of all reactants to products. Figure 4a-c shows the photocatalytic DRM performance of all seven materials. At the lowest 0.25 mmol / hr feed rate, maximum conversions for the highest performers Ta 2 O 5 -G A , TiO 2 -Film, and Ta 2 O 5 -G D were 81.6%, 77.8% and 75.1%, respectively. These conversion values all exceeded the 50-64% conversion by the most active DRM room-temperature photocatalysts to date, i.e., Rh/SrTiO 3 and Rh#CeO 2 nanocomposites [14,15]. The G A and thin film catalysts exhibit a similar flow-rate dependence above 1 mmol / hr, with both types of catalyst supports showing conversions that outpace the performance of all other samples. Both the G A and asymmetric film catalysts are templated by terpolymers with only ~7-12 vol% hydrophilic blocks (as compared to ~46% for all other structures, Supplementary Table 1), consistent with more accessible surface area of openly porous materials compared to the other catalysts. Since the asymmetric thin film catalyst has ~50x less mass (Supplementary Figure 5) for the same illuminated area than other materials tested, its mass-normalized performance shows a record photocatalytic mass activity (Figure 4b), substantially outperforming all other samples across all flow rates tested in this performance metric. The two catalysts with G A morphology outperform all other equilibrium derived and periodically ordered photocatalysts in this metric (especially above a flow rate of ~1 mmol / hr) due to their high-porosity-derived reduced density. Typical plateaus in production occur at 10 mmol / hr for Hex / G D catalysts, 10-20 mmol/hr for G A catalysts, and 20 mmol / hr for the asymmetric TiO 2 film (Figure 4b). For both studied oxides, surface area was significantly higher for the gyroidal supports as compared to their hexagonal counterparts (Table 1). But using the performance metric of production per surface area, the asymmetric film also comes out on top by a large margin across all flow rates tested (Figure 4c). Due to the inability of the BJH method to characterize pores larger than 300 nm, the measured surface area of the asymmetric TiO 2 film is likely slightly underestimated. But since the surface area of the limited number of >300 nm macropores is minute compared to that of the many < 50 nm mesopores, this overestimation cannot account for the large margin by which the TiO 2 film outperforms the remaining structures on a surface-area-normalized basis. Within the family of equilibrium derived periodically ordered catalysts, when normalized to the internal (BET) surface area, the production rates of tantalum oxide-based catalysts are higher than those of their titania counterparts across all flow rates measured. In part, this performance difference results from TiO 2 ’s higher surface area, around a factor of 3 across all morphologies (Table 1). Other contributing effects (e.g., side reactions) are discussed in the Supplementary Information. Within the set of samples for each oxide, at slow feed rates ( 2 mmol / hr), the surface-area-normalized production rates of catalysts with G A morphology increasingly outperform those of catalysts with either hexagonal or G D morphology (by 2-3x at 20 mmol / hr). A durability test was conducted over 72 hours with photocatalyst Ta 2 O 5 -G A at its maximum mass-normalized reaction condition, i.e., at a high flow rate of 18.5 mmol / hr (Supplementary Figure 8). Photocatalyst performance only moderately declined to ~75% of its initial activity over the 72hr time period, reaching a turnover frequency, defined as mole of CO and H 2 (averaged) produced per mole of Rh over time, of 38,320 / hr or 10.6 / s. Additional comparisons to the porous catalysts were performed with commercial non-porous Ta 2 O 5 and TiO 2 particle powder catalysts (Supplementary Figure 9, Supplementary Table 3). These reference results verify that the used reactors adequately reproduce the performance of reference catalysts relative to the literature. As expected, all porous catalysts outperform the non-porous catalysts in percentage of reactants converted, mass-normalized production, and surface-area-normalized production (Supplementary Figure 9a-c). The product ratio between CO and H 2­ as a function of flow rate is shown in Figure 4d. Notably, the CO/H 2 ratio substantially changed with feed gas concentration, with ratios below and above 1 for feed gas concentrations of 1% and 10% CH 4 /CO 2 , respectively. Overall, there seems to be qualitatively different behavior for tantalum oxide and titania based photocatalysts, with product ratios at high flow rates (>2 mmol / hr) converging towards 1 for tantalum oxide-based catalysts, while those of titania diverge towards a higher CO to H 2 ratio in the product stream. The asymmetric TiO 2 film catalyst is the exception to this rule as its behavior converges towards 1, similar to the tantalum oxide-based materials. For further in-depth analysis and discussion of this behavior, we refer to the supplementary information (Supplementary Discussion; Supplementary Table 4). Figure 4e and Supplementary Table 3 provide an overall comparison of the (meso-) porous catalysts studied in this work to published works in photocatalytic and photo-thermal DRM in the form of a bar chart of production per illuminated area (spot size). This measure of performance is relevant for photocatalyst deployment since reactor design is primarily limited by the illuminated area of the catalyst, rather than its mass. Notably, Rh/TiO 2 -G A can be directly compared to a non-structured powder Rh/TiO 2 catalyst [15], where Rh/TiO 2 -G A demonstrates both a higher maximum reactant conversion (50.3% vs 20.7%) and a 240x improvement in the maximum measured production per illuminated area. Mesostructure variations alone account for this substantial uplift in both single-pass conversion and maximum production for Rh/TiO 2 . The highest activity catalyst studied, the asymmetric TiO 2 film, demonstrated a 719x improvement over the previously studied room-temperature Rh/TiO 2 catalyst in terms of production per illuminated area. This performance metric is not affected by the very low mass of the thin film, rather, the highly porous material and hierarchical pore network drove improvements in both conversion and production over all other TiO 2 structures studied. When normalized by mass, the asymmetric TiO 2 film achieved between 150-1500x improvements (depending on flow rate) compared to previously studied Rh/TiO­ 2 . Flow simulations were performed to estimate the tortuosity for each of the catalyst structures used (Figure 5, Materials and Methods). Tortuosity in this study is defined as the path length of a simulated gas flow line versus the length of the structure studied. Each of the simulations provided qualitative insights into gas transport through these porous photocatalysts. As expected, of all the equilibrium-based periodically ordered structures tested, the highly porous G A structure with approximately 85% porosity had the lowest simulated tortuosity of T = 1.2 (Figure 5c). The path of gas through this structure would be 1.2x longer than a direct path. Tortuosity is inversely related to diffusivity through catalyst structures, so it follows that the G A structure with the lowest tortuosity has the most advantageous gas flow characteristics for catalysis, and thus the highest activity. The G D structure had an estimated tortuosity of T = 2.0, while the hexagonal structure resulted in an estimate of T = 3.3 (Figure 5a, b). Conceptually, 1-dimensional pores should have about 3x higher tortuosity compared to a 3-D pore network (G A ), which agrees with these estimates. Determining tortuosity in the porous asymmetric thin film structure required a separate approach derived from a previously described method (Materials and Methods) [18]. From associated simulations, tortuosity varied as a function of membrane thickness (Supplementary Figure 10). The top 8 µm mesoporous layer of the film, dominated by BCP SA, has a tortuosity slightly above T = 1.3. However, when averaged over the entire ~100 μm thick asymmetric film (Figure 2i, Supplementary Figure 10), including the essentially open macroporous substructure, tortuosity of the membrane decreases to below T = 1.1, the lowest tortuosity of all catalyst structures studied. This is consistent with the high conversion efficiency of this structure measured in the catalysis experiments (Figure 4). Conclusions Rh metal nanoparticles on semiconducting titanium and tantalum oxide supports with porous periodic alternating gyroid, double gyroid, hexagonally-packed cylinder, and asymmetric thin-film structures were studied to evaluate the impact of pore geometry, connectivity, and asymmetry on photocatalytic DRM at ambient pressure in the absence of external heating. Porous supports were prepared by BCP SA directed sol-gel synthesis from either ISO triblock terpolymers (periodic structures) or an ISV triblock terpolymer (asymmetric films) followed by thermal processing, and Rh metal decoration. A combination of SAXS, WAXS, SEM, TEM, and nitrogen sorption/ desorption characterization demonstrated that the oxide supports had either periodically ordered mesopores or asymmetric hierarchical pore structures exhibiting meso- to macro-porosity derived from equilibrium or non-equilibrium formation processes, respectively. In all cases, oxide crystallization occurred without mesostructure collapse, while Rh metal nanoparticle sizes were significantly smaller than the pore diameters of the oxide supports, preventing pore clogging. Photocatalytic DRM showed conversion rates of over 81% for Ta 2 O 5 -G A and 77% for the asymmetric TiO 2 -Film at low flow rates. At higher flow rates, activity increased, reaching a maximum production rate of over 28,560 mmol / (hr·g) for the TiO 2 -Film, and 780 mmol / (hr·g) for the Ta 2 O 5 -G A structure. To the best of our knowledge, these photocatalysts showed the highest reported activities to date for photocatalytic DRM without external heating. Furthermore, comparing periodic titanium- to tantalum-based oxide mesostructure supports, the latter showed better performance and more optimal DRM product ratios, especially at high flow rates. Comparing samples with different periodic mesopore structures derived from the same material (e.g., Ta 2 O 5 -G A vs Ta 2 O 5 -Hex) demonstrated that details of the pore geometry and connectivity are critical to optimizing photocatalysis. Widely open alternating gyroids with three-dimensionally co-continuous network pore structures enhanced activity, whereas one-dimensional hexagonal pore structures met early performance plateaus. Photocatalytic results align with insights from flow simulations, suggesting that interconnected pores improve gas diffusion dynamics, thereby significantly enhancing performance of photocatalysts for DRM. Additionally, to the best of our knowledge, this first-time study of an asymmetric, hierarchically porous DRM photocatalyst film suggests that such membrane-type structures, combining fast mass transport through (finger-like) macropores and high surface area from mesopores distributed throughout the material, may be well-suited for not only photocatalytic DRM, but also other photocatalytic reactions. Such low-density thin membrane-type catalysts effectively achieve high reactant conversion while minimizing the required mass of expensive metal promoters. While this study focused on improvements in catalytic materials using simple reactor designs, further performance gains should be possible through improved process designs to recycle unreacted gas, advanced reactor designs to minimize unilluminated catalyst, and optimized low-power LED illuminations. We hope that our results of enhancing photocatalytic performance of a given class of catalysts (here: of semiconductor-metal photocatalysts) via fine control over pore geometry, connectivity, and asymmetry in mesoporous supports will stimulate further efforts to not only control atomic level structure but also meso- to macro-structural aspects to develop next generation high-performance reaction systems. Declarations AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (U.W.) and [email protected] (S.S.) Author Contributions S.S. and U.W. conceived this project. W.M. and S.S. contributed equally to the work. S.S. and W.M. conducted materials synthesis, structural analysis, and catalytic testing. P.T. and F.Y. synthesized and analyzed the ISO terpolymers. F.Y and L.T. collected SEM images and performed subsequent image analysis. W.T. assisted with the nitrogen sorption analysis. A.S. performed flow simulations of gyroid and hexagonal structures. M.S.R. constructed the thin-film model and performed flow simulations of the thin-film. A.R. fabricated and donated the top-loading reactor and assisted catalytic testing. U.W. and J.S. continuously reviewed and discussed the materials synthesis/characterization and catalysis results with W.M and S.S. to continuously advance the project. W.M., S.S., and U.W. wrote the manuscript, with input from all co-authors. ACKNOWLEDGMENT S.S. thanks the Kavli Institute at Cornell (KIC) for nanoscale science as well as the Japan Society for the Promotion of the Science (JSPS) for fellowship funding. U.W. and J.S. acknowledge support from NSF (DMR-2307013 to U.W. and CBET-1805400 to J.S.). This work made further use of the Cornell Center for Materials Research Shared Facilities which are supported through the NSF MRSEC program (DMR-1719875). We acknowledge Karl Termini and the Cornell CAS Professional Glass Shop for their contributions to designing and fabricating equipment used in the study. S.S. and W.M. thank Sarah Hesse for fabrication of the ISV terpolymer used in this study. This research used beamline 11-BM (CMS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. The authors thank Peter Beaucage for the collection of this data. 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(2022) doi: 10.1016/j.jechem.2022.04.022 MKS Newport. 6258 Xenon Arc Lamp. https://www.newport.com/p/6258 Fogler. Elements of Chemical Engineering . (2020). Additional Declarations There is NO Competing Interest. Supplementary Files MooreShojiDRMSupplementaryInformation.docx Cite Share Download PDF Status: Posted 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-3830664","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":265868655,"identity":"49445891-b045-45f0-9bc3-a5632825d016","order_by":0,"name":"William Moore","email":"","orcid":"https://orcid.org/0000-0002-0407-5347","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"William","middleName":"","lastName":"Moore","suffix":""},{"id":265868656,"identity":"2d711b17-1400-499f-b669-b91a063100cb","order_by":1,"name":"Shusaku Shoji","email":"","orcid":"","institution":"National Institute of Materials Science","correspondingAuthor":false,"prefix":"","firstName":"Shusaku","middleName":"","lastName":"Shoji","suffix":""},{"id":265868657,"identity":"bb047d93-b0b5-4e8e-9260-e42cf06b7059","order_by":2,"name":"Lieihn Tsaur","email":"","orcid":"https://orcid.org/0000-0002-7120-8453","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"Lieihn","middleName":"","lastName":"Tsaur","suffix":""},{"id":265868658,"identity":"a7bb2bd9-f7e1-4665-bd87-3619bad29f05","order_by":3,"name":"Fei Yu","email":"","orcid":"https://orcid.org/0000-0002-8191-8096","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"Fei","middleName":"","lastName":"Yu","suffix":""},{"id":265868659,"identity":"7d7a60dc-c43b-40c0-8402-dfb07d183adc","order_by":4,"name":"R. Paxton Thedford","email":"","orcid":"https://orcid.org/0000-0003-0811-227X","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"R.","middleName":"Paxton","lastName":"Thedford","suffix":""},{"id":265868660,"identity":"62603673-935e-4241-abc5-893c9cbddf79","order_by":5,"name":"William Tait","email":"","orcid":"https://orcid.org/0000-0001-8932-9416","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"William","middleName":"","lastName":"Tait","suffix":""},{"id":265868661,"identity":"4a6341ec-cdde-4882-8196-1793f12e8ece","order_by":6,"name":"M. Raisi","email":"","orcid":"","institution":"University of Cincinnati","correspondingAuthor":false,"prefix":"","firstName":"M.","middleName":"","lastName":"Raisi","suffix":""},{"id":265868662,"identity":"d4d858a5-be39-4017-81ec-5ec98b684753","order_by":7,"name":"Aniruddha Saha","email":"","orcid":"","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"Aniruddha","middleName":"","lastName":"Saha","suffix":""},{"id":265868663,"identity":"4074e777-b202-4b70-9329-a855280bedd1","order_by":8,"name":"Austin Reese","email":"","orcid":"","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"Austin","middleName":"","lastName":"Reese","suffix":""},{"id":265868664,"identity":"396c767b-0d22-4cd8-9d00-892d5e856f64","order_by":9,"name":"Sol Gruner","email":"","orcid":"https://orcid.org/0000-0002-1171-4426","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"Sol","middleName":"","lastName":"Gruner","suffix":""},{"id":265868665,"identity":"b7ef9a9e-6bb4-4e05-bfed-02f89e239ae2","order_by":10,"name":"Lilit Yeghiazarian","email":"","orcid":"","institution":"University of Cincinnati","correspondingAuthor":false,"prefix":"","firstName":"Lilit","middleName":"","lastName":"Yeghiazarian","suffix":""},{"id":265868666,"identity":"98a8762b-957a-49c4-a402-11a2932309d7","order_by":11,"name":"Sadaf Sobhani","email":"","orcid":"","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"Sadaf","middleName":"","lastName":"Sobhani","suffix":""},{"id":265868667,"identity":"5e0f57ba-f16d-46e4-8992-e8020f2910dc","order_by":12,"name":"Jin Suntivich","email":"","orcid":"https://orcid.org/0000-0002-3427-4363","institution":"Cornell University","correspondingAuthor":false,"prefix":"","firstName":"Jin","middleName":"","lastName":"Suntivich","suffix":""},{"id":265868654,"identity":"7a7dd8e3-d2ce-4a18-b945-d5a2a05fbdc6","order_by":13,"name":"Ulrich Wiesner","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAs0lEQVRIiWNgGAWjYDACCQaGAx/ALObGA0CCKC2MB2eAWYwNRGthPsxDkhaD2z0Gh21qbPLN2RuBWiqsExsIarlzxuBwzrE0y509B4FazqQToeVG7obDuQ2HDQxuJDYcYGw7TKQWS5CW+w+BWv4Rq4URbAvQ+0AGYS2Sd85/ONhzLM3A4AzQYQnH0o0JauG73Zb84UeNjYHB8cMHH3yosZYlqAUVJJCmfBSMglEwCkYBLgAAyzpLEp13L58AAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0001-6934-3755","institution":"Cornell University","correspondingAuthor":true,"prefix":"","firstName":"Ulrich","middleName":"","lastName":"Wiesner","suffix":""}],"badges":[],"createdAt":"2024-01-03 01:10:22","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3830664/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3830664/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":50410616,"identity":"9ab81c91-df6a-45bb-a483-9553893d0a5f","added_by":"auto","created_at":"2024-01-31 06:32:16","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":184411,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic of the synthesis steps for the different types of porous metal oxide supports. (Top) For gyroidal and hexagonal materials, a mixture of ISO triblock terpolymer and Ta or Ti oxide sol nanoparticles undergoes evaporation induced self-assembly (EISA) at 40°C to yield hybrids with alternating gyroid (G\u003csup\u003eA\u003c/sup\u003e), double gyroid (G\u003csup\u003eD\u003c/sup\u003e) or hexagonally packed cylinders (Hex) equilibrium structures. The hybrids are calcined at 550°C (TiO\u003csub\u003e2\u003c/sub\u003e) or 700°C (Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e) for 3hr in air to remove the polymer template and obtain mesoporous oxide supports. (Bottom) For asymmetric TiO\u003csub\u003e2\u003c/sub\u003e films, solutions of ISV triblock terpolymer and TiO­\u003csub\u003e2\u003c/sub\u003e sol are combined, cast onto glass, allowed to partially evaporate, then plunged into water; yielding freestanding polymer-inorganic-hybrid thin films with hierarchical asymmetric large pore structure superimposed onto a mesoporous mesh. Subsequent heat treatment at 550°C yields crystalline TiO\u003csub\u003e­2\u003c/sub\u003e thin film supports. Polyisoprene, polystyrene, polyethylene oxide and poly(4-vinyl-pyridine) blocks are shown in red, green, dark blue and light blue, respectively. On the far right, larger illustrations of the G\u003csup\u003eA\u003c/sup\u003e and asymmetric support structures are shown, with the former emphasizing the open and continuous pore space, and the latter exhibiting a finger-like substructure with large macropores extending from the bottom toward the surface of the universally mesoporous films.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3830664/v1/755495751c51d098827aff32.png"},{"id":50410846,"identity":"7e100ffd-39e5-4fa8-9116-1c8af287d394","added_by":"auto","created_at":"2024-01-31 06:40:16","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":165926,"visible":true,"origin":"","legend":"\u003cp\u003eCharacterization of porous catalyst supports. (a) SAXS results for the gyroidal or hexagonal oxide support materials studied as indicated. For each sample, visible peaks are indexed according to expected peak positions for G\u003csup\u003eA\u003c/sup\u003e, G\u003csup\u003eD\u003c/sup\u003e, or Hex lattices (as indicated). (b-i) SEM micrographs of the catalyst supports studied. Micrographs b, f and c, g are consistent with network morphologies for G\u003csup\u003eA\u003c/sup\u003e and G\u003csup\u003eD\u003c/sup\u003e samples, respectively. Micrographs d, h establish hexagonally packed cylinder morphologies for TiO\u003csub\u003e2\u003c/sub\u003e-Hex and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-Hex samples, respectively. Insets in panels b, f and c, g show simulated [111] projections of a G\u003csup\u003eA\u003c/sup\u003e structure and [211] projections of a G\u003csup\u003eD\u003c/sup\u003e structure, respectively, consistent with distinctive observed features in the associated SEMs. Micrographs e, i show top surface layer and film cross section, respectively, of the asymmetric TiO\u003csub\u003e2\u003c/sub\u003e film support. The micrograph of the top-surface of the TiO­\u003csub\u003e2\u003c/sub\u003e film, e, shows disordered pores in the 20-30 nm regime, while the cross-section, i, shows the 10-20 µm sized macroporous fingers extending almost to the top surface and lined with mesoporous walls (see inset).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3830664/v1/eef6a9dbb7cb47b4b4591934.png"},{"id":50410615,"identity":"4e1ed14e-4321-42b2-8cbe-21baa1c9c82b","added_by":"auto","created_at":"2024-01-31 06:32:16","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":291924,"visible":true,"origin":"","legend":"\u003cp\u003eTEM microscopy characterization of the three most active catalyst supports. TEM micrographs of (a, d) Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e, (b, e) TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e, and (c, f) the TiO\u003csub\u003e2\u003c/sub\u003e-Film materials after catalytic evaluation. (a-c) Lower resolution images of all three structures. The region of the TiO\u003csub\u003e2\u003c/sub\u003e film shown likely stems from the more periodically ordered top-surface layer of the film. (d-f) High-magnification images with indexed lattice spacings for Rh and each oxide. Observed Rh metal particles varied between 2-10 nm in size, highlighting contributions from particles smaller than the average values obtained from XRD peak fitting based Scherrer analysis (Supplementary Figure 2, Table 1).\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3830664/v1/3257ebaa0ee78351cc103937.png"},{"id":50410613,"identity":"323cff41-f141-4671-9948-8fa1c303dc51","added_by":"auto","created_at":"2024-01-31 06:32:16","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":128327,"visible":true,"origin":"","legend":"\u003cp\u003ePhotocatalytic DRM activity of the photocatalysts studied (as indicated). (a) Conversion of CH\u003csub\u003e4\u003c/sub\u003e and CO\u003csub\u003e2\u003c/sub\u003e to CO and H\u003csub\u003e2\u003c/sub\u003e, (b) averaged production of CO and H\u003csub\u003e2\u003c/sub\u003e per gram of catalyst, (c) averaged production per catalyst surface area, (d) and product ratio of CO/H­\u003csub\u003e2\u003c/sub\u003e produced. Data representations are interrupted between 1%/1% CH\u003csub\u003e4\u003c/sub\u003e/CO\u003csub\u003e2\u003c/sub\u003e (0.25-2.1 mmol / hr) and 10%/10% CH\u003csub\u003e4\u003c/sub\u003e/CO\u003csub\u003e2\u003c/sub\u003e (2.5-25 mmol / hr) feed gas streams to help visually distinguish the two data sets. Individual data points in (a-d) are connected via straight lines. (e) Comparison of this work (red: highest production rate; green: highest conversion of reactants to products) to other published photocatalytic or photothermal DRM results, normalized by illuminated area of catalyst and averaged between CO and H\u003csub\u003e2\u003c/sub\u003e. External heating temperature is noted for prior photo-thermal work. All catalysts without external heating operating at room temperature are denoted (R.T.) Detailed values are summarized in Supplementary Table 3.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3830664/v1/b44f68cd7938766646b6b315.png"},{"id":50410614,"identity":"a36e3738-7e6a-4972-bea9-4d5e408974af","added_by":"auto","created_at":"2024-01-31 06:32:16","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":140162,"visible":true,"origin":"","legend":"\u003cp\u003eGas flow simulations through the different porous media studied. (a) Hex, (b) G\u003csup\u003eD\u003c/sup\u003e, and (c) G\u003csup\u003eA\u003c/sup\u003e periodic mesostructures and (d) asymmetric film structures exhibiting 45%, 55%, 85%, and 95% porosity, respectively. Simulated flow pathways of gas are shown below (or next to) each structure, with gas flowing left-to-right (a-c), or top-down (d). Tortuosity was estimated for each structure based on the ratio of the path length of each flow line to the length of the simulated structures. For clarity, fewer flow lines are shown than were produced from the simulations (note: in a-c straight lines result from gas flowing past rather than through the porous structures). Based on these simulations, estimated tortuosity values for the Hex, G\u003csup\u003eD\u003c/sup\u003e, G\u003csup\u003eA\u003c/sup\u003e, and asymmetric film (with 100 μm thickness) structures are 3.3, 2.0, 1.2, and 1.1, respectively.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3830664/v1/256c1c4d36715a4576e87306.png"},{"id":69933138,"identity":"88065cee-1570-4b47-b692-897e04698fb8","added_by":"auto","created_at":"2024-11-26 18:13:31","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1518018,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3830664/v1/063a663d-859d-48fc-8dc9-e79e6890280e.pdf"},{"id":50410619,"identity":"e464eebd-ccf9-4846-85c7-186e569fe1ab","added_by":"auto","created_at":"2024-01-31 06:32:17","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":12725510,"visible":true,"origin":"","legend":"","description":"","filename":"MooreShojiDRMSupplementaryInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-3830664/v1/4e9cd6f2afef104583585afc.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Low-temperature photocatalytic dry reforming of methane over porous cylindrical, gyroidal, and asymmetric catalyst structures","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe drastic increase in atmospheric greenhouse gases such as carbon dioxide (CO\u003csub\u003e2\u003c/sub\u003e) and methane (CH\u003csub\u003e4\u003c/sub\u003e) is a primary driver of climate change. Dry reforming of methane (DRM: CO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;CH\u003csub\u003e4\u003c/sub\u003e \u0026rarr; 2CO\u0026thinsp;+\u0026thinsp;2H\u003csub\u003e4\u003c/sub\u003e) has been attracting attention as one of the most promising ways to convert CO\u003csub\u003e2\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e into a valuable synthesis gas (syngas) consisting of carbon monoxide (CO) and hydrogen (H\u003csub\u003e2\u003c/sub\u003e) [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. This technology can potentially reduce environmental harms associated with emissions from the extraction and utilization of natural gas, shale gas, biogas, methane hydrates, and other natural resources, while providing a pathway to creating feedstocks for organic chemistry precursors [\u003cspan additionalcitationids=\"CR4 CR5\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. DRM is a highly endothermic reaction (Δ\u003cem\u003eH\u003c/em\u003e\u0026thinsp;=\u0026thinsp;+\u0026thinsp;247 kJ/mol) that traditionally requires temperatures of 800\u0026deg;C or higher to proceed efficiently. Due to these high reaction temperatures, DRM catalysts suffer from deactivation by thermal aggregation of co-catalysts and carbon deposition, limiting their practical use.\u003c/p\u003e \u003cp\u003eRecent advances have been made toward photocatalytic, rather than thermally activated, DRM. These systems use metals supported by oxide semiconductors such as Ga\u003csub\u003e2\u003c/sub\u003eO₃, SrTiO\u003csub\u003e3\u003c/sub\u003e, TiO\u003csub\u003e2\u003c/sub\u003e, or CeO\u003csub\u003e2\u003c/sub\u003e, or metal localized surface plasmon resonances in reactant activation [\u003cspan additionalcitationids=\"CR8 CR9 CR10 CR11 CR12\" citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Very recently, it has been reported that rhodium nanoparticle-loaded strontium titanate (Rh/SrTiO\u003csub\u003e3\u003c/sub\u003e) and rhodium intertwined with cerium oxide (Rh#CeO\u003csub\u003e2\u003c/sub\u003e) considerably exceeded the theoretical thermal catalyst thermodynamic limit by utilizing light rather than heat [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. Mechanistic investigations via isotope studies of the photocatalytic DRM system identified that lattice oxygen in the oxide mediates oxidation, while charge density in the supported metal mediates the reduction of CO\u003csub\u003e2\u003c/sub\u003e, suggesting that the metal-semiconductor interface is key to the photocatalytic reaction. In particular, the Rh#CeO\u003csub\u003e2\u003c/sub\u003e photocatalyst with many exposed nanoscopic metal-semiconductor interfaces exhibited a methane conversion rate exceeding 60% due to the efficient charge separation of photoexcited electron-hole pairs and diffusion of lattice oxygen. The photocatalysts described above were used in the form of non-porous solids, however, thus limiting the accessible surface area per unit volume. Furthermore, despite relatively high reactant conversions, these studies were performed at very low flow rates of dilute reactants, achieving impractically low production rates of CO and H\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003eHere photocatalysts for DRM were developed from porous semiconducting oxides decorated with rhodium metal nanoparticles. To that end, block copolymer self-assembly (BCP SA) directed periodically ordered mesoporous TiO\u003csub\u003e2\u003c/sub\u003e and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e supports with hexagonally-packed cylinders (Hex), co-continuous double gyroid (G\u003csup\u003eD\u003c/sup\u003e), or alternating gyroid (G\u003csup\u003eA\u003c/sup\u003e) morphologies and homogeneous 15\u0026ndash;30 nm diameter pores were synthesized from evaporation induced SA (EISA): a (close to) equilibrium process. For comparison, TiO\u003csub\u003e2\u003c/sub\u003e film supports combining asymmetric, hierarchical pore structures across the film normal with well-defined mesoporosity throughout the material were derived from a non-equilibrium BCP SA approach referred to as SNIPS (\u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003es\u003c/span\u003eelf-assembly plus \u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003en\u003c/span\u003eon-solvent \u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003ei\u003c/span\u003enduced \u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003ep\u003c/span\u003ehase \u003cspan type=\"Underline\" class=\"Underline\" name=\"Emphasis\"\u003es\u003c/span\u003eeparation). Rhodium metal nanoparticles were generated on supports by reduction of rhodium chloride hydrate to rhodium metal. Photocatalytic DRM conversions were studied under light irradiation without external heating, achieving up to 75% (Rh/Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eD\u003c/sup\u003e), 78% (Rh/TiO\u003csub\u003e2\u003c/sub\u003e-Film) and 82% (Rh/Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e) CO\u003csub\u003e2\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e conversion at low flow rates. In concentrated gas at high flow rates, CO/H\u003csub\u003e2\u003c/sub\u003e production rates up to 28,500 mmol / (hr\u0026middot;g) at 9.7% CO\u003csub\u003e2\u003c/sub\u003e/CH\u003csub\u003e4\u003c/sub\u003e conversion were achieved (Rh/TiO\u003csub\u003e2\u003c/sub\u003e-Film). This mass-normalized production rate is more than 400 times higher than that of previous state-of-the-art ambient-temperature photocatalysts. All mesoporous catalysts outperformed commercial non-mesoporous Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e and TiO\u003csub\u003e2\u003c/sub\u003e powder based catalysts. Furthermore, only moderate performance degradation was observed over a 72-hour long test run for Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e supports, yielding a turnover frequency of 38,300/hr. Especially at high flow rates, G\u003csup\u003eA\u003c/sup\u003e and asymmetric film supports demonstrated enhanced single-pass conversions as well as production rates on the bases of mass and surface area over hexagonal and G\u003csup\u003eD\u003c/sup\u003e supports. With respect to the latter two performance metrics, the asymmetric thin film catalyst substantially outperformed all other samples across all flow rates tested. Results demonstrate the importance of asymmetric hierarchical pore structures that optimize both mass transport and surface area, thereby allowing substantial improvements in DRM photocatalytic reactivity.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003e\u003cstrong\u003eSynthesis and characterization of porous supports and metal decorated photocatalysts\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eSeven porous catalyst supports were synthesized for this study from two materials and with four morphologies: mesoporous TiO\u003csub\u003e2\u003c/sub\u003e and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e supports with alternating gyroid (G\u003csup\u003eA\u003c/sup\u003e), double-gyroid (G\u003csup\u003eD\u003c/sup\u003e), and hexagonal-cylindrical (Hex) structures, as well as a porous TiO\u003csub\u003e2\u003c/sub\u003e thin film combining asymmetric, hierarchical pore structures across the film normal with well-defined mesoporosity throughout the material (Figure 1, Materials and Methods) [16]. Gyroidal and hexagonal supports were fabricated via BCP SA with one of two poly(isoprene-\u003cem\u003eblock\u003c/em\u003e-styrene-\u003cem\u003eblock\u003c/em\u003e-ethylene oxide) (PI-\u003cem\u003eb\u003c/em\u003e-PS-\u003cem\u003eb\u003c/em\u003e-PEO or ISO) terpolymers (ISO-1 and ISO-2, Supplementary Table 1), depending on the desired mesostructure: G\u003csup\u003eA\u003c/sup\u003e from ISO-1; G\u003csup\u003eD\u003c/sup\u003e and Hex from ISO-2. Structure formation for gyroidal and hexagonal structures occurred overnight via evaporation-induced self-assembly (EISA) at 40\u0026deg;C. The TiO\u003csub\u003e2\u003c/sub\u003e thin film was fabricated via SNIPS using a poly(isoprene-\u003cem\u003eblock\u003c/em\u003e-styrene-\u003cem\u003eblock\u0026shy;-\u003c/em\u003e4-vinyl-pyridine) (PI-\u003cem\u003eb\u003c/em\u003e-PS-\u003cem\u003eb\u003c/em\u003e-P4VP or ISV) terpolymer (ISV-1, Supplementary Table 1). Hybrid polymer/oxide materials were subsequently heat treated at 130\u0026deg;C for 5 hours in vacuum, followed by calcination in air to remove the ISO or ISV terpolymer and crystallize the oxide phase. TiO\u003csub\u003e2\u003c/sub\u003e and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e materials were calcined at 550\u0026deg;C and 700\u0026deg;C, respectively. After calcination, porous supports were characterized via a combination of small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and nitrogen sorption to establish sample structure and porosity (Materials and Methods). \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe corresponding scattering patterns for the six periodically ordered materials are shown in Figure 2a. The asymmetric SNIPS derived TiO\u003csub\u003e2\u003c/sub\u003e-Film sample lacking mesoscale periodic order was not included in the SAXS analysis. The low signal intensity for all support materials due to the strongly absorbing nature of these crystalline oxides, together with the relatively broad observed peaks, makes assignments to underlying lattices challenging. Tentative indexing of the observed peaks is shown in the figure. The four peaks assigned to samples TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e and Ta\u003csub\u003e2\u003c/sub\u003eO\u0026shy;\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e are consistent with an alternating gyroid (G\u003csup\u003eA\u003c/sup\u003e) lattice with cubic unit cell lattice parameters of 52.3 nm and 44.8 nm, respectively. For sample TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eD\u003c/sup\u003e, the first two indexed peaks of the pattern have been tentatively assigned to a double gyroid lattice with cubic lattice parameter of a = 135.8 nm. For sample Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eD\u003c/sup\u003e, three of the observed peaks have been tentatively assigned to a double gyroid lattice with cubic lattice parameter a = 94.0 nm. SAXS results for samples TiO\u003csub\u003e2\u003c/sub\u003e-Hex and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-Hex both show a very broad first order peak and one additional higher order reflection tentatively assigned to hexagonal lattices. Associated (10) lattice dimensions, d\u003csub\u003e10\u003c/sub\u003e, were 47.6 nm and 39.8 nm, respectively. Interestingly, although TiO\u003csub\u003e2\u003c/sub\u003e and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e samples were synthesized from the same terpolymers, all TiO\u003csub\u003e2\u003c/sub\u003e structures showed patterns shifted to smaller values of q, i.e., larger mesostructure unit cell sizes than Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e counterparts. This shift is likely due to the higher density of Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e, resulting in higher degrees of shrinkage during calcination.\u003c/p\u003e\n\u003cp\u003eTo corroborate lattice interpretations from SAXS (Table 1), sample mesostructure was further investigated via SEM (Figure 2b-i). Supports were imaged after calcination (to increase contrast), but prior to rhodium deposition. SEM images for G\u003csup\u003eA\u003c/sup\u003e and G\u003csup\u003eD\u0026nbsp;\u003c/sup\u003esamples clearly show continuous network morphologies, while those of TiO\u003csub\u003e2\u003c/sub\u003e-Hex and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-Hex both show cylinders, consistent with gyroidal and hexagonally-packed cylinder lattice assignments from SAXS, respectively. In the G\u003csup\u003eA\u003c/sup\u003e morphology, the d\u003csub\u003e100\u003c/sub\u003e distance can be measured as the distance between the wall of a pore, and the center of the neighboring pore. From the visible [111] projection of the G\u003csup\u003eA\u003c/sup\u003e samples in Figure 2b, f lattice parameters of d\u003csub\u003e100\u003c/sub\u003e = 51 \u0026plusmn; 2 nm for TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e and d\u003csub\u003e100\u003c/sub\u003e = 45 \u0026plusmn; 3 nm for Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e\u003csub\u003e\u0026nbsp;\u003c/sub\u003ewere obtained. These are similar to the respective d\u003csub\u003e100\u003c/sub\u003e values obtained from SAXS (52.3 nm and 44.8 nm). Along the G\u003csup\u003eD\u003c/sup\u003e structure [211] projection, the width of each row of coils is approximately 80% of the d\u003csub\u003e100\u003c/sub\u003e length, which was determined as d\u003csub\u003e100\u003c/sub\u003e = 132 \u0026plusmn;5 nm for TiO\u003csub\u003e2\u003c/sub\u003e and d\u003csub\u003e100\u003c/sub\u003e = 88 \u0026plusmn; 6 nm for Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e from suitably orientated grains in Figure 2c, g [17]. This is again similar to the values for TiO\u003csub\u003e2\u0026nbsp;\u003c/sub\u003e(d\u003csub\u003e100\u003c/sub\u003e = 135.8 nm) and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e (d\u003csub\u003e100\u003c/sub\u003e = 94.0 nm) derived from SAXS. SEM images of the respective gyroid structures in Figure 2b, c, f, g have visible features in agreement with simulated projections of these structures (see insets) corroborating the lattice assignments. SEM analysis of the (10) spacing for the hexagonal structures (Figure 2d, h), the distance between rows of pores, yields 48 \u0026plusmn; 2 nm and 42 \u0026plusmn; 3 nm for the TiO\u003csub\u003e2\u003c/sub\u003e-Hex and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-Hex structures, respectively, consistent with values of 47.6 nm and 39.8 nm from SAXS results. SEM images of the asymmetric TiO\u003csub\u003e2\u003c/sub\u003e film (Figure 2e, i) show a finger-like asymmetric cross-section with mesoporous walls and a mesoporous top surface. In the context of photocatalysis applications, these images collectively suggest that pore accessibility should increase in the following order: hexagonally packed cylinder \u0026lt; networked gyroidal \u0026lt; asymmetric structures. Finally, all seven supports were characterized by quantitative sorption/desorption analyses (Supplementary Discussion, Supplementary Figure 1). Results summarized in Table 1 show systematic decreases in surface area for both TiO\u003csub\u003e2\u003c/sub\u003e- and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-supports across morphologies (G\u003csup\u003eA\u003c/sup\u003e \u0026gt; G\u003csup\u003eD\u003c/sup\u003e \u0026gt; Hex) and higher values for TiO\u003csub\u003e2\u003c/sub\u003e as compared to Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e.\u003c/p\u003e\n\u003cp\u003eTable 1: Summary of structural characterization results for oxide catalyst supports and rhodium particles. BJH pore statistics do not include pores larger than 300 nm, thus the TiO\u003csub\u003e2\u003c/sub\u003e film values marked with asterisks (BET surface area, average pore width, pore volume, and overall porosity) are likely slight underestimations.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\"\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eThe seven catalyst supports were decorated with Rh metal nanoparticles via hydrothermal infiltration of Rh and subsequent photoreduction under illumination during catalytic evaluation (Materials and Methods). Resulting metal photocatalysts were characterized by X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS) (Supplementary Figure 2), with quantitative XPS results summarized in Supplementary Table 2. All materials measured were phase-pure and fully crystalline, indicated by the lack of broad amorphous background scattering, with metallic Rh detected on all samples. Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e supports could be matched to the orthorhombic tantalum oxide lattice structure. TiO\u003csub\u003e2\u003c/sub\u003e supports exclusively showed an anatase titania lattice structure. XPS results confirmed no chemical discrepancies between different structures of each material (Supplementary Figure 2b, d). Corroboratory UV-vis measurements (Supplementary Figure 3) confirmed all oxides have approximately 3 eV band gaps. Samples were not intentionally doped but may have lower than expected band gaps due to either unintentional impurities or the higher surface-to-bulk ratio resulting from the 10-30 nm diameter strut networks. Rhodium particles were fully reduced to the metallic phase, without remnant rhodium chloride precursor detected in XRD, although some remnant Cl was detected in XPS as a low-intensity peak around 200 eV. Oxide crystallite sizes and rhodium particle sizes were calculated via Scherrer analysis from XRD patterns (Supplementary Figure 2a, c). XRD-based structural information for oxide supports and rhodium particles is summarized in Table 1. Oxide crystallite sizes can be compared to oxide domain dimensions as reflected by SEM results (Figure 2b-i). From SEM, the TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u0026nbsp;\u003c/sup\u003estructures have ~12 nm thick struts, slightly smaller than the XRD derived crystallite sizes of 14 nm and 18 nm. TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eD\u003c/sup\u003e and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eD\u0026nbsp;\u003c/sup\u003eoxide strut dimensions were ~25 nm, larger than the TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eD\u003c/sup\u003e 9 nm crystallite size and close to the ~27-28 nm Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e XRD crystallite size. SEM derived oxide domain dimensions for both hexagonal supports were also ~25 nm, larger than the XRD based crystallite sizes of ~9 nm and ~18 nm for TiO\u003csub\u003e2\u003c/sub\u003e-Hex and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-Hex, respectively. Oxide crystallite sizes for most samples were therefore either close to (for G\u003csup\u003eD\u003c/sup\u003e structures) or smaller (for hexagonal structures) than the associated oxide domain dimensions. Slightly larger domain sizes in G\u003csup\u003eA\u003c/sup\u003e structures without loss of mesostructure may suggest elongation of crystallites along the sample strut direction. All this is consistent with periodic mesoscale structure retention after high temperature thermal processing, as substantial crystalline overgrowth beyond the confinement of BCP SA directed nanoscale domains is typically associated with loss of mesoscale structure.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eTEM micrographs were collected for the three most active catalyst supports (TiO\u003csub\u003e2\u003c/sub\u003e-Film and G\u003csup\u003eA\u0026nbsp;\u003c/sup\u003ecatalysts, \u003cem\u003evide infra\u003c/em\u003e) to confirm the presence of metallic rhodium. Figure 3a-c show open pore networks for all structures, including the TiO\u0026shy;\u003csub\u003e2\u003c/sub\u003e-Film (Figure 3c) which is likely a fragment from the more-ordered top surface layer. The micrograph of the TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e structure (Figure 3b) suggests slightly improved periodic order relative to the Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e\u003csub\u003e\u0026nbsp;\u003c/sub\u003ematerial (Figure 3a), consistent with the slightly improved peak definition observed in its SAXS pattern (Figure 2a). Figure 3d-f depicts high-magnification images of the same structures revealing lattice spacings (see insets) that can be indexed to Rh metal (200) and various oxide lattice planes. Results agree with earlier XRD and XPS datasets suggesting the presence of metallic Rh in catalyst samples.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003ePhotocatalytic DRM\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003ePhotocatalysts were evaluated in a flow-through setup (Materials and Methods). Feed gas streams of either 1%/1%/98% or 10%/10%/80% CH₄/CO₂/Ar were delivered to the photocatalysts at flow rates of 0.2-2.1 mmol / hr for the 1% feed gas and 2.5-25 mmol / hr for the 10% feed gas. A large range of flow rates was used to enable a more comprehensive investigation of catalyst behavior relative to singe flow rate studies. The gyroidal and hexagonal catalyst materials were held in a quartz glass reactor (Supplementary Figure 4a), while the TiO\u003csub\u003e2\u003c/sub\u003e film was held in a top-loading brass reactor designed to accept samples in a film geometry (Supplementary Figure 4b and 5). Both reactors were illuminated by a 300W Xe lamp (Supplementary Figure 6) and oriented to make the reactant gas incident to the top illuminated surface. For a performance comparison of both reactors, please see Materials and Methods section. Products were measured with a gas chromatograph (Supplementary Figure 7). Volumetric flow rates ranged from 10-100 mL / min for each gas concentration. Conversion (%) is defined as the amount of products generated relative to the complete conversion of all reactants to products.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFigure 4a-c shows the photocatalytic DRM performance of all seven materials. At the lowest 0.25 mmol / hr feed rate, maximum conversions for the highest performers Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e, TiO\u003csub\u003e2\u003c/sub\u003e-Film, and Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eD\u003c/sup\u003e were 81.6%, 77.8% and 75.1%, respectively. These conversion values all exceeded the 50-64% conversion by the most active DRM room-temperature photocatalysts to date, i.e., Rh/SrTiO\u003csub\u003e3\u003c/sub\u003e and Rh#CeO\u003csub\u003e2\u003c/sub\u003e nanocomposites [14,15]. The G\u003csup\u003eA\u003c/sup\u003e and thin film catalysts exhibit a similar flow-rate dependence above 1 mmol / hr, with both types of catalyst supports showing conversions that outpace the performance of all other samples. Both the G\u003csup\u003eA\u003c/sup\u003e and asymmetric film catalysts are templated by terpolymers with only ~7-12 vol% hydrophilic blocks (as compared to ~46% for all other structures, Supplementary Table 1), consistent with more accessible surface area of openly porous materials compared to the other catalysts. Since the asymmetric thin film catalyst has ~50x less mass (Supplementary Figure 5) for the same illuminated area than other materials tested, its mass-normalized performance shows a record photocatalytic mass activity (Figure 4b), substantially outperforming all other samples across all flow rates tested in this performance metric. The two catalysts with G\u003csup\u003eA\u0026nbsp;\u003c/sup\u003emorphology outperform all other equilibrium derived and periodically ordered photocatalysts in this metric (especially above a flow rate of ~1 mmol / hr) due to their high-porosity-derived reduced density. Typical plateaus in production occur at 10 mmol / hr for Hex / G\u003csup\u003eD\u003c/sup\u003e catalysts, 10-20 mmol/hr for G\u003csup\u003eA\u003c/sup\u003e catalysts, and 20 mmol / hr for the asymmetric TiO\u003csub\u003e2\u003c/sub\u003e film (Figure 4b).\u003c/p\u003e\n\u003cp\u003eFor both studied oxides, surface area was significantly higher for the gyroidal supports as compared to their hexagonal counterparts (Table 1). But using the performance metric of production per surface area, the asymmetric film also comes out on top by a large margin across all flow rates tested (Figure 4c). Due to the inability of the BJH method to characterize pores larger than 300 nm, the measured surface area of the asymmetric TiO\u003csub\u003e2\u003c/sub\u003e film is likely slightly underestimated. But since the surface area of the limited number of \u0026gt;300 nm macropores is minute compared to that of the many \u0026lt; 50 nm mesopores, this overestimation cannot account for the large margin by which the TiO\u003csub\u003e2\u003c/sub\u003e film outperforms the remaining structures on a surface-area-normalized basis. Within the family of equilibrium derived periodically ordered catalysts, when normalized to the internal (BET) surface area, the production rates of tantalum oxide-based catalysts are higher than those of their titania counterparts across all flow rates measured. In part, this performance difference results from TiO\u003csub\u003e2\u003c/sub\u003e\u0026rsquo;s higher surface area, around a factor of 3 across all morphologies (Table 1). Other contributing effects (e.g., side reactions) are discussed in the Supplementary Information. Within the set of samples for each oxide, at slow feed rates (\u0026lt; 2 mmol / hr), surface-area-normalized performance of the gyroidal and hexagonally structured samples are comparable (Figure 4c). In contrast, at high flow rates (\u0026gt; 2 mmol / hr), the surface-area-normalized production rates of catalysts with G\u003csup\u003eA\u003c/sup\u003e morphology increasingly outperform those of catalysts with either hexagonal or G\u003csup\u003eD\u003c/sup\u003e morphology (by 2-3x at 20 mmol / hr).\u003c/p\u003e\n\u003cp\u003eA durability test was conducted over 72 hours with photocatalyst Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e at its maximum mass-normalized reaction condition, i.e., at a high flow rate of 18.5 mmol / hr (Supplementary Figure 8). Photocatalyst performance only moderately declined to ~75% of its initial activity over the 72hr time period, reaching a turnover frequency, defined as mole of CO and H\u003csub\u003e2\u003c/sub\u003e (averaged) produced per mole of Rh over time, of 38,320 / hr or 10.6 / s. Additional comparisons to the porous catalysts were performed with commercial non-porous Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e and TiO\u003csub\u003e2\u003c/sub\u003e particle powder catalysts (Supplementary Figure 9, Supplementary Table 3). These reference results verify that the used reactors adequately reproduce the performance of reference catalysts relative to the literature. As expected, all porous catalysts outperform the non-porous catalysts in percentage of reactants converted, mass-normalized production, and surface-area-normalized production (Supplementary Figure 9a-c).\u003c/p\u003e\n\u003cp\u003eThe product ratio between CO and H\u003csub\u003e2\u0026shy;\u003c/sub\u003e as a function of flow rate is shown in Figure 4d. Notably, the CO/H\u003csub\u003e2\u003c/sub\u003e ratio substantially changed with feed gas concentration, with ratios below and above 1 for feed gas concentrations of 1% and 10% CH\u003csub\u003e4\u003c/sub\u003e/CO\u003csub\u003e2\u003c/sub\u003e, respectively. Overall,\u0026nbsp;there seems to be qualitatively different behavior for tantalum oxide and titania based photocatalysts, with product ratios at high flow rates (\u0026gt;2 mmol / hr) converging towards 1 for tantalum oxide-based catalysts, while those of titania diverge towards a higher CO to H\u003csub\u003e2\u003c/sub\u003e ratio in the product stream. The asymmetric TiO\u003csub\u003e2\u003c/sub\u003e film catalyst is the exception to this rule as its behavior converges towards 1, similar to the tantalum oxide-based materials. For further in-depth analysis and discussion of this behavior, we refer to the supplementary information (Supplementary Discussion; Supplementary Table 4).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFigure 4e and Supplementary Table 3 provide an overall comparison of the (meso-) porous catalysts studied in this work to published works in photocatalytic and photo-thermal DRM in the form of a bar chart of production per illuminated area (spot size). This measure of performance is relevant for photocatalyst deployment since reactor design is primarily limited by the illuminated area of the catalyst, rather than its mass. Notably, Rh/TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eA\u0026nbsp;\u003c/sup\u003ecan be directly compared to a non-structured powder Rh/TiO\u003csub\u003e2\u003c/sub\u003e catalyst [15], where Rh/TiO\u003csub\u003e2\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e demonstrates both a higher maximum reactant conversion (50.3% vs 20.7%) and a 240x improvement in the maximum measured production per illuminated area. Mesostructure variations alone account for this substantial uplift in both single-pass conversion and maximum production for Rh/TiO\u003csub\u003e2\u003c/sub\u003e. The highest activity catalyst studied, the asymmetric TiO\u003csub\u003e2\u003c/sub\u003e film, demonstrated a 719x improvement over the previously studied room-temperature Rh/TiO\u003csub\u003e2\u003c/sub\u003e catalyst in terms of production per illuminated area. This performance metric is not affected by the very low mass of the thin film, rather, the highly porous material and hierarchical pore network drove improvements in both conversion and production over all other TiO\u003csub\u003e2\u003c/sub\u003e structures studied. When normalized by mass, the asymmetric TiO\u003csub\u003e2\u003c/sub\u003e film achieved between 150-1500x improvements (depending on flow rate) compared to previously studied Rh/TiO\u0026shy;\u003csub\u003e2\u003c/sub\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFlow simulations were performed to estimate the tortuosity for each of the catalyst structures used (Figure 5, Materials and Methods). Tortuosity in this study is defined as the path length of a simulated gas flow line versus the length of the structure studied. Each of the simulations provided qualitative insights into gas transport through these porous photocatalysts. As expected, of all the equilibrium-based periodically ordered structures tested, the highly porous G\u003csup\u003eA\u0026nbsp;\u003c/sup\u003estructure with approximately 85% porosity had the lowest simulated tortuosity of T = 1.2 (Figure 5c). The path of gas through this structure would be 1.2x longer than a direct path. Tortuosity is inversely related to diffusivity through catalyst structures, so it follows that the G\u003csup\u003eA\u003c/sup\u003e structure with the lowest tortuosity has the most advantageous gas flow characteristics for catalysis, and thus the highest activity. The G\u003csup\u003eD\u003c/sup\u003e structure had an estimated tortuosity of T = 2.0, while the hexagonal structure resulted in an estimate of T = 3.3 (Figure 5a, b). Conceptually, 1-dimensional pores should have about 3x higher tortuosity compared to a 3-D pore network (G\u003csup\u003eA\u003c/sup\u003e), which agrees with these estimates.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eDetermining tortuosity in the porous asymmetric thin film structure required a separate approach derived from a previously described method (Materials and Methods) [18]. From associated simulations, tortuosity varied as a function of membrane thickness (Supplementary Figure 10). The top 8 \u0026micro;m mesoporous layer of the film, dominated by BCP SA, has a tortuosity slightly above T = 1.3. However, when averaged over the entire ~100 \u0026mu;m thick asymmetric film (Figure 2i, Supplementary Figure 10), including the essentially open macroporous substructure, tortuosity of the membrane decreases to below T = 1.1, the lowest tortuosity of all catalyst structures studied. This is consistent with the high conversion efficiency of this structure measured in the catalysis experiments (Figure 4).\u0026nbsp;\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eRh metal nanoparticles on semiconducting titanium and tantalum oxide supports with porous periodic alternating gyroid, double gyroid, hexagonally-packed cylinder, and asymmetric thin-film structures were studied to evaluate the impact of pore geometry, connectivity, and asymmetry on photocatalytic DRM at ambient pressure in the absence of external heating. Porous supports were prepared by BCP SA directed sol-gel synthesis from either ISO triblock terpolymers (periodic structures) or an ISV triblock terpolymer (asymmetric films) followed by thermal processing, and Rh metal decoration. A combination of SAXS, WAXS, SEM, TEM, and nitrogen sorption/ desorption characterization demonstrated that the oxide supports had either periodically ordered mesopores or asymmetric hierarchical pore structures exhibiting meso- to macro-porosity derived from equilibrium or non-equilibrium formation processes, respectively. In all cases, oxide crystallization occurred without mesostructure collapse, while Rh metal nanoparticle sizes were significantly smaller than the pore diameters of the oxide supports, preventing pore clogging. Photocatalytic DRM showed conversion rates of over 81% for Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e and 77% for the asymmetric TiO\u003csub\u003e2\u003c/sub\u003e-Film at low flow rates. At higher flow rates, activity increased, reaching a maximum production rate of over 28,560 mmol / (hr\u0026middot;g) for the TiO\u003csub\u003e2\u003c/sub\u003e-Film, and 780 mmol / (hr\u0026middot;g) for the Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e structure. To the best of our knowledge, these photocatalysts showed the highest reported activities to date for photocatalytic DRM without external heating. Furthermore, comparing periodic titanium- to tantalum-based oxide mesostructure supports, the latter showed better performance and more optimal DRM product ratios, especially at high flow rates. Comparing samples with different periodic mesopore structures derived from the same material (e.g., Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-G\u003csup\u003eA\u003c/sup\u003e vs Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e-Hex) demonstrated that details of the pore geometry and connectivity are critical to optimizing photocatalysis. Widely open alternating gyroids with three-dimensionally co-continuous network pore structures enhanced activity, whereas one-dimensional hexagonal pore structures met early performance plateaus. Photocatalytic results align with insights from flow simulations, suggesting that interconnected pores improve gas diffusion dynamics, thereby significantly enhancing performance of photocatalysts for DRM. Additionally, to the best of our knowledge, this first-time study of an asymmetric, hierarchically porous DRM photocatalyst film suggests that such membrane-type structures, combining fast mass transport through (finger-like) macropores and high surface area from mesopores distributed throughout the material, may be well-suited for not only photocatalytic DRM, but also other photocatalytic reactions. Such low-density thin membrane-type catalysts effectively achieve high reactant conversion while minimizing the required mass of expensive metal promoters. While this study focused on improvements in catalytic materials using simple reactor designs, further performance gains should be possible through improved process designs to recycle unreacted gas, advanced reactor designs to minimize unilluminated catalyst, and optimized low-power LED illuminations. We hope that our results of enhancing photocatalytic performance of a given class of catalysts (here: of semiconductor-metal photocatalysts) via fine control over pore geometry, connectivity, and asymmetry in mesoporous supports will stimulate further efforts to not only control atomic level structure but also meso- to macro-structural aspects to develop next generation high-performance reaction systems.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003eAUTHOR INFORMATION\u003c/p\u003e\n\u003cp\u003eCorresponding Authors\u003c/p\u003e\n\u003cp\u003e*E-mail: [email protected] (U.W.) and [email protected] (S.S.)\u003c/p\u003e\n\u003cp\u003eAuthor Contributions\u003c/p\u003e\n\u003cp\u003eS.S. and U.W. conceived this project. W.M. and S.S. contributed equally to the work. S.S. and W.M. conducted materials synthesis, structural analysis, and catalytic testing. P.T. and F.Y. synthesized and analyzed the ISO terpolymers. F.Y and L.T. collected SEM images and performed subsequent image analysis. W.T. assisted with the nitrogen sorption analysis. A.S. performed flow simulations of gyroid and hexagonal structures. M.S.R. constructed the thin-film model and performed flow simulations of the thin-film. A.R. fabricated and donated the top-loading reactor and assisted catalytic testing. U.W. and J.S. continuously reviewed and discussed the materials synthesis/characterization and catalysis results with W.M and S.S. to continuously advance the project. W.M., S.S., and U.W. wrote the manuscript, with input from all co-authors.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eACKNOWLEDGMENT\u003c/p\u003e\n\u003cp\u003eS.S. thanks the Kavli Institute at Cornell (KIC) for nanoscale science as well as the Japan Society for the Promotion of the Science (JSPS) for fellowship funding. U.W. and J.S. acknowledge support from NSF (DMR-2307013 to U.W. and CBET-1805400 to J.S.). This work made further use of the Cornell Center for Materials Research Shared Facilities which are supported through the NSF MRSEC program (DMR-1719875).\u003c/p\u003e\n\u003cp\u003eWe acknowledge Karl Termini and the Cornell CAS Professional Glass Shop for their contributions to designing and fabricating equipment used in the study.\u003c/p\u003e\n\u003cp\u003eS.S. and W.M. thank Sarah Hesse for fabrication of the ISV terpolymer used in this study.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThis research used beamline 11-BM (CMS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. The authors thank Peter Beaucage for the collection of this data.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThis work is based on research conducted at the Center for High-Energy X-ray Sciences (CHEXS), which is supported by the National Science Foundation (BIO, ENG and MPS Directorates) under award DMR-1829070.\u003c/p\u003e\n\u003cp\u003eWe thank\u0026nbsp;Rajesh Bhaskaran and ANSYS Inc. for the ANSYS License Key.\u003c/p\u003e\n\u003cp\u003eProton nuclear magnetic resonance (\u003csup\u003e1\u003c/sup\u003eH NMR) spectroscopy was performed at the Cornell University NMR facility, which is supported in part by the NSF through an MRI award (CHE1531632).\u0026nbsp;\u003cbr\u003e\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eAshcroft, A. Cheetham, A. and Green, M. Partial oxidation of methane to synthesis gas using carbon dioxide. \u003cem\u003eNature\u003c/em\u003e 352, 225\u0026ndash;226. 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(2020).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-3830664/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3830664/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eRecent advances in the photocatalytic activation of dry reforming of methane (DRM: CO\u003csub\u003e2\u003c/sub\u003e + CH\u003csub\u003e4\u003c/sub\u003e → 2CO + 2H\u003csub\u003e2\u003c/sub\u003e) at low temperature and ambient pressure have generated considerable interest as a promising route to convert greenhouse gases into valuable synthetic gas (syngas). While detailed studies have revealed the mechanisms involved in photocatalytic DRM at metal-semiconductor interfaces, less attention has been devoted to how high surface area semiconductor supports may enhance such conversions. Here we structure triblock terpolymer self-assembly directed sol-gel derived transition metal oxide (Ta\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e or TiO\u003csub\u003e2\u003c/sub\u003e) supports of Rh-decorated photocatalysts into various equilibrium and non-equilibrium derived porous morphologies and show how they modulate single-pass conversion, total production rate, and material efficiency. Supported by in-depth materials characterization and flow simulations rationalizing observed trends, results reveal record catalyst performance. Our work suggests that asymmetric pore structures simultaneously optimizing mass transport and surface area may be well-suited to maximize photocatalyst performance.\u003c/p\u003e","manuscriptTitle":"Low-temperature photocatalytic dry reforming of methane over porous cylindrical, gyroidal, and asymmetric catalyst structures","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-01-31 06:32:11","doi":"10.21203/rs.3.rs-3830664/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"9eb98965-c002-4d71-8165-c10273844c2f","owner":[],"postedDate":"January 31st, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":28007301,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Photocatalysis"},{"id":28007302,"name":"Physical sciences/Materials science/Soft materials/Polymers"},{"id":28007303,"name":"Physical sciences/Materials science/Materials for energy and catalysis/Porous materials"}],"tags":[],"updatedAt":"2024-11-26T18:05:23+00:00","versionOfRecord":[],"versionCreatedAt":"2024-01-31 06:32:11","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3830664","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3830664","identity":"rs-3830664","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}