Metal Incorporated Mesoporous Silica for Hydrogen Isotope Gas Separation Application in Heavy Water Nuclear Power Plant

Metal Incorporated Mesoporous Silica for Hydrogen Isotope Gas Separation Application in Heavy Water Nuclear Power Plant | 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 Research Article Metal Incorporated Mesoporous Silica for Hydrogen Isotope Gas Separation Application in Heavy Water Nuclear Power Plant Daeuk Kang, Chan Woo Park, Hyung-Ju Kim This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7613043/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 26 Nov, 2025 Read the published version in Korean Journal of Chemical Engineering → Version 1 posted 4 You are reading this latest preprint version Abstract The separation of hydrogen isotopologues, such as protium (H₂), deuterium (D₂) and tritium, is necessary for the stable and consistent operation of heavy water nuclear power plants, where deuterium oxide is used as both moderator and coolant. As conventional processes, cryogenic distillation and catalytic exchange are widely applied for hydrogen isotopologues separation. However, those techniques have been encountered the intrinsic limitations including high energy consumption, slow reaction rates and large facility expenses. As an alternative, separation techniques based on the mechanism of chemical affinity quantum sieving have been studied to separate isotopes at temperate ranging from liquid nitrogen (N 2 ) temperature (77 K) to upwards through differences in adsorption. In this study, mesoporous silica modified with silver or copper (Cu) was prepared and applied for hydrogen isotopologues separation at 77 K. Their structural, morphological and surface chemical properties were analyzed using X-ray diffraction, scanning electron microscopy, N 2 physisorption, X-ray photoelectron spectroscopy and solid-state magic angle spinning silicon-29 nuclear magnetic resonance spectroscopy. Single gas adsorption isotherms of H 2 and D 2 were measured and binary separation performance was evaluated using equilibrium modeling. Cu-incorporated mesoporous silica showed the highest D 2 over H 2 selectivity, reaching 5.52 under the D 2 diluted conditions (1:99). This is attributed to the dispersed Cu oxide species in the silica framework as well as the silanol rich domains of mesoporous silica which both enhance interaction with D 2 . These results suggest that isotope selectivity (D 2 /H 2 ) can be tuned by adjusting the surface structure, property and pore network of mesoporous silica, offering a practical approach for hydrogen isotopologues separation in nuclear facility. Hydrogen isotopologues separation Mesoporous silica Metal incorporation Chemical affinity quantum sieving Cryogenic adsorption Ideal adsorbed solution theory Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 INTRODUCTION Stable and consistent operation of heavy water nuclear power plants (NPPs) depends on isotopic purity of deuterium oxide (D 2 O), which works as both a neutron moderator and coolant due to its extremely low neutron capture cross-section [ 1 ]. Especially, nuclear power plant systems such as the Canadian heavy water reactor require precise control of D 2 O concentration to maintain consistent fission and reactor safety against radiation of tritium (T 2 ) [ 2 ]. Over the time of reactor operation, neutron irradiation and radiolysis of D 2 O gradually alter the hydrogen isotopologues composition in moderator and coolant systems, creating conditions that can lead to hazardous T 2 radiation and decreased efficiency of neutron moderator and coolant [ 3 ]. To maintain the required isotopic purity during reactor operation, especially under accumulation of radioactive T 2 or dilution of deuterium (D 2 ) conditions, techniques for hydrogen isotopologues separation are necessary to selectively remove T 2 and maintain D 2 concentration [ 4 ]. In South Korea, T 2 removal facility have been implemented at the Wolsong NPP site to support reactor operation and secure the release of radioactive T 2 and high purity of D 2 O supply since 2007 [ 5 , 6 ]. First part of this system is liquid phase catalytic exchange that tritiated heavy water passes through a catalyst column to remove T 2 from the D 2 O. Even if this method is widely applied, it is constrained by slow reaction kinetics and the requirement for packed columns with high performance catalyst that often exceed 20 m in height to achieve practical levels of separation [ 7 ]. Second part is T 2 separation by cryogenic distillation, which separates hydrogen isotopologues based on extremely small differences in boiling point, specifically 20.3 K for potium (H 2 ), 23.7 K for D 2 and 25.04 K for T 2 [ 8 ]. This process is constrained by the limited separation factor, around 1.5 maximum, coupled with the extremely high energy demand of cryogenic operation and the resulting elevated overall costs [ 9 ]. Other techniques, including palladium alloy membrane separation [ 10 ], laser-based isotope fractionation [ 11 ] and the Girdler sulfide process [ 12 ], have been also considered. However, these approaches are encountered troubles in low throughput, complicated operational facility, expensive material costs or environmental hazards. Thus, alternative ways have been actively explored to achieve the T 2 separation. As one of the alternatives, quantum mechanical approaches have been tried to separate hydrogen isotopologues with greater efficiency and scalability [ 13 ]. Recent research has significantly focused on quantum sieving mechanisms coming from intrinsic difference in zero-point energy (ZPE) between hydrogen isotopologues [ 14 , 15 ]. The ZPE indicates the residual vibrational energy that molecules retain at absolute zero temperature, 0 K, and is inversely proportional to mass of each molecule. Therefore, lighter isotopologues, i.e., H 2 here, remain more vibrationally delocalized, making them less susceptible to confinement in adsorption potential fields [ 16 ]. This mass-dependent behavior forms the basis of kinetic quantum sieving (KQS), in which ultra-micropores smaller than 0.35 nm selectively retentate lighter isotopes by preferentially adsorbing heavier molecules, i.e., D 2 here. However, the KQS effect occurs only at extremely low temperatures, typically below 30 K, thereby requires intensive energy and highly stable and ordered porous structure under aggressive conditions. These strict energy and structural demands limit its scale-up and long-term application in practical systems [ 17 ]. On the other hand, the concept of chemical affinity quantum sieving (CAQS) has been subjected under less aggressive conditions, temperate ranging from 77 K upwards, to enable selective adsorption of hydrogen isotopologues [ 18 ]. Selectivity caused by CAQS originates from both quantum delocalization effects and slight variations in physisorption energy [ 19 ]. Heavier isotopes, possessing lower ZPE, strongly adsorbed onto the active sites and are more likely to be stabilized in deeper potential wells [ 20 ]. Since the low temperature conditions are relatively less aggressive for CAQS, it is feasible to expand the range of materials and save the cost of energy. Several metal functionalized porous materials have been explored for their potential to separate hydrogen isotopologues at liquid nitrogen (N 2 ) temperature, 77 K, via CAQS. Silver (Ag) exchanged zeolite Socony Mobil–5 has demonstrated a D 2 /H 2 selectivity of ~ 8.7, driven by the localized electrostatic fields around Ag ions that preferentially stabilize D 2 . Regardless of its effectiveness in isotope separation, its practical use is limited due to the low density of exchanged Ag ions, which restricts the overall adsorption capacity and hinders large scale implementation [ 21 ]. Copper (Cu) substituted zeolitic imidazolate framework with gismondine topology, while showing D 2 /H 2 selectivity of ~ 4.0, exhibits very low D 2 uptake and limited adsorption capacity even under an exposure pressure of 2000 mbar due to slow adsorption kinetics [ 22 ]. Nickel based metal-organic framework-74 (Ni-MOF-74) exhibited the highest D 2 /H 2 selectivity of approximately 4.8 at near-zero pressure and the selectivity decreased with increasing pressure. Both Cobalt and magnesium based MOF-74 showed D 2 /H 2 selectivity of approximately 3.5 and also exhibited decreasing trends with increasing pressure. Zinc (Zn) based MOF-74 showed a lower D 2 /H 2 selectivity of approximately 1.7, attributed to weaker interactions between hydrogen isotopologues and Zn²⁺ coordination sites [ 23 ]. To address these challenges, this study investigates mesoporous silica modified with metal species, such as Ag and Cu, as a candidate material for hydrogen isotopologues separation at 77 K. Mesoporous silica provides several advantages for this purpose, including a high specific surface area, tunable pore structures and excellent thermal and mechanical stability [ 24 ]. Furthermore, its surface, composed of plenty of silanol group, can be easily tailored by incorporating metal species, enabling enhancement of isotope-specific surface interactions [ 25 ]. In this study, metal incorporated mesoporous silica was synthesized and its physico-chemical properties were characterized then applied for D 2 /H 2 separation. Ag and Cu were successfully incorporated into the mesoporous silica framework through co-condensation method followed by calcination. The resulting materials were precisely characterized using diverse techniques to access the structural, surface property, silanol density as well as siloxane network condensation. Single component adsorption isotherms were obtained and binary isotope separation behavior was analyzed using ideal adsorbed solution theory (IAST) to understand the effect of surface modifications on selectivity of D 2 /H 2 . EXPERIMENTAL 1. Materials The following chemicals and gases were used as received without further purification. Tetraethyl orthosilicate (TEOS, 98%), cetyltrimethylammonium bromide (CTAB, >98%), ethanol (EtOH, 99.99%), ammonium hydroxide solution (NH 3 , 28.0 ~ 30.0 wt%), Ag nitrate (AgNO 3 , ≥ 99.0%) and Cu (II) nitrate trihydrate (CuN 2 O 6 ·3H 2 O, 99 ~ 104%) were purchased from Sigma-Aldrich. Deionized (DI) water was supplied from Direct-Q® 3 water purification system with resistivity of 18.2 MΩ cm at 298 K. H 2 gas (99.999%) and N 2 gas (99.999%) were purchased from Daesung Industrial Gases Co., Ltd. D 2 gas (99.999%) and neon gas (Ne, 99. 999%) were purchased from Noble gas Co., Ltd. 2. Preparation of mesoporous silica Mesoporous silica was prepared as reported somewhere else [ 26 ]. CTAB (2.4 g) was dissolved in the equivolume mixture of DI water (50 mL) and ethanol (50 mL). After 10 min of fierce stirring, NH 3 (12 mL) was added. Subsequently, TEOS (3.4 g) was added drop-wisely into the mixture solution. The mixed solution was additionally stirred for another 2 h until it converted as gel. The molar composition of the final gel was TEOS: 0.43 CTAB: 12.5 NH 3 : 54.3 EtOH: 416 H 2 O. The resulting gel was washed with deionized water for 5 times and solid/liquid was separated by centrifugation at each cycle. Then, the resulting solid was dried in the oven at 338 K overnight. The CTAB template, pore directing agent here, was removed by calcination at 823 K with a heating rate of 274 K min − 1 for 6 h under stagnant air conditions in the furnace. 3. Preparation of Ag- and Cu-mesoporous silica CTAB (5.1 g) was dissolved in the mixed solution of DI water (200 mL) and ethanol (100 mL). Then, NH 3 (6.78 mL) was added. After 10 min of fierce stirring, TEOS (6.7 g) was added drop-wisely into the solution mixture. After that, the AgNO 3 (0.112 g) or CuN 2 O 6 (0.156 g) precursor was doped into the solution. The mixed solution was stirred for another 4 h. The molar composition of the gel was TEOS: 0.02 x: 0.41 CTAB: 12 NH 3 : 54 EtOH: 173 H 2 O, where x stands for Ag or Cu. The final gel was washed, centrifuged, dried identical way as described in the previous section. The CTAB template was removed by calcination at 823 K with a heating rate of 276 K min − 1 for 6 h under stagnant air conditions in furnace. 4. Characterizations The X-ray diffraction (XRD) patterns of the samples were measured using a D2 PHASER (Bruker) from 0 to 8˚ (low angle) and 10 to 80˚ (high angle) of 2 θ at a rate of 0.002˚ per step with a counting time of 0.5 s per step using a Cu-K-alpha radiation source. The scanning electron microscopy (SEM) images were obtained SU-8020 (Hitachi) at a landing energy of 15 kV. The samples were prepared on the top of carbon tape and coated with gold. The N 2 physisorption isotherms were measured at 77 K using an Autosorb iQ-XR Viton (Quantachrome). Before measurement, the samples were degassed overnight at 423 K under vacuum to remove the pre-adsorbed gases, moisture and any other impurities. The N 2 physisorption isotherms were analyzed to specify the specific surface area, pore volume and pore size distribution (PSD) of the samples. The specific surface area and PSD were determined by the Brunauer-Emmett-Teller (BET) method and by Broekhoff-de Boer/Frenkel-Halsey-Hill (BdB-FHH) method, respectively. The X-ray photoelectron spectroscopy (XPS) spectra of the samples were obtained using a K-alpha + spectrometer (Thermo Scientific) with a monochromatic Al-K-alpha radiation source (1486.6 eV). The spectra were acquired with a pass energy of 50 eV for high-resolution scans. Data analysis was performed using Avantage software. 29 Si magic angle spinning-nuclear magnetic resonance analysis ( 29 Si MAS-NMR) spectra were using an AVANCE Ⅲ HD 400 MHz solid state NMR spectrometer (Bruker). The probe used was 4 mm double resonance CPMAS probe. 29 Si MAS NMR experiments were performed at 79.495 MHz. These spectra were acquired with a one pulse sequence. Spinning frequencies of 11 kHz, π/4 pulse widths of 2 µs, contact times of 2 ms, delay times of 20 s were used. 5. Single gas (H and D) isotherm measurements The single gas (H 2 and D 2 ) adsorption isotherm was measured at 77 K using an Autosorb iQ-XR (Quantachrome). Before measurement, the samples were degassed overnight at 423 K under vacuum to remove pre-adsorbed gases, moisture and any other impurities. Adsorption measurements were conducted over a relative pressure (P/P 0 ) ranging from 0 to 1 to determine the equilibrium adsorption capacities of H 2 and D 2 . The separation performance (adsorption capacity and selectivity) of hydrogen isotopologues separation was evaluated using the IAST [ 27 ]. The IAST is a well-established method for predicting binary mixture adsorption behaviors of various types of adsorbents [ 28 ]. The IAST selectivities were obtained at the range from equimolar to D 2 depleted conditions. The single gas adsorption isotherms of H₂ and D₂ were fitted to the Langmuir-Freundlich equation (Eq. (1)) to obtain the parameters required for IAST calculations: $$\:\begin{array}{c}{\:q}_{i}=\:{q}_{max,\:\:i}\left(\frac{{\left({K}_{i}{P}_{i}\right)}^{n}}{{1+\left({K}_{i}{P}_{i}\right)}^{n}}\right) \left(1\right)\end{array}$$ All parameters are denoted with subscript \(\:i\) , representing the species H 2 or D 2 . \(\:q\) is the amount adsorbed (mmol g −1 ), \(\:{q}_{max}\:\) is the maximum adsorption capacity (mmol g −1 ), \(\:K\) is the equilibrium constant (kPa −1 ), \(\:P\) is the absolute pressure (kPa​) and \(\:n\) is the heterogeneity factor. The parameters \(\:{q}_{max}\) ​, \(\:K\) and \(\:n\) were obtained by fitting the H 2 and D 2 adsorption isotherms to Eq. (1). The binary adsorption equilibria of H 2 /D 2 mixtures are predicted through IAST. The spreading pressures were calculated from the fitted isotherms and the partial pressures in the gas phase were derived by solving the IAST equations numerically. Then, selectivity ( \(\:{S}_{{D}_{2}/{H}_{2}}\) ) was calculated as following Eq. (2): $$\:\begin{array}{c}{S}_{{D}_{2}/{H}_{2}}=\:\frac{{q}_{{D}_{2}}{/q}_{{H}_{2}}}{{P}_{{D}_{2}}{/P}_{{H}_{2}}} \left(2\right)\end{array}$$ Here, \(\:{q}_{{D}_{2}}\) ​​ and \(\:{q}_{{H}_{2}}\) represent the adsorbed amounts (mmol g −1 ) of D 2 and H 2 , respectively, while \(\:{P}_{{D}_{2}}\) ​​ and \(\:{P}_{{H}_{2}}\) ​​ are the absolute pressures (kPa) of D 2 and H 2 in the gas phase. RESULTS AND DISCUSSION 1. Physico-chemical characterizations of metal incorporated mesoporous silica Figure 1 shows the low and high angle XRD patterns of bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica. In Fig. 1 a, every silica exhibits a broad diffraction peak centered at 2θ = 3.3°, corresponding to the (211) reflection of an ordered mesoporous framework, indicating that the periodic structure remained intact even after metal incorporation [ 29 ]. In Fig. 1 b, a broad feature centered at 2θ = 21–23° is observed in all samples, confirming the amorphous nature of the mesoporous silica matrix. In addition, Ag-mesoporous silica displays distinct peaks at 2θ = 30.8, 44.2, 54.9, 64.3 and 73.1°, corresponding to crystallinity of metallic Ag [ 30 ], while Cu-mesoporous silica exhibits two additional peaks at 2θ = 35.4 and 38.6°, attributed to Cu oxide [ 31 ]. These results collectively confirm that both Ag and Cu species were successfully incorporated into the mesoporous silica framework without destruction of its mesoporous structure. Figure 2 displays SEM images of bare, Ag- and Cu-mesoporous silica. All three samples exhibit a spherical morphology that is commonly observed in mesoporous silica. The particle size is ranging from 300 to 800 nm. Also, the shape and size of the particles remained consistent regardless of metal incorporation. This indicates that Ag and Cu incorporation does not significantly affect the nucleation and growth process of silica, thereby having consistent external morphology of the mesoporous silica. Figure 3 presents the N₂ physisorption isotherms and textural properties of bare, Ag- and Cu-mesoporous silica samples. Every mesoporous silica exhibited IUPAC Type IV N 2 physisorption isotherms, which are characteristic of mesoporous material. The highest N 2 adsorbed amount observed for bare mesoporous silica was 612.2 mmol g −1 , while Ag- and Cu-mesoporous silica showed slightly lower adsorption amount of 555.0 and 562.8 mmol g −1 , respectively due to the metal incorporation. The PSD of every mesoporous silica showed a narrow and unimodal distribution approximately centered at 4 nm. Combining with low angle XRD patterns in Fig. 1 a, this indicates that the ordered mesoporous framework was preserved, even after the incorporation of Ag and Cu into the silica matrix. As summarized in Table 1 , the BET surface area decreased from 1800 m² g⁻¹ of bare mesoporous silica to 1410 m² g⁻¹ for Ag-mesoporous silica and to 1360 m² g −1 for Cu-mesoporous silica, also indicating a reduction in accessible internal surface area due to the metal incorporation. In contrast, the pore volume increased marginally from 0.80 cm³ g −1 of bare mesoporous silica to 0.87 and 0.86 cm³ g −1 , suggesting that the open pore structure and interconnected network remained. Overall, the observations imply that Ag and Cu incorporation altered surface property without any collapsing the mesoporous framework. Table 1 Textural property of bare, Ag- and Cu-mesoporous silica. Adsorbent Pore volume (cm 3 g −1 ) BET surface area (m 2 g −1 ) Mesoporous silica 0.80 1800 Ag-mesoporous silica 0.87 1410 Cu-mesoporous silica 0.86 1360 Figure 4 shows the narrow XPS spectra of Ag 3d and Cu 2p regions for Ag- and Cu-mesoporous silica, respectively, while additional information on C 1s and O 1s narrow XPS spectra is provided in Fig. S1 of Supporting Information. In the Ag 3d spectrum, two distinct peaks are observed at 367.78 and 373.38 eV, which correspond to Ag 3d 5/2 and Ag 3d 3/2 , indicating the presence of metallic Ag [ 32 ]. The Cu 2p spectrum shows peaks at 932.28 and 952.17 eV, assigned to Cu 2p 3/2 and Cu 2p 1/2 , respectively [ 33 ]. In addition, a weak and broad satellite feature is detected near 943 eV, suggesting the presence of Cu 2+ species [ 34 ]. These results indicate that Ag and Cu were successfully introduced into the mesoporous silica and further the Cu species are present in mixed oxidation states. Figure 5 and Table 2 present the ²⁹Si MAS-NMR spectra and the relative signal intensities of Q², Q³ and Q⁴ species for bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica. Every mesoporous silica exhibits characteristic signals near − 90, − 100 and − 110 ppm, corresponding to Q² [(OH) 2 Si(OSi) 2 ], Q³ [(OH)Si(OSi) 3 ] and Q⁴ [Si(OSi) 4 ] [ 35 ], which represent silicon atoms bonded to two, three or four bridging oxygen atoms, respectively. In bare mesoporous silica, the Q², Q³ and Q⁴ intensities are 2.87, 12.07 and 12.25, respectively. The relatively strong Q² and Q³ signals reflect the presence of terminal silanol groups and partially condensed siloxane linkages. These features are characteristic of mesoporous silica, which is widely used due to its high surface area, tunable porosity and favorable mechanical stability arising from a partially interconnected silicate network [ 36 ]. For Ag-mesoporous silica, Q² and Q³ intensities decrease to 1.25 and 8.69, respectively, while Q⁴ slightly increases to 12.38. This change indicates that Ag incorporation promotes further network condensation by facilitating the formation of bridging siloxane bonds, resulting in a denser and more cross-linked silicate structure with reduced non-bridging oxygen content. On the other hand, Cu-mesoporous silica has two strong Q² signals at − 89 and − 94 ppm with intensity of 10.5 and 12.5, along with lower Q³ intensity of 8.5 and Q⁴ intensity of 10.3. The dominant Q² signals suggest a higher concentration of under-condensed silicate species, likely terminated by hydroxyl groups or associated with local structural irregularities. This result implies that Cu incorporation on mesoporous silica significantly interferes the siloxane network formation than Ag incorporation on mesoporous silica. These results highlight the distinct effects of metal incorporation on the degree of siloxane network condensation and surface silanol density. While Ag incorporation enhances framework stability through increased siloxane condensation, Cu incorporation relatively disrupts network formation, presumably increasing surface active sites relevant to isotope adsorption behavior discussed in subsequent sections. Table 2 Relative intensities of at Q² (δ ≈ −90 ppm), Q³ (δ ≈ −100 ppm) and Q⁴ (δ ≈ −110 ppm) peaks from 29 Si MAS-NMR spectra of bare, Ag- and Cu-mesoporous silica recorded with chemical shifts referenced to tetramethyl silane. Adsorbent Q 2 [(OH) 2 (SiO) 2 ] Q 3 [(OH)]Si(SiO) 3 ] Q 4 [Si(SiO) 4 ] Mesoporous silica 2.87 12.07 12.25 Ag-mesoporous silica 1.25 8.69 12.38 Cu-mesoporous silica 10.5 12.5 8.5 10.3 2. Single gas (H and D) adsorption/desorption isotherms Figure 6 shows the H₂ and D₂ adsorption–desorption isotherms of bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica measured at 77 K. Every isotherm exhibits higher uptake of D 2 than H 2 across the whole relative pressure range. Bare mesoporous silica displays the highest total adsorption capacity for both gases, with 61.3 mmol g −1 for H 2 and 70.1 mmol g −1 for D 2 . On the other hand, Ag-mesoporous silica shows a reduced uptake of 50.3 mmol g −1 for H₂ and 59.4 mmol g −1 for D 2 . Cu-mesoporous silica also has reduced adsorption as 57.3 mmol g −1 of H 2 and 75.3 mmol g −1 of D 2 , but presenting the largest difference between the two molecules among the three silicas. These adsorption trends suggest that differences in the internal pore structure and surface chemistry influence the affinity toward each gas molecules. The relatively low uptake in Ag-mesoporous silica implies a denser siloxane network and fewer accessible binding sites, possibly due to reduced surface hydroxyl groups or blocked pores as also demonstrated in ²⁹Si MAS-NMR analysis. In contrast, the enhanced adsorption in Cu-mesoporous silica, especially for D 2 , indicates the presence of more available interaction sites. These sites may include open silanol groups or coordinatively unsaturated metal oxygen environments, which may contribute to stronger interactions with heavier isotopes. 3. IAST-predicted D/H selectivity in binary mixture conditions To evaluate the potential of metal incorporated mesoporous silica for separating D 2 /H 2 mixture, D 2 /H 2 selectivities were predicted based on experimentally measured single-component isotherms by using IAST. Figure 7 presents the D₂/H₂ selectivity at 77 K, derived from IAST calculations using Langmuir–Freundlich fits of single-component isotherms shown in Fig. S2 of Supporting Information, for bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica under three different feed molar compositions of H 2 and D 2 : 1:1, 9:1 and 99:1. The following values refer to the condition at absolute pressure 1 kPa. At a 1:1 molar ratio of feed, the selectivity was 1.15 for bare mesoporous silica, 1.17 for Ag-mesoporous silica and 1.32 for Cu-mesoporous silica. When the applied H 2 and D 2 feed composition of 9:1, Cu-mesoporous silica exhibited a selectivity of 2.94, which was approximately 25% higher than that of Ag-mesoporous silica at 2.36 and bare mesoporous silica at 2.37. Under the extremely diluted condition for D 2 (99:1), the selectivity further increased to 5.52 for Cu-mesoporous silica, 4.06 for Ag-mesoporous silica and 3.78 for bare mesoporous silica, clearly indicating the most enhanced separation performance in the presence of Cu. As the ratio of D 2 decreased from 1:1 to 9:1 and 99:1, every silica showed a gradual increase in D 2 selectivity. Cu-mesoporous silica maintained the highest selectivity across the absolute pressure up to 1 kPa. This trend is attributed to the lower degree of network condensation and the presence of surface dispersed Cu oxide, demonstrated by physico-chemical characterizations, which enhance adsorption affinity toward D 2 . The presence of partially oxidized Cu species by XPS analysis (Fig. 4 b) and the dominance of Q 2 species by 29 Si NMR analysis (Fig. 5 ) and support this interpretation. In contrast, Ag-mesoporous silica contains metallic Ag within the pore structure, which modifies surface chemistry and improves selectivity compared to bare mesoporous silica, in line with the increased Q 4 fraction observed 29 Si NMR analysis (Fig. 5 ). Without any metal component, bare mesoporous silica lacks adsorption sites capable of separating between hydrogen isotopologues, leading to the lowest selectivity. Overall, the structural and compositional factors that govern D 2 interaction appear to enhance preferential adsorption, supporting the CAQS effect under the tested conditions. In Table 3 , the present adsorbents are compared to other classes of D 2 selective adsorbents recently applied for D 2 /H 2 separation as reported in the literature. The adsorbents listed in Table 3 were operated with molar feed ratio of 1:1 at 77 K. The comparison focuses on D 2 /H 2 selectivity under absolute pressure. The selectivities are low under low absolute pressure, and gradually increases as absolute pressure increases. There are literatures applied hydrogen isotopologues separation with MOF and carbon molecular sieve, but no research performed using mesoporous silica up to the best of our knowledge and based on the available literature. Considering absolute pressure, Cu-mesoporous silica under 1 kPa exhibits higher selectivity than ZIF-8 (1.1 under 10 kPa) and is close to the value of CMS T3A (2.05 under 1–2 kPa). This indicates metal incorporated mesoporous silica has good separation performance. The availability of many different mesoporous materials, metal incorporation agents and techniques for metal incorporation on mesoporous materials, is optimistic that adsorbents with better performance can be attained. Significant work remains behind to understand the performance and stability on real operation, especially T 2 /D 2 radioactive separation. However, the availability of a mesoporous material synthesis and metal incorporation process with co-condensation method, as shown in this work, is expected to be advantageous. Table 3 Summary of adsorption conditions and reported selectivity in previous studies, evaluated using IAST with a molar feed ratio of 1:1 (H 2 :D 2 ) at 77 K. Adsorbent D 2 /H 2 Selectivity Absolute pressure (kPa) References Mesoporous silica 1.15 1 This work Ag-mesoporous silica 1.17 1 This work Cu-mesoporous silica 1.32 1 This work Cu-BDC-NH 2 a 1.6 100 [ 28 ] Cu-BDCNH 2 @rGO b 2.2 100 [ 28 ] Ni-MOF-74 2 100 [ 37 ] ZIF-8 c 1.1 10 [ 38 ] Ni-MOF-74 4.6 10 [ 37 ] a Cu-amino-terephthalate MOF; b Cu MOF on reduced graphene oxide; and c zeolitic imidazolate framework-8. CONCLUSIONS Ag and Cu have been successfully incorporated into ordered mesoporous silica frameworks, thereby suggesting a platform for the application of hydrogen isotopologues separation. The resulting structural and surface property have been elucidated by XRD, SEM, N 2 physisorption, XPS and NMR. Simultaneously, the hydrogen isotopologues separation performance has been evaluated at 77 K. Ag incorporation forms a more condensed siloxane framework, resulting in a slight increase in D 2 selectivity (4.06) comparing to that of bare mesoporous silica (3.78) in the feed composition of 99:1 (H 2 :D 2 ). Further, Cu incorporation leads to the formation of silanol rich domains and surface dispersed Cu oxide species, which enhanced interactions with D 2 resulting selectivity of 5.52 in the feed composition of 99:1 (H 2 :D 2 ). These D 2 favorable surface properties from mesoporous silica and incorporated metal contribute to the CAQS effect, evidenced by surface composition and structural condensation influence D 2 /H 2 selectivity. These results demonstrate the potential of Ag and Cu incorporated mesoporous silica as a functional material for hydrogen isotopologues separation in heavy water nuclear power plant. Also, due to the available range of mesoporous materials, functionalizing agents and mesopore incorporation techniques, it is quite possible that the separation performance and long-term stability can be greatly enhanced on hydrogen isotope separation via CAQS. Declarations CONFLICT OF INTEREST The authors declare no conflict of interest. ACKNOWLEDGEMENT The authors are grateful for the financial support from National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (No. RS-2022-00155422). This research was also financially supported by the Institute of Civil Military Technology cooperation funded by the Defense Acquisition Program Administration and Ministry of Trade, Industry and Energy of Korea government under grant No. 22-CM-BR-14. References R. Ananthanarayanan, P. 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Nachtigall (Elsevier, 2005), pp. 455–460. J. Trébosc, J. W. Wiench, S. Huh, V. S.-Y. Lin, and M. Pruski, J Am Chem Soc 127, 3057 (2005). S. A. FitzGerald, C. J. Pierce, J. L. C. Rowsell, E. D. Bloch, and J. A. Mason, J Am Chem Soc 135, 9458 (2013). H. Oh, K. S. Park, S. B. Kalidindi, R. A. Fischer, and M. Hirscher, J Mater Chem A Mater 1, 3244 (2013). Supplementary Files 20250914GasseparationSI.docx Cite Share Download PDF Status: Published Journal Publication published 26 Nov, 2025 Read the published version in Korean Journal of Chemical Engineering → Version 1 posted Reviewers agreed at journal 18 Sep, 2025 Reviewers invited by journal 18 Sep, 2025 Editor assigned by journal 17 Sep, 2025 First submitted to journal 14 Sep, 2025 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. 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15:31:45","extension":"xml","order_by":47,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":98356,"visible":true,"origin":"","legend":"","description":"","filename":"KJCED25010470structuring.xml","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/f2fb9e5146ad83d6a99b5d12.xml"},{"id":92525816,"identity":"11542078-e2e0-4e5e-b42a-1293f45d9907","added_by":"auto","created_at":"2025-09-30 15:39:45","extension":"html","order_by":48,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":103509,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/f05e0839fa3750cfb646b424.html"},{"id":92524602,"identity":"3e310fa9-664d-41cb-b626-3f8ee51f73b8","added_by":"auto","created_at":"2025-09-30 15:31:44","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":57961,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a) low and (b) high angle XRD patterns of bare, Ag- and Cu-mesoporous silica.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/8f1f94089cf29f3c79c44604.png"},{"id":92524600,"identity":"48964282-af64-4cfa-a124-55033ca6b31c","added_by":"auto","created_at":"2025-09-30 15:31:44","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":2145055,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eSEM images of (a) bare, (b) Ag- and (c) Cu-mesoporous silica (scale bar is 1 μm).\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image2.tiff.png","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/85011985646e8f0dfaab01bc.png"},{"id":92524601,"identity":"2624f152-e6bd-4eae-a84a-449ee00e96a1","added_by":"auto","created_at":"2025-09-30 15:31:44","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":74633,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(a) N\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e adsorption (filled squares) and desorption (open squares) isotherms at 77 K and (b) pore size distributions calculated from N\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e adsorption isotherms by BdB-FHH method for bare, Ag- and Cu-mesoporous silica.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/76a3eb8666c208f5c62d9219.png"},{"id":92525795,"identity":"68e00a7f-c36a-4a3c-a64a-5b1ed09e82c6","added_by":"auto","created_at":"2025-09-30 15:39:44","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":442330,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eXPS spectra of (a) Ag 3d spectra of Ag-mesoporous silica and (b) Cu 2p spectra of Cu-mesoporous silica.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image4.tiff.png","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/ad03f1717fd1934767580116.png"},{"id":92525794,"identity":"79b32ece-0454-4162-b795-b4c295f02158","added_by":"auto","created_at":"2025-09-30 15:39:44","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":315490,"visible":true,"origin":"","legend":"\u003cp\u003e\u003csup\u003e\u003cstrong\u003e29\u003c/strong\u003e\u003c/sup\u003e\u003cstrong\u003eSi MAS-NMR spectra of bare, Ag- and Cu-mesoporous silica, with chemical shifts referenced to tetramethylsilane at Q² (δ ≈ -90 ppm), Q³ (δ ≈ -100 ppm) and Q⁴ (δ ≈ -110 ppm), recorded at a spinning frequency of 11 kHz.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image5.tiff.png","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/fb7f8e56d98b7d7e19471642.png"},{"id":92524609,"identity":"bb948154-8844-4025-8cf0-1b3e883816b7","added_by":"auto","created_at":"2025-09-30 15:31:44","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":903107,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eH\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e and D\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2 \u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eadsorption (filled square) and desorption (open square) isotherms of (a) bare, (b) Ag- and (c) Cu-mesoporous silica at 77 K.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image6.tiff.png","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/eacc1f9b9d812e9ce277e491.png"},{"id":92524608,"identity":"115c935c-d568-4b9a-a86a-6384bc1d4b5c","added_by":"auto","created_at":"2025-09-30 15:31:44","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":560788,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eIAST-predicted selectivity (D\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e/H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e) in diverse feed composition (1:1, 1:9 and 1:99 of D\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e and H\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e) for (a) bare, (b) Ag- and (c) Cu-mesoporous silica at 77 K.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image7.tiff.png","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/d2b0ca11d0c46e769aac04b1.png"},{"id":97179433,"identity":"88618ce1-7892-40d4-9f75-c465e97c71cd","added_by":"auto","created_at":"2025-12-01 16:15:33","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5332648,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/7176f1eb-5d11-41d3-b825-c04fde4ec321.pdf"},{"id":92524621,"identity":"6f56b5b2-a9f6-4baa-a999-e39407f0f324","added_by":"auto","created_at":"2025-09-30 15:31:44","extension":"docx","order_by":13,"title":"","display":"","copyAsset":false,"role":"supplement","size":407894,"visible":true,"origin":"","legend":"","description":"","filename":"20250914GasseparationSI.docx","url":"https://assets-eu.researchsquare.com/files/rs-7613043/v1/7634a953f6c9b07a068564e8.docx"}],"financialInterests":"","formattedTitle":"Metal Incorporated Mesoporous Silica for Hydrogen Isotope Gas Separation Application in Heavy Water Nuclear Power Plant","fulltext":[{"header":"INTRODUCTION","content":"\u003cp\u003eStable and consistent operation of heavy water nuclear power plants (NPPs) depends on isotopic purity of deuterium oxide (D\u003csub\u003e2\u003c/sub\u003eO), which works as both a neutron moderator and coolant due to its extremely low neutron capture cross-section [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. Especially, nuclear power plant systems such as the Canadian heavy water reactor require precise control of D\u003csub\u003e2\u003c/sub\u003eO concentration to maintain consistent fission and reactor safety against radiation of tritium (T\u003csub\u003e2\u003c/sub\u003e) [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Over the time of reactor operation, neutron irradiation and radiolysis of D\u003csub\u003e2\u003c/sub\u003eO gradually alter the hydrogen isotopologues composition in moderator and coolant systems, creating conditions that can lead to hazardous T\u003csub\u003e2\u003c/sub\u003e radiation and decreased efficiency of neutron moderator and coolant [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. To maintain the required isotopic purity during reactor operation, especially under accumulation of radioactive T\u003csub\u003e2\u003c/sub\u003e or dilution of deuterium (D\u003csub\u003e2\u003c/sub\u003e) conditions, techniques for hydrogen isotopologues separation are necessary to selectively remove T\u003csub\u003e2\u003c/sub\u003e and maintain D\u003csub\u003e2\u003c/sub\u003e concentration [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. In South Korea, T\u003csub\u003e2\u003c/sub\u003e removal facility have been implemented at the Wolsong NPP site to support reactor operation and secure the release of radioactive T\u003csub\u003e2\u003c/sub\u003e and high purity of D\u003csub\u003e2\u003c/sub\u003eO supply since 2007 [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. First part of this system is liquid phase catalytic exchange that tritiated heavy water passes through a catalyst column to remove T\u003csub\u003e2\u003c/sub\u003e from the D\u003csub\u003e2\u003c/sub\u003eO. Even if this method is widely applied, it is constrained by slow reaction kinetics and the requirement for packed columns with high performance catalyst that often exceed 20 m in height to achieve practical levels of separation [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. Second part is T\u003csub\u003e2\u003c/sub\u003e separation by cryogenic distillation, which separates hydrogen isotopologues based on extremely small differences in boiling point, specifically 20.3 K for potium (H\u003csub\u003e2\u003c/sub\u003e), 23.7 K for D\u003csub\u003e2\u003c/sub\u003e and 25.04 K for T\u003csub\u003e2\u003c/sub\u003e [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. This process is constrained by the limited separation factor, around 1.5 maximum, coupled with the extremely high energy demand of cryogenic operation and the resulting elevated overall costs [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. Other techniques, including palladium alloy membrane separation [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], laser-based isotope fractionation [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e] and the Girdler sulfide process [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e], have been also considered. However, these approaches are encountered troubles in low throughput, complicated operational facility, expensive material costs or environmental hazards. Thus, alternative ways have been actively explored to achieve the T\u003csub\u003e2\u003c/sub\u003e separation. As one of the alternatives, quantum mechanical approaches have been tried to separate hydrogen isotopologues with greater efficiency and scalability [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eRecent research has significantly focused on quantum sieving mechanisms coming from intrinsic difference in zero-point energy (ZPE) between hydrogen isotopologues [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. The ZPE indicates the residual vibrational energy that molecules retain at absolute zero temperature, 0 K, and is inversely proportional to mass of each molecule. Therefore, lighter isotopologues, i.e., H\u003csub\u003e2\u003c/sub\u003e here, remain more vibrationally delocalized, making them less susceptible to confinement in adsorption potential fields [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. This mass-dependent behavior forms the basis of kinetic quantum sieving (KQS), in which ultra-micropores smaller than 0.35 nm selectively retentate lighter isotopes by preferentially adsorbing heavier molecules, i.e., D\u003csub\u003e2\u003c/sub\u003e here. However, the KQS effect occurs only at extremely low temperatures, typically below 30 K, thereby requires intensive energy and highly stable and ordered porous structure under aggressive conditions. These strict energy and structural demands limit its scale-up and long-term application in practical systems [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. On the other hand, the concept of chemical affinity quantum sieving (CAQS) has been subjected under less aggressive conditions, temperate ranging from 77 K upwards, to enable selective adsorption of hydrogen isotopologues [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Selectivity caused by CAQS originates from both quantum delocalization effects and slight variations in physisorption energy [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Heavier isotopes, possessing lower ZPE, strongly adsorbed onto the active sites and are more likely to be stabilized in deeper potential wells [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Since the low temperature conditions are relatively less aggressive for CAQS, it is feasible to expand the range of materials and save the cost of energy.\u003c/p\u003e\u003cp\u003eSeveral metal functionalized porous materials have been explored for their potential to separate hydrogen isotopologues at liquid nitrogen (N\u003csub\u003e2\u003c/sub\u003e) temperature, 77 K, via CAQS. Silver (Ag) exchanged zeolite Socony Mobil\u0026ndash;5 has demonstrated a D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivity of ~\u0026thinsp;8.7, driven by the localized electrostatic fields around Ag ions that preferentially stabilize D\u003csub\u003e2\u003c/sub\u003e. Regardless of its effectiveness in isotope separation, its practical use is limited due to the low density of exchanged Ag ions, which restricts the overall adsorption capacity and hinders large scale implementation [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. Copper (Cu) substituted zeolitic imidazolate framework with gismondine topology, while showing D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivity of ~\u0026thinsp;4.0, exhibits very low D\u003csub\u003e2\u003c/sub\u003e uptake and limited adsorption capacity even under an exposure pressure of 2000 mbar due to slow adsorption kinetics [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. Nickel based metal-organic framework-74 (Ni-MOF-74) exhibited the highest D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivity of approximately 4.8 at near-zero pressure and the selectivity decreased with increasing pressure. Both Cobalt and magnesium based MOF-74 showed D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivity of approximately 3.5 and also exhibited decreasing trends with increasing pressure. Zinc (Zn) based MOF-74 showed a lower D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivity of approximately 1.7, attributed to weaker interactions between hydrogen isotopologues and Zn\u0026sup2;⁺ coordination sites [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eTo address these challenges, this study investigates mesoporous silica modified with metal species, such as Ag and Cu, as a candidate material for hydrogen isotopologues separation at 77 K. Mesoporous silica provides several advantages for this purpose, including a high specific surface area, tunable pore structures and excellent thermal and mechanical stability [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. Furthermore, its surface, composed of plenty of silanol group, can be easily tailored by incorporating metal species, enabling enhancement of isotope-specific surface interactions [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. In this study, metal incorporated mesoporous silica was synthesized and its physico-chemical properties were characterized then applied for D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e separation. Ag and Cu were successfully incorporated into the mesoporous silica framework through co-condensation method followed by calcination. The resulting materials were precisely characterized using diverse techniques to access the structural, surface property, silanol density as well as siloxane network condensation. Single component adsorption isotherms were obtained and binary isotope separation behavior was analyzed using ideal adsorbed solution theory (IAST) to understand the effect of surface modifications on selectivity of D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e"},{"header":"EXPERIMENTAL","content":"\n\u003ch3\u003e1. Materials\u003c/h3\u003e\n\u003cp\u003eThe following chemicals and gases were used as received without further purification. Tetraethyl orthosilicate (TEOS, 98%), cetyltrimethylammonium bromide (CTAB, \u0026gt;98%), ethanol (EtOH, 99.99%), ammonium hydroxide solution (NH\u003csub\u003e3\u003c/sub\u003e, 28.0\u0026thinsp;~\u0026thinsp;30.0 wt%), Ag nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e, \u0026ge; 99.0%) and Cu (II) nitrate trihydrate (CuN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003e\u0026middot;3H\u003csub\u003e2\u003c/sub\u003eO, 99\u0026thinsp;~\u0026thinsp;104%) were purchased from Sigma-Aldrich. Deionized (DI) water was supplied from Direct-Q\u0026reg; 3 water purification system with resistivity of 18.2 MΩ cm at 298 K. H\u003csub\u003e2\u003c/sub\u003e gas (99.999%) and N\u003csub\u003e2\u003c/sub\u003e gas (99.999%) were purchased from Daesung Industrial Gases Co., Ltd. D\u003csub\u003e2\u003c/sub\u003e gas (99.999%) and neon gas (Ne, 99. 999%) were purchased from Noble gas Co., Ltd.\u003c/p\u003e\n\u003ch3\u003e2. Preparation of mesoporous silica\u003c/h3\u003e\n\u003cp\u003eMesoporous silica was prepared as reported somewhere else [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. CTAB (2.4 g) was dissolved in the equivolume mixture of DI water (50 mL) and ethanol (50 mL). After 10 min of fierce stirring, NH\u003csub\u003e3\u003c/sub\u003e (12 mL) was added. Subsequently, TEOS (3.4 g) was added drop-wisely into the mixture solution. The mixed solution was additionally stirred for another 2 h until it converted as gel. The molar composition of the final gel was TEOS: 0.43 CTAB: 12.5 NH\u003csub\u003e3\u003c/sub\u003e: 54.3 EtOH: 416 H\u003csub\u003e2\u003c/sub\u003eO. The resulting gel was washed with deionized water for 5 times and solid/liquid was separated by centrifugation at each cycle. Then, the resulting solid was dried in the oven at 338 K overnight. The CTAB template, pore directing agent here, was removed by calcination at 823 K with a heating rate of 274 K min\u003csup\u003e\u003cb\u003e\u0026minus;\u003c/b\u003e1\u003c/sup\u003e for 6 h under stagnant air conditions in the furnace.\u003c/p\u003e\n\u003ch3\u003e3. Preparation of Ag- and Cu-mesoporous silica\u003c/h3\u003e\n\u003cp\u003eCTAB (5.1 g) was dissolved in the mixed solution of DI water (200 mL) and ethanol (100 mL). Then, NH\u003csub\u003e3\u003c/sub\u003e (6.78 mL) was added. After 10 min of fierce stirring, TEOS (6.7 g) was added drop-wisely into the solution mixture. After that, the AgNO\u003csub\u003e3\u003c/sub\u003e (0.112 g) or CuN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003e (0.156 g) precursor was doped into the solution. The mixed solution was stirred for another 4 h. The molar composition of the gel was TEOS: 0.02 x: 0.41 CTAB: 12 NH\u003csub\u003e3\u003c/sub\u003e: 54 EtOH: 173 H\u003csub\u003e2\u003c/sub\u003eO, where x stands for Ag or Cu. The final gel was washed, centrifuged, dried identical way as described in the previous section. The CTAB template was removed by calcination at 823 K with a heating rate of 276 K min\u003csup\u003e\u003cb\u003e\u0026minus;\u003c/b\u003e1\u003c/sup\u003e for 6 h under stagnant air conditions in furnace.\u003c/p\u003e\n\u003ch3\u003e4. Characterizations\u003c/h3\u003e\n\u003cp\u003eThe X-ray diffraction (XRD) patterns of the samples were measured using a D2 PHASER (Bruker) from 0 to 8˚ (low angle) and 10 to 80˚ (high angle) of 2\u003cem\u003eθ\u003c/em\u003e at a rate of 0.002˚ per step with a counting time of 0.5 s per step using a Cu-K-alpha radiation source. The scanning electron microscopy (SEM) images were obtained SU-8020 (Hitachi) at a landing energy of 15 kV. The samples were prepared on the top of carbon tape and coated with gold. The N\u003csub\u003e2\u003c/sub\u003e physisorption isotherms were measured at 77 K using an Autosorb iQ-XR Viton (Quantachrome). Before measurement, the samples were degassed overnight at 423 K under vacuum to remove the pre-adsorbed gases, moisture and any other impurities. The N\u003csub\u003e2\u003c/sub\u003e physisorption isotherms were analyzed to specify the specific surface area, pore volume and pore size distribution (PSD) of the samples. The specific surface area and PSD were determined by the Brunauer-Emmett-Teller (BET) method and by Broekhoff-de Boer/Frenkel-Halsey-Hill (BdB-FHH) method, respectively. The X-ray photoelectron spectroscopy (XPS) spectra of the samples were obtained using a K-alpha\u0026thinsp;+\u0026thinsp;spectrometer (Thermo Scientific) with a monochromatic Al-K-alpha radiation source (1486.6 eV). The spectra were acquired with a pass energy of 50 eV for high-resolution scans. Data analysis was performed using Avantage software. \u003csup\u003e29\u003c/sup\u003eSi magic angle spinning-nuclear magnetic resonance analysis (\u003csup\u003e29\u003c/sup\u003eSi MAS-NMR) spectra were using an AVANCE Ⅲ HD 400 MHz solid state NMR spectrometer (Bruker). The probe used was 4 mm double resonance CPMAS probe. \u003csup\u003e29\u003c/sup\u003eSi MAS NMR experiments were performed at 79.495 MHz. These spectra were acquired with a one pulse sequence. Spinning frequencies of 11 kHz, π/4 pulse widths of 2 \u0026micro;s, contact times of 2 ms, delay times of 20 s were used.\u003c/p\u003e\n\u003ch3\u003e5. Single gas (H and D) isotherm measurements\u003c/h3\u003e\n\u003cp\u003eThe single gas (H\u003csub\u003e2\u003c/sub\u003e and D\u003csub\u003e2\u003c/sub\u003e) adsorption isotherm was measured at 77 K using an Autosorb iQ-XR (Quantachrome). Before measurement, the samples were degassed overnight at 423 K under vacuum to remove pre-adsorbed gases, moisture and any other impurities. Adsorption measurements were conducted over a relative pressure (P/P\u003csub\u003e0\u003c/sub\u003e) ranging from 0 to 1 to determine the equilibrium adsorption capacities of H\u003csub\u003e2\u003c/sub\u003e and D\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\u003cp\u003eThe separation performance (adsorption capacity and selectivity) of hydrogen isotopologues separation was evaluated using the IAST [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. The IAST is a well-established method for predicting binary mixture adsorption behaviors of various types of adsorbents [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. The IAST selectivities were obtained at the range from equimolar to D\u003csub\u003e2\u003c/sub\u003e depleted conditions.\u003c/p\u003e\u003cp\u003eThe single gas adsorption isotherms of H₂ and D₂ were fitted to the Langmuir-Freundlich equation (Eq.\u0026nbsp;(1)) to obtain the parameters required for IAST calculations:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:\\begin{array}{c}{\\:q}_{i}=\\:{q}_{max,\\:\\:i}\\left(\\frac{{\\left({K}_{i}{P}_{i}\\right)}^{n}}{{1+\\left({K}_{i}{P}_{i}\\right)}^{n}}\\right) \\left(1\\right)\\end{array}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eAll parameters are denoted with subscript \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:i\\)\u003c/span\u003e\u003c/span\u003e, representing the species H\u003csub\u003e2\u003c/sub\u003e or D\u003csub\u003e2\u003c/sub\u003e. \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:q\\)\u003c/span\u003e\u003c/span\u003e is the amount adsorbed (mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e), \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{q}_{max}\\:\\)\u003c/span\u003e\u003c/span\u003eis the maximum adsorption capacity (mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e), \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:K\\)\u003c/span\u003e\u003c/span\u003e is the equilibrium constant (kPa\u003csup\u003e\u0026minus;1\u003c/sup\u003e), \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:P\\)\u003c/span\u003e\u003c/span\u003e is the absolute pressure (kPa​) and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:n\\)\u003c/span\u003e\u003c/span\u003e is the heterogeneity factor. The parameters \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{q}_{max}\\)\u003c/span\u003e\u003c/span\u003e​, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:K\\)\u003c/span\u003e\u003c/span\u003e and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:n\\)\u003c/span\u003e\u003c/span\u003e were obtained by fitting the H\u003csub\u003e2\u003c/sub\u003e and D\u003csub\u003e2\u003c/sub\u003e adsorption isotherms to Eq.\u0026nbsp;(1).\u003c/p\u003e\u003cp\u003eThe binary adsorption equilibria of H\u003csub\u003e2\u003c/sub\u003e/D\u003csub\u003e2\u003c/sub\u003e mixtures are predicted through IAST. The spreading pressures were calculated from the fitted isotherms and the partial pressures in the gas phase were derived by solving the IAST equations numerically. Then, selectivity (\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{S}_{{D}_{2}/{H}_{2}}\\)\u003c/span\u003e\u003c/span\u003e) was calculated as following Eq.\u0026nbsp;(2):\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equb\" name=\"EquationSource\"\u003e\n$$\\:\\begin{array}{c}{S}_{{D}_{2}/{H}_{2}}=\\:\\frac{{q}_{{D}_{2}}{/q}_{{H}_{2}}}{{P}_{{D}_{2}}{/P}_{{H}_{2}}} \\left(2\\right)\\end{array}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eHere, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{q}_{{D}_{2}}\\)\u003c/span\u003e\u003c/span\u003e​​ and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{q}_{{H}_{2}}\\)\u003c/span\u003e\u003c/span\u003e represent the adsorbed amounts (mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e) of D\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e, respectively, while \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{P}_{{D}_{2}}\\)\u003c/span\u003e\u003c/span\u003e​​ and \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:{P}_{{H}_{2}}\\)\u003c/span\u003e\u003c/span\u003e​​ are the absolute pressures (kPa) of D\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e in the gas phase.\u003c/p\u003e"},{"header":"RESULTS AND DISCUSSION","content":"\n\u003ch3\u003e1. Physico-chemical characterizations of metal incorporated mesoporous silica\u003c/h3\u003e\n\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows the low and high angle XRD patterns of bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica. In Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, every silica exhibits a broad diffraction peak centered at 2θ\u0026thinsp;=\u0026thinsp;3.3\u0026deg;, corresponding to the (211) reflection of an ordered mesoporous framework, indicating that the periodic structure remained intact even after metal incorporation [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. In Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, a broad feature centered at 2θ\u0026thinsp;=\u0026thinsp;21\u0026ndash;23\u0026deg; is observed in all samples, confirming the amorphous nature of the mesoporous silica matrix. In addition, Ag-mesoporous silica displays distinct peaks at 2θ\u0026thinsp;=\u0026thinsp;30.8, 44.2, 54.9, 64.3 and 73.1\u0026deg;, corresponding to crystallinity of metallic Ag [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e], while Cu-mesoporous silica exhibits two additional peaks at 2θ\u0026thinsp;=\u0026thinsp;35.4 and 38.6\u0026deg;, attributed to Cu oxide [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. These results collectively confirm that both Ag and Cu species were successfully incorporated into the mesoporous silica framework without destruction of its mesoporous structure.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e displays SEM images of bare, Ag- and Cu-mesoporous silica. All three samples exhibit a spherical morphology that is commonly observed in mesoporous silica. The particle size is ranging from 300 to 800 nm. Also, the shape and size of the particles remained consistent regardless of metal incorporation. This indicates that Ag and Cu incorporation does not significantly affect the nucleation and growth process of silica, thereby having consistent external morphology of the mesoporous silica.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e presents the N₂ physisorption isotherms and textural properties of bare, Ag- and Cu-mesoporous silica samples. Every mesoporous silica exhibited IUPAC Type IV N\u003csub\u003e2\u003c/sub\u003e physisorption isotherms, which are characteristic of mesoporous material. The highest N\u003csub\u003e2\u003c/sub\u003e adsorbed amount observed for bare mesoporous silica was 612.2 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e, while Ag- and Cu-mesoporous silica showed slightly lower adsorption amount of 555.0 and 562.8 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e, respectively due to the metal incorporation. The PSD of every mesoporous silica showed a narrow and unimodal distribution approximately centered at 4 nm. Combining with low angle XRD patterns in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, this indicates that the ordered mesoporous framework was preserved, even after the incorporation of Ag and Cu into the silica matrix. As summarized in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, the BET surface area decreased from 1800 m\u0026sup2; g⁻\u0026sup1; of bare mesoporous silica to 1410 m\u0026sup2; g⁻\u0026sup1; for Ag-mesoporous silica and to 1360 m\u0026sup2; g\u003csup\u003e\u0026minus;1\u003c/sup\u003e for Cu-mesoporous silica, also indicating a reduction in accessible internal surface area due to the metal incorporation. In contrast, the pore volume increased marginally from 0.80 cm\u0026sup3; g\u003csup\u003e\u0026minus;1\u003c/sup\u003e of bare mesoporous silica to 0.87 and 0.86 cm\u0026sup3; g\u003csup\u003e\u0026minus;1\u003c/sup\u003e, suggesting that the open pore structure and interconnected network remained. Overall, the observations imply that Ag and Cu incorporation altered surface property without any collapsing the mesoporous framework.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eTextural property of bare, Ag- and Cu-mesoporous silica.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"3\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAdsorbent\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003ePore volume (cm\u003csup\u003e3\u003c/sup\u003e g\u003csup\u003e\u0026minus;1\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eBET surface area (m\u003csup\u003e2\u003c/sup\u003e g\u003csup\u003e\u0026minus;1\u003c/sup\u003e)\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e0.80\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1800\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAg-mesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e0.87\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1410\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCu-mesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e0.86\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1360\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shows the narrow XPS spectra of Ag 3d and Cu 2p regions for Ag- and Cu-mesoporous silica, respectively, while additional information on C 1s and O 1s narrow XPS spectra is provided in Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e of Supporting Information. In the Ag 3d spectrum, two distinct peaks are observed at 367.78 and 373.38 eV, which correspond to Ag 3d\u003csub\u003e5/2 \u003c/sub\u003eand Ag 3d\u003csub\u003e3/2\u003c/sub\u003e, indicating the presence of metallic Ag [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. The Cu 2p spectrum shows peaks at 932.28 and 952.17 eV, assigned to Cu 2p\u003csub\u003e3/2\u003c/sub\u003e and Cu 2p\u003csub\u003e1/2\u003c/sub\u003e, respectively [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. In addition, a weak and broad satellite feature is detected near 943 eV, suggesting the presence of Cu\u003csup\u003e2+\u003c/sup\u003e species [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. These results indicate that Ag and Cu were successfully introduced into the mesoporous silica and further the Cu species are present in mixed oxidation states.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e present the \u0026sup2;⁹Si MAS-NMR spectra and the relative signal intensities of Q\u0026sup2;, Q\u0026sup3; and Q⁴ species for bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica. Every mesoporous silica exhibits characteristic signals near \u0026minus;\u0026thinsp;90, \u0026minus;\u0026thinsp;100 and \u0026minus;\u0026thinsp;110 ppm, corresponding to Q\u0026sup2; [(OH)\u003csub\u003e2\u003c/sub\u003eSi(OSi)\u003csub\u003e2\u003c/sub\u003e], Q\u0026sup3; [(OH)Si(OSi)\u003csub\u003e3\u003c/sub\u003e] and Q⁴ [Si(OSi)\u003csub\u003e4\u003c/sub\u003e] [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e], which represent silicon atoms bonded to two, three or four bridging oxygen atoms, respectively. In bare mesoporous silica, the Q\u0026sup2;, Q\u0026sup3; and Q⁴ intensities are 2.87, 12.07 and 12.25, respectively. The relatively strong Q\u0026sup2; and Q\u0026sup3; signals reflect the presence of terminal silanol groups and partially condensed siloxane linkages. These features are characteristic of mesoporous silica, which is widely used due to its high surface area, tunable porosity and favorable mechanical stability arising from a partially interconnected silicate network [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]. For Ag-mesoporous silica, Q\u0026sup2; and Q\u0026sup3; intensities decrease to 1.25 and 8.69, respectively, while Q⁴ slightly increases to 12.38. This change indicates that Ag incorporation promotes further network condensation by facilitating the formation of bridging siloxane bonds, resulting in a denser and more cross-linked silicate structure with reduced non-bridging oxygen content. On the other hand, Cu-mesoporous silica has two strong Q\u0026sup2; signals at \u0026minus;\u0026thinsp;89 and \u0026minus;\u0026thinsp;94 ppm with intensity of 10.5 and 12.5, along with lower Q\u0026sup3; intensity of 8.5 and Q⁴ intensity of 10.3. The dominant Q\u0026sup2; signals suggest a higher concentration of under-condensed silicate species, likely terminated by hydroxyl groups or associated with local structural irregularities. This result implies that Cu incorporation on mesoporous silica significantly interferes the siloxane network formation than Ag incorporation on mesoporous silica. These results highlight the distinct effects of metal incorporation on the degree of siloxane network condensation and surface silanol density. While Ag incorporation enhances framework stability through increased siloxane condensation, Cu incorporation relatively disrupts network formation, presumably increasing surface active sites relevant to isotope adsorption behavior discussed in subsequent sections.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eRelative intensities of at Q\u0026sup2; (δ \u0026asymp; \u0026minus;90 ppm), Q\u0026sup3; (δ \u0026asymp; \u0026minus;100 ppm) and Q⁴ (δ \u0026asymp; \u0026minus;110 ppm) peaks from \u003csup\u003e29\u003c/sup\u003eSi MAS-NMR spectra of bare, Ag- and Cu-mesoporous silica recorded with chemical shifts referenced to tetramethyl silane.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"4\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAdsorbent\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eQ\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e\u003cp\u003e[(OH)\u003csub\u003e2\u003c/sub\u003e(SiO)\u003csub\u003e2\u003c/sub\u003e]\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eQ\u003csup\u003e3\u003c/sup\u003e\u003c/p\u003e\u003cp\u003e[(OH)]Si(SiO)\u003csub\u003e3\u003c/sub\u003e]\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eQ\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e\u003cp\u003e[Si(SiO)\u003csub\u003e4\u003c/sub\u003e]\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e2.87\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e12.07\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e12.25\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAg-mesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e1.25\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e8.69\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e12.38\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCu-mesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e10.5 12.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e8.5\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e10.3\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\n\u003ch3\u003e2. Single gas (H and D) adsorption/desorption isotherms\u003c/h3\u003e\n\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows the H₂ and D₂ adsorption\u0026ndash;desorption isotherms of bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica measured at 77 K. Every isotherm exhibits higher uptake of D\u003csub\u003e2\u003c/sub\u003e than H\u003csub\u003e2\u003c/sub\u003e across the whole relative pressure range. Bare mesoporous silica displays the highest total adsorption capacity for both gases, with 61.3 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e for H\u003csub\u003e2\u003c/sub\u003e and 70.1 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e for D\u003csub\u003e2\u003c/sub\u003e. On the other hand, Ag-mesoporous silica shows a reduced uptake of 50.3 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e for H₂ and 59.4 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e for D\u003csub\u003e2\u003c/sub\u003e. Cu-mesoporous silica also has reduced adsorption as 57.3 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e of H\u003csub\u003e2\u003c/sub\u003e and 75.3 mmol g\u003csup\u003e\u0026minus;1\u003c/sup\u003e of D\u003csub\u003e2\u003c/sub\u003e, but presenting the largest difference between the two molecules among the three silicas. These adsorption trends suggest that differences in the internal pore structure and surface chemistry influence the affinity toward each gas molecules. The relatively low uptake in Ag-mesoporous silica implies a denser siloxane network and fewer accessible binding sites, possibly due to reduced surface hydroxyl groups or blocked pores as also demonstrated in \u0026sup2;⁹Si MAS-NMR analysis. In contrast, the enhanced adsorption in Cu-mesoporous silica, especially for D\u003csub\u003e2\u003c/sub\u003e, indicates the presence of more available interaction sites. These sites may include open silanol groups or coordinatively unsaturated metal oxygen environments, which may contribute to stronger interactions with heavier isotopes.\u003c/p\u003e\n\u003ch3\u003e3. IAST-predicted D/H selectivity in binary mixture conditions\u003c/h3\u003e\n\u003cp\u003e\u003c/p\u003e\u003cp\u003eTo evaluate the potential of metal incorporated mesoporous silica for separating D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e mixture, D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivities were predicted based on experimentally measured single-component isotherms by using IAST. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e presents the D₂/H₂ selectivity at 77 K, derived from IAST calculations using Langmuir\u0026ndash;Freundlich fits of single-component isotherms shown in Fig. S2 of Supporting Information, for bare mesoporous silica, Ag-mesoporous silica and Cu-mesoporous silica under three different feed molar compositions of H\u003csub\u003e2\u003c/sub\u003e and D\u003csub\u003e2\u003c/sub\u003e: 1:1, 9:1 and 99:1. The following values refer to the condition at absolute pressure 1 kPa. At a 1:1 molar ratio of feed, the selectivity was 1.15 for bare mesoporous silica, 1.17 for Ag-mesoporous silica and 1.32 for Cu-mesoporous silica. When the applied H\u003csub\u003e2\u003c/sub\u003e and D\u003csub\u003e2\u003c/sub\u003e feed composition of 9:1, Cu-mesoporous silica exhibited a selectivity of 2.94, which was approximately 25% higher than that of Ag-mesoporous silica at 2.36 and bare mesoporous silica at 2.37. Under the extremely diluted condition for D\u003csub\u003e2\u003c/sub\u003e (99:1), the selectivity further increased to 5.52 for Cu-mesoporous silica, 4.06 for Ag-mesoporous silica and 3.78 for bare mesoporous silica, clearly indicating the most enhanced separation performance in the presence of Cu. As the ratio of D\u003csub\u003e2\u003c/sub\u003e decreased from 1:1 to 9:1 and 99:1, every silica showed a gradual increase in D\u003csub\u003e2\u003c/sub\u003e selectivity. Cu-mesoporous silica maintained the highest selectivity across the absolute pressure up to 1 kPa. This trend is attributed to the lower degree of network condensation and the presence of surface dispersed Cu oxide, demonstrated by physico-chemical characterizations, which enhance adsorption affinity toward D\u003csub\u003e2\u003c/sub\u003e. The presence of partially oxidized Cu species by XPS analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb) and the dominance of Q\u003csup\u003e2\u003c/sup\u003e species by \u003csup\u003e29\u003c/sup\u003eSi NMR analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e) and support this interpretation. In contrast, Ag-mesoporous silica contains metallic Ag within the pore structure, which modifies surface chemistry and improves selectivity compared to bare mesoporous silica, in line with the increased Q\u003csup\u003e4\u003c/sup\u003e fraction observed \u003csup\u003e29\u003c/sup\u003eSi NMR analysis (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e). Without any metal component, bare mesoporous silica lacks adsorption sites capable of separating between hydrogen isotopologues, leading to the lowest selectivity. Overall, the structural and compositional factors that govern D\u003csub\u003e2\u003c/sub\u003e interaction appear to enhance preferential adsorption, supporting the CAQS effect under the tested conditions.\u003c/p\u003e\u003cp\u003eIn Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, the present adsorbents are compared to other classes of D\u003csub\u003e2\u003c/sub\u003e selective adsorbents recently applied for D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e separation as reported in the literature. The adsorbents listed in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e were operated with molar feed ratio of 1:1 at 77 K. The comparison focuses on D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivity under absolute pressure. The selectivities are low under low absolute pressure, and gradually increases as absolute pressure increases. There are literatures applied hydrogen isotopologues separation with MOF and carbon molecular sieve, but no research performed using mesoporous silica up to the best of our knowledge and based on the available literature. Considering absolute pressure, Cu-mesoporous silica under 1 kPa exhibits higher selectivity than ZIF-8 (1.1 under 10 kPa) and is close to the value of CMS T3A (2.05 under 1\u0026ndash;2 kPa). This indicates metal incorporated mesoporous silica has good separation performance. The availability of many different mesoporous materials, metal incorporation agents and techniques for metal incorporation on mesoporous materials, is optimistic that adsorbents with better performance can be attained. Significant work remains behind to understand the performance and stability on real operation, especially T\u003csub\u003e2\u003c/sub\u003e/D\u003csub\u003e2\u003c/sub\u003e radioactive separation. However, the availability of a mesoporous material synthesis and metal incorporation process with co-condensation method, as shown in this work, is expected to be advantageous.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eSummary of adsorption conditions and reported selectivity in previous studies, evaluated using IAST with a molar feed ratio of 1:1 (H\u003csub\u003e2\u003c/sub\u003e:D\u003csub\u003e2\u003c/sub\u003e) at 77 K.\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"4\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAdsorbent\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eD\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e Selectivity\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eAbsolute pressure (kPa)\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eReferences\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eMesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1.15\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eThis work\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eAg-mesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1.17\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eThis work\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCu-mesoporous silica\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1.32\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003eThis work\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCu-BDC-NH\u003csub\u003e2\u003c/sub\u003e\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e100\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCu-BDCNH\u003csub\u003e2\u003c/sub\u003e@rGO\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2.2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e100\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eNi-MOF-74\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e100\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eZIF-8\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e1.1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e10\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eNi-MOF-74\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e4.6\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e10\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e[\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003e\u003csup\u003ea\u003c/sup\u003eCu-amino-terephthalate MOF; \u003csup\u003eb\u003c/sup\u003eCu MOF on reduced graphene oxide; and \u003csup\u003ec\u003c/sup\u003ezeolitic imidazolate framework-8.\u003c/p\u003e"},{"header":"CONCLUSIONS","content":"\u003cp\u003eAg and Cu have been successfully incorporated into ordered mesoporous silica frameworks, thereby suggesting a platform for the application of hydrogen isotopologues separation. The resulting structural and surface property have been elucidated by XRD, SEM, N\u003csub\u003e2\u003c/sub\u003e physisorption, XPS and NMR. Simultaneously, the hydrogen isotopologues separation performance has been evaluated at 77 K. Ag incorporation forms a more condensed siloxane framework, resulting in a slight increase in D\u003csub\u003e2\u003c/sub\u003e selectivity (4.06) comparing to that of bare mesoporous silica (3.78) in the feed composition of 99:1 (H\u003csub\u003e2\u003c/sub\u003e:D\u003csub\u003e2\u003c/sub\u003e). Further, Cu incorporation leads to the formation of silanol rich domains and surface dispersed Cu oxide species, which enhanced interactions with D\u003csub\u003e2\u003c/sub\u003e resulting selectivity of 5.52 in the feed composition of 99:1 (H\u003csub\u003e2\u003c/sub\u003e:D\u003csub\u003e2\u003c/sub\u003e). These D\u003csub\u003e2\u003c/sub\u003e favorable surface properties from mesoporous silica and incorporated metal contribute to the CAQS effect, evidenced by surface composition and structural condensation influence D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e selectivity. These results demonstrate the potential of Ag and Cu incorporated mesoporous silica as a functional material for hydrogen isotopologues separation in heavy water nuclear power plant. Also, due to the available range of mesoporous materials, functionalizing agents and mesopore incorporation techniques, it is quite possible that the separation performance and long-term stability can be greatly enhanced on hydrogen isotope separation via CAQS.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eCONFLICT OF INTEREST\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no conflict of interest.\u003c/p\u003e\u003ch2\u003eACKNOWLEDGEMENT\u003c/h2\u003e\u003cp\u003eThe authors are grateful for the financial support from National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (No. RS-2022-00155422). This research was also financially supported by the Institute of Civil Military Technology cooperation funded by the Defense Acquisition Program Administration and Ministry of Trade, Industry and Energy of Korea government under grant No. 22-CM-BR-14.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eR. Ananthanarayanan, P. Sahoo, and N. Murali, J Radioanal Nucl Chem 299, 293 (2014).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eG. M. Allison, Can J Chem Eng 36, 217 (1958).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eX. Hou, Journal of Nuclear Fuel Cycle and Waste Technology 16, 11 (2018).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eM. Yassari, A. Bagherzadeh, A. Docoslis, M. R. Daymond, and M. Sadrzadeh, Sep Purif Technol 374, 133666 (2025).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eH. Chung, D. Koo, D. Chung, D. Jung, S. Paek, M. Lee, S.-P. Yim, S. Lee, K.-S. Seo, S. 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C. Rowsell, E. D. Bloch, and J. A. Mason, J Am Chem Soc 135, 9458 (2013).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eH. Oh, K. S. Park, S. B. Kalidindi, R. A. Fischer, and M. Hirscher, J Mater Chem A Mater 1, 3244 (2013).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"korean-journal-of-chemical-engineering","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"kjce","sideBox":"Learn more about [Korean Journal of Chemical Engineering](http://link.springer.com/journal/11814)","snPcode":"11814","submissionUrl":"https://www.editorialmanager.com/kjce/default2.aspx","title":"Korean Journal of Chemical Engineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Subscription","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Hydrogen isotopologues separation, Mesoporous silica, Metal incorporation, Chemical affinity quantum sieving, Cryogenic adsorption, Ideal adsorbed solution theory","lastPublishedDoi":"10.21203/rs.3.rs-7613043/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7613043/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe separation of hydrogen isotopologues, such as protium (H₂), deuterium (D₂) and tritium, is necessary for the stable and consistent operation of heavy water nuclear power plants, where deuterium oxide is used as both moderator and coolant. As conventional processes, cryogenic distillation and catalytic exchange are widely applied for hydrogen isotopologues separation. However, those techniques have been encountered the intrinsic limitations including high energy consumption, slow reaction rates and large facility expenses. As an alternative, separation techniques based on the mechanism of chemical affinity quantum sieving have been studied to separate isotopes at temperate ranging from liquid nitrogen (N\u003csub\u003e2\u003c/sub\u003e) temperature (77 K) to upwards through differences in adsorption. In this study, mesoporous silica modified with silver or copper (Cu) was prepared and applied for hydrogen isotopologues separation at 77 K. Their structural, morphological and surface chemical properties were analyzed using X-ray diffraction, scanning electron microscopy, N\u003csub\u003e2\u003c/sub\u003e physisorption, X-ray photoelectron spectroscopy and solid-state magic angle spinning silicon-29 nuclear magnetic resonance spectroscopy. Single gas adsorption isotherms of H\u003csub\u003e2\u003c/sub\u003e and D\u003csub\u003e2\u003c/sub\u003e were measured and binary separation performance was evaluated using equilibrium modeling. Cu-incorporated mesoporous silica showed the highest D\u003csub\u003e2\u003c/sub\u003e over H\u003csub\u003e2\u003c/sub\u003e selectivity, reaching 5.52 under the D\u003csub\u003e2\u003c/sub\u003e diluted conditions (1:99). This is attributed to the dispersed Cu oxide species in the silica framework as well as the silanol rich domains of mesoporous silica which both enhance interaction with D\u003csub\u003e2\u003c/sub\u003e. These results suggest that isotope selectivity (D\u003csub\u003e2\u003c/sub\u003e/H\u003csub\u003e2\u003c/sub\u003e) can be tuned by adjusting the surface structure, property and pore network of mesoporous silica, offering a practical approach for hydrogen isotopologues separation in nuclear facility.\u003c/p\u003e","manuscriptTitle":"Metal Incorporated Mesoporous Silica for Hydrogen Isotope Gas Separation Application in Heavy Water Nuclear Power Plant","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-09-30 15:31:39","doi":"10.21203/rs.3.rs-7613043/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"reviewerAgreed","content":"","date":"2025-09-19T02:31:37+00:00","index":0,"fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-09-19T02:27:05+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-09-17T15:33:08+00:00","index":"","fulltext":""},{"type":"submitted","content":"Korean Journal of Chemical Engineering","date":"2025-09-14T10:02:33+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"korean-journal-of-chemical-engineering","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"kjce","sideBox":"Learn more about [Korean Journal of Chemical Engineering](http://link.springer.com/journal/11814)","snPcode":"11814","submissionUrl":"https://www.editorialmanager.com/kjce/default2.aspx","title":"Korean Journal of Chemical Engineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Subscription","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"e1cdb992-4ca9-4a0b-acba-f70cb1710a9b","owner":[],"postedDate":"September 30th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-12-01T16:10:33+00:00","versionOfRecord":{"articleIdentity":"rs-7613043","link":"https://doi.org/10.1007/s11814-025-00606-x","journal":{"identity":"korean-journal-of-chemical-engineering","isVorOnly":false,"title":"Korean Journal of Chemical Engineering"},"publishedOn":"2025-11-26 15:57:16","publishedOnDateReadable":"November 26th, 2025"},"versionCreatedAt":"2025-09-30 15:31:39","video":"","vorDoi":"10.1007/s11814-025-00606-x","vorDoiUrl":"https://doi.org/10.1007/s11814-025-00606-x","workflowStages":[]},"version":"v1","identity":"rs-7613043","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7613043","identity":"rs-7613043","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}