Borophene Nanosheets grafted Covalent Organic Framework: A 2D Hybrid Porous Material for Hydrogen Adsorption Studies

Borophene Nanosheets grafted Covalent Organic Framework: A 2D Hybrid Porous Material for Hydrogen Adsorption Studies | 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 Borophene Nanosheets grafted Covalent Organic Framework: A 2D Hybrid Porous Material for Hydrogen Adsorption Studies Anamika Gogoi, Somnath Sengupta, Abhishek Rathore, V.M. Kabilan, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9236591/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Two-dimensional hybrid porous materials have emerged as potential materials in recent years for advancing gas adsorption strategies, particularly in the field of physisorbed H 2 storage for future energy demand. Owing to their unique features, hybrid porous materials exhibit enhanced induction interactions with H 2 that assist in storing relatively higher gravimetric hydrogen capacities compared to their parent materials. In this study, we report a two-dimensional crystalline hybrid porous material, borophene-TpPa-1, synthesized by integrating borophene nanosheets in a covalent organic framework, TpPa-1. The hybrid remarkably exhibits enhanced hydrogen adsorption at 1.999 bar and 77 K, achieving a 1.6-fold higher uptake relative to TpPa-1. GCMC simulations attribute this observation to the enhanced enthalpy of adsorption (~ 13 kJmol -1 ), reflecting the strengthened interactions between H 2 and the hybrid. Furthermore, the DFT calculation identifies favorable sites of adsorption and confirms the formation of the hybrid structure. It also validates the enhanced H 2 adsorption in terms of adsorption energies and charge re-distribution. These results reveal that incorporation of borophene in a porous material can significantly enhance hydrogen adsorption. Materials Chemistry Physical Chemistry borophene COF H2 adsorption 2D materials porous materials hybrid materials Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Full Text Two-dimensional hybrid porous materials have emerged as potential materials in recent years for advancing gas adsorption strategies, particularly in the field of physisorbed H 2 storage for future energy demand. Owing to their unique features, hybrid porous materials exhibit enhanced induction interactions with H 2 that assist in storing relatively higher gravimetric hydrogen capacities compared to their parent materials. In this study, we report a two-dimensional crystalline hybrid porous material, borophene-TpPa-1, synthesized by integrating borophene nanosheets in a covalent organic framework, TpPa-1. The hybrid remarkably exhibits enhanced hydrogen adsorption at 1.999 bar and 77 K, achieving a 1.6-fold higher uptake relative to TpPa-1. GCMC simulations attribute this observation to the enhanced enthalpy of adsorption (~ 13 kJmol -1 ), reflecting the strengthened interactions between H 2 and the hybrid. Furthermore, the DFT calculation identifies favorable sites of adsorption and confirms the formation of the hybrid structure. It also validates the enhanced H 2 adsorption in terms of adsorption energies and charge re-distribution. These results reveal that incorporation of borophene in a porous material can significantly enhance hydrogen adsorption. Hybrid materials exhibit intriguing properties tailored due to the synergistic interactions originated from the intrinsic characteristics of their components. [1] These fine-tuned properties impart multifunctionality and establish them in the field of catalysis, optoelectronics, energy storage, gas storage and separation, to name a few. 1, 2 The continuous advancements in porous materials such as zeolites, carbon materials, metal-organic frameworks (MOFs), and covalent-organic frameworks (COFs), have propelled the emergence of a new class of two-dimensional (2D) hybrid porous materials via precise integration and rationally engineered structural designs. 3-8 Owing to their tailored properties, these materials have been explored for hydrogen storage and CO 2 -adsorbents in recent years, compelled by the clean energy demand. 7, 9, 10 Amid the global transition toward renewable energy, hydrogen is widely regarded as a promising energy source due to its high gravimetric energy density of 33.3 kWhkg -1 . Nevertheless, its inherently low volumetric energy density causes challenges on efficient storage and the sustainable development of the hydrogen economy. 11 Consequently, to address these challenges material-based hydrogen storage strategies are being explored as an alternative to conventional storage methods. Such materials-based H 2 storage systems are broadly classified into chemisorption and physisorption based on the interactions between H 2 and the material. Chemisorption-based materials including metal hydrides, ammonia-borane, and liquid organic hydrogen carriers (LOHCs) offer viable storage capacities but are often limited by high absorption enthalpies, sluggish kinetics and elevated desorption temperatures. 12 In contrast, physisorption involves weak Van der Waals interactions, enabling rapid adsorption-desorption kinetics and superior reversibility. 13 In particular, hydrogen storage in organic porous materials via non-covalent interactions highlight a potential avenue, where the judicious design of scaffolds and functional groups can yield compact and lightweight storage media with high specific surface areas. 13 Among porous materials, COFs represent a versatile class of two- and three-dimensional (2D/3D) crystalline organic materials constructed from light elements. 6, 14 With pre-designable structures and distinctive properties, they have been explored for various applications such as catalysis, gas sorption, pollutants degradation, energy storage, to name a few. 14-17 Notably, the high specific surface areas, ordered and tunable pores, and abundant adsorption functional sites render COFs as a promising hydrogen storage material. 13 Over the past decades, numerous theoretical and also experimental studies have been reported highlighting the exceptional H 2 uptake capabilities of COFs under high pressure and cryogenic conditions. 13, 18-20 However, the intrinsically weak interactions between H 2 and the adsorption sites in pristine COFs significantly limit the gravimetric hydrogen storage capacity at low pressure regime. Thus, enhancing the induction interactions between adsorbents and H 2 represents a prospective strategy to achieve better performance in physisorption materials. In this regard, lithium-doped and palladium nanoparticles decorated COFs have been reported to exhibit superior hydrogen adsorption capability compared to their pristine forms due to the imparted stronger interactions. 21, 22 The enhanced isosteric heat of adsorption (Q st ) induced by doping and synergistic effect at the hetero interfaces promotes significant increment in H 2 adsorption in hybrid materials. 21, 23, 24 Nonetheless, incorporation of light-element components without excessive loading is crucial to sustain the specific surface area and the structural integrity while simultaneously inducing stronger interactions that are favorable for enhanced hydrogen adsorption in hybrid materials. In recent years, borophene emerged as the lightest 2D anisotropic crystalline material with distinctive features and exhibits outstanding mechanical, electrical, and optical properties. 25 These attributes have facilitated the exploration of borophene in diverse fields such as catalysis, sensors, energy storage and many more. 26-29 Within the context of energy storage, borophene has potential avenue for hydrogen storage with theoretical studies predicting high gravimetric densities for metal decorated borophene. 29, 30 However, experimental validation has yet to be realized. As metal-doped borophene can exceptionally enhance H 2 storage capacities (Table S7), due to polarization effect arises from electron depletion and accumulation which generate localized electric field that favor H 2 adsorption. By analogy, it is hypothesized that incorporating borophene with a COF may also induce similar phenomena because of the presence of electron rich nitrogen and oxygen within the framework. Moreover, boron-doped carbon materials were known to exhibit superior H 2 adsorption capacity as compared to their parent materials, underscoring the role of boron-induced effects in enhancing H 2 physisorption. 31-33 In the present work, we report a crystalline 2D hybrid porous material, borophene-TpPa-1 where the borophene nanosheets (BNS) are integrated with the stable β-ketoenamine COF, TpPa-1, via a very facile room temperature synthesis. The as-synthesized hybrid material was examined for H 2 adsorption performance at a pressure range 0.667 to 1.999 bar, achieving a 1.6-fold increase in gravimetric H 2 adsorption capacity compared to pristine TpPa-1. GCMC simulation further ascribes this enhancement to the increased isosteric heat of adsorption in the hybrid material while DFT confirms the formation of hybrid and identifies the favorable adsorption-sites. The synthesis processes for 2D BNS, TpPa-1 and borophene-TpPa-1 hybrid (referred to as BNS@TpPa-1 henceforth) were illustrated in Figure 1. BNS were synthesized from crystalline boron powder via DMF-assisted liquid phase exfoliation approach. 34 Subsequently, the as-synthesized BNS were used to fabricate a 2D hybrid material at room temperature with TpPa-1 (Figure 1b). The microstructural analysis of BNS, TpPa-1, and BNS@TpPa-1 were conducted using high-resolution transmission electron microscopy (HRTEM) to elucidate their chemical composition, crystallinity, morphology and atomic-level structural properties. Low-resolution TEM micrograph (Figure S2a) showed the formation of few-layered BNS, which validated the successful exfoliation of bulk boron. Further, HRTEM imaging uncovered the atomic arrangement of the exfoliated nanosheets with apparent lattice fringes with a d-spacing of 0.51 nm (Figure 2a), corresponding to the (001) plane of β 12 borophene sheets, which stands out as most stable phase. 27, 35 The presence of distinct interference fringes signified the localized crystalline nature of BNS, though PXRD of the same (Figure S1) resulted in no observation of any diffraction pattern. This may be due to the disruption of the long-range ordered structure of boron powder under the cavitation effect of the probe sonication during the exfoliation process. The surface morphology of TpPa-1 and BNS@TpPa-1 showed no discernible differences at low-resolution (Figure 2b & e), indicating that integration of BNS did not alter the overall morphology. The HRTEM micrograph (Figure 2f & h) depicted the BNS were well integrated with TpPa-1, showing well-defined lattice fringes with the characteristic d-spacing of β 12 sheets of borophene. This suggests that during the in-situ confinement of BNS in the TpPa-1 framework preserves the phase of BNS. In addition, the fast fourier transform (FFT) carried out in Figure 2c for TpPa-1 exhibited circular rings, a typical observation for β-ketoenamine COFs. The FFT on BNS@TpPa-1 image revealed characteristics of TpPa-1 along with parallel rows of dot patterns (Figure 2g) attributable to BNS indicating the heterostructure interface in the hybrid. Furthermore, EDS mapping revealed the uniform integration of BNS within TpPa-1 framework, suggesting the coexistence of both components in the BNS@TpPa-1 hybrid (Figure 2i). Quantitative EDX analysis further confirmed ~ 5% boron (Figure S3f) content in the hybrid material. The crystalline and porous nature of the BNS@TpPa-1 hybrid was examined by PXRD and BET analysis. The PXRD of the hybrid material showed the characteristic crystalline nature of the COF, which coincides with the TpPa-1 XRD reflections at 2θ = 4.8° (100), 8.5° (200), and 26.6° (001) (Figure 3a). 36 The BET analysis (Figure 3b) of the hybrid exhibited the porous nature of the material, though it exhibited a lower surface area and pore volume than that of TpPa-1. The pristine TpPa-1 possessed a surface area of 849 m 2 g -1 and a pore volume of 0.778 cc g -1 , which were decreased to 624 m 2 g -1 and 0.383 cc g -1 in the hybrid structure. This is probably due to the obstruction in the pore channels caused by the stacking of BNS upon TpPa-1. Further, XPS analysis was employed to probe the surface composition and chemical states in the pristine BNS, TpPa-1, and BNS@TpPa-1 hybrid. The high-resolution B 1s spectra of BNS and BNS@TpPa-1 could be resolved into three component peaks corresponding to 186.9 and 188.4 eV for the B-B bond and 191 eV for B-O bond (Figure 3g) in borophene, and a shift of 0.3 eV for B-B bond in the B 1s spectra of the hybrid structure was noticed, which may be attributed to gain of electron density from the TpPa-1 framework. 37 Similarly, in the high-resolution spectra of C 1s of TpPa-1, three peaks at 284.1, 285.3 and 286.8 eV corresponding to C=C, C-N and C=O bonds, respectively which were located at 284.2, 285.2 and 288.1 eV for BNS@TpPa-1 (Figure 3d). As for the N 1s , one single peak located at 399.4 eV revealing the C-N-H bond formation in the keto form of TpPa-1 but showed a shift of 0.2 eV in the hybrid (Figure 3e). Likewise, the high-resolution O 1s spectra (Figure 3f) of the pristine TpPa-1 and the hybrid also revealed a change of peak positions. This indicates that there may be interactions between the lone pair electron density of TpPa-1 with the boron of BNS, and consequently, the electron density distribution in the framework may be changed resulting in the changes in the binding energies. The Raman analysis was also carried out for borophene, TpPa-1, and BNS@TpPa-1 to obtain a better insight into the phase and structural arrangement. BNS exhibited multiple peaks in the lower frequency region (Figure S5a). These peaks confirmed the presence of β 12 polymorphs of 2D borophene which corresponds 1068 cm -1 for B 1g 1 mode, 1147 and 911 cm -1 corresponds to in-plane stretching mode of A g 1 and (A g 2 (S)), 378 cm -1 ascribed to B 1g 2 vibration modes of β 12 phase. 38 However, the Raman analysis results for TpPa-1 and BNS@TpPa-1 appeared to be the same, as the vibration modes corresponding to borophene were not discernible in the hybrid, which may be due to the low content of BNS in the TpPa-1 matrix. Despite this, we successfully integrated BNS within TpPa-1 and the porous crystalline 2D hybrid of TpPa-1 was further studied for hydrogen adsorption at low pressures. Hydrogen adsorption studies were conducted using TpPa-1 and BNS@TpPa-1 to understand the influence of BNS on H 2 uptake in the hybrid. As discussed, heterogeneity and synergetic effects therein improve the hydrogen adsorption performance of porous materials, accordingly, higher efficiency in H 2 uptake was anticipated for BNS@TpPa-1. To validate our hypothesis, we performed the adsorption studies at pressure range (0.667-1.999 bar) using a Sievert apparatus at a temperature of 77 K. First, we measured the pressure drop (ΔP) (Table S1) for the empty sample holder at different pressures when the temperature changed from the room temperature (RT) to 77 K. Then, the net pressure difference due to hydrogen adsorption for TpPa-1 and BNS@TpPa-1 was calculated by subtracting the empty cell ΔP from the total pressure drop for the samples. The hydrogen adsorption capacity (weight%) was calculated using the equation 1 given below, The pressure difference and H 2 adsorption weight% were summarized in Table S2 for TpPa-1 and BNS@TpPa-1. In both samples, the adsorbed H 2 weight% increased with pressure, consistent with the adsorption behavior of porous materials. It is worth noting that by introducing BNS to the TpPa-1 framework, H 2 adsorption weight% greatly enhanced from 0.175 to 0.277 (Figure 3c), which is 1.6-fold higher than that of pristine TpPa-1 at 1.999 bar and 77 K. Even with lower pore volume and surface area, BNS@TpPa-1 showed greater H 2 adsorption. This observation suggests that BNS may play a significant role in enhancing the H 2 adsorption of BNS@TpPa-1 hybrid material. The kinetics of H 2 adsorption strongly depends on the operating pressure. As pressure decreased from 1.999 to 0.667 bar, the adsorption profile showed a sharp initial uptake followed by gradual uptake (Figure 4a-e). Due to the highly porous nature of TpPa-1 and BNS@TpPa-1, a rapid H 2 adsorption rate was observed, reaching saturation within 2 minutes at each applied pressure. Along with the adsorption rate, the desorption of H 2 from the materials is crucial to release the gas without much effort. Desorption studies were conducted by recording the pressure increase when the sample temperature changed from 77 K to RT. Both samples desorbed H 2 within 10 minutes, at all the pressures after reaching to RT (Figure S6). The desorbed H 2 weight% were calculated by using equation 2 and was listed in Table S3, and a comparative representation of adsorption-desorption behavior between both samples was shown in Figure 4f. Notably, both samples desorbed almost all adsorbed H 2 indicating the characteristics of physisorption. We also have parameterized the H 2 adsorption isotherms for TpPa-1 and BNS@TpPa-1 according to the Freundlich and Langmuir model. Correlation coefficients (R 2 ) obtained for both the fittings were close to 0.99, which suggests that the data were fitted for both the models (Figure 4g & h). This suggests monolayer adsorption in low-pressure regions. Further investigation was carried out with Grand Canonical Monte Carlo (GCMC) simulations to understand the adsorption behavior of TpPa-1and BNS@TpPa-1. The hydrogen adsorption capacities of TpPa-1 and BNS@TpPa-1 (Figure 5d & e) were compared across experiment and simulations. Fig. 5b & c presents snapshots from GCMC simulations for both the pristine TpPa-1 and BNS@TpPa-1. It was observed that for both pristine and the hybrid structures, the H 2 uptake (Table S3) increased consistently with increasing pressure, which is in agreement with the experimental results. This trend reflects the typical physisorption behavior dominated by Van der Waals interactions, where higher pressures enhance the adsorbate-adsorbent interaction probability. However, as shown in Figure 5, for the TpPa-1 and BNS@TpPa-1, the GCMC-predicted capacity was consistently higher than the experimental results throughout the pressure range. Several factors as discussed in the literature to comprehend the results from GCMC simulations that of experimental measurements. One of the primary reasons is the neglect of quantum effects such as zero-point energy and tunneling in classical GCMC, which leads to overestimation of adsorption, particularly at cryogenic temperatures like 77 K. Additionally, simulations often assume idealized, rigid, and defect-free frameworks, whereas real materials may exhibit structural defects, pore blockage, or flexibility that reduce accessible surface area. 39-41 Also in case of BNS@TpPa-1 , substantial overestimation of hydrogen uptake in the GCMC simulation compared to experiment arises from the idealized interface and uniform stacking of the simulation model in which the TpPa-1 fragment is ideally positioned between two borophene layers. This will create maximum available surface area and potential for stronger interaction via π–H 2 . In practice, however, the interface of BNS@TpPa-1 will be more disordered with potential aggregation, pore blocking, or limited interfacial exposure leading to lower experimental activity. While discrepancies exist in absolute adsorption values, both theoretical and experimental findings consistently highlight that the incorporation of BNS significantly enhances hydrogen uptake compared to the pristine TpPa-1. This observed trend is of primary importance, highlighting the potential of borophene as a pore-modifying or confinement-enhancing additive. The isosteric heat of adsorption (Q st ) is a crucial thermodynamic parameter that quantifies the interaction strength between adsorbate molecules and the surface of a porous material. It provides insight into the nature of the adsorption mechanism whether it is dominated by weak Van der Waals forces (physisorption) or stronger chemisorptive interactions. For hydrogen storage applications, an ideal Q st lies in the moderate range of 4-15 kJmol -1 , balancing strong enough binding to enable uptake at ambient or cryogenic conditions while avoiding excessive binding that impedes release. In this study, GCMC simulations at 77 K revealed that the pristine TpPa-1 exhibits a relatively low and nearly constant Q st of about 2.85 kJmol -1 across a wide pressure range (0.667-1.999 bar), indicative of weak physisorption on homogeneous adsorption sites. Such values are typical of COFs composed purely of organic linkers, where hydrogen interacts primarily via dispersive forces with aromatic surfaces. In contrast, the hybrid material demonstrated a significantly higher Q st of nearly 13 kJmol -1 , nearly four times that of the unmodified TpPa-1, which is higher as compared to reported Q st value for COFs (Table S6). This increase suggests that the incorporation of BNS introduces higher-energy adsorption sites, likely due to a combination of π–metal interactions, electronic polarization effects, and nanoconfinement between the 2D layers. Borophene, being an electron-deficient, anisotropic material with metallic conductivity can induce polarization effects through electron density distribution with TpPa-1, while the hybrid abled to adsorb hydrogen molecules more effectively than an organic-only framework, thereby enhancing the adsorption enthalpy. 20, 42 The Q st value of ~13 kJmol -1 falls within the optimal range reported for advanced porous materials such as MOFs and doped carbons, and is consistent with literature-reported values for hydrogen adsorption on frameworks incorporating conductive or polarizable components. 43, 44 The observed trend, where the Q st is less for TpPa-1 and appreciably increases in the hybrid material, reflects the generation of energetically more diverse and stronger binding environments in the hybrid structure. These results confirm that structural modification through 2D material integration is a viable strategy to enhance gas adsorption performance. Furthermore, the moderate increase in Q st still ensures that hydrogen remains easily desorbable, preserving reversibility, an important criterion for practical storage applications. Thus, the Q st data not only validates the superior adsorption capacity observed experimentally for the BNS@TpPa-1 hybrid but also highlights the fundamental thermodynamic advantage conferred by hybrid interface engineering. The overall statistical behavior of TpPa-1/borophene/H 2 system is revealed by the GCMC calculations. To unfold the fundamental, however, the microscopic interaction between the COF, borophene and H 2 molecules, DFT is employed on (i) TpPa-1, (ii) borophene and (iii) BNS@TpPa-1 hybrid. We calculate the site-specific adsorption energies ( E ads ) for all three cases (Table S5 & Table1). Active sites of interest have been identified based on the functional groups and the number of bonds for TpPa-1 and borophene, respectively. These sites are enumerated and shown on schematic for TpPa-1 and borophene (Figure S7 and S8, respectively). We considered the active sites for TpPa-1 and hybrid to be the same. We find from the E ads values tabulated in Table S5 that apparently all the selected sites are energetically favorable for both TpPa-1 and borophene. Although the active sites across TpPa-1 and borophene are not chemically equivalent, broadly, E ads for TpPa-1 and borophene vary ~eV and 10s of meV, respectively. This variation is attributed to the presence of functional groups on the TpPa-1 where relatively stronger interactions are expected with H 2 . The adsorption energy values for our structure are very much comparable with the literature for β 12 and bilayer borophene (Table S8). While E ads values of our borophene are about one order lower compared with the literature on doped (Li, Y, Na, K or Ca) borophene (Table S8). 45, 46 This variation is well justified, since the H 2 is adsorbed on the dopant atom in contrast to that of pristine borophene. Within TpPa-1, the E ads is not site specific indicating similar kind of interaction across the framework. In contrast, for borophene the E ads values vary from -10 to -67 meV while the sites 5, 6, 8 and 9 are comparable. In the case of TpPa-1 (borophene), the corresponding sites of the minimum and maximum E ads are 5(7) and 10(1), respectively. The variation of E ads across the two systems is attributed to the type of interaction that H 2 poses with metallic (semiconducting) borophene (TpPa-1), apart from the active edge atoms of TpPa-1. The typical distance between H 2 and borophene (TpPa-1) is ~ 3.7 Å (~3 Å). H 2 adsorption experiments indicated that the hybrid depicted improved performance. To identify the sites that would possibly host H 2 we have inserted it at the interface of hybrid as well as the edges of TpPa-1. The corresponding E ads values are tabulated in Table 1. Clearly, the positive value of E ads for TpPa-1/H 2 /borophene is not energetically favored for positions 1 and 7. Also, as per the optimized geometry, the borophene layer is significantly deformed in the hybrid due to the presence of H 2 at the interface (Figure S09 and S10) as comprehended from the E ads values (Table 1). In clear contrast, at the edge (configurations 2 to 9), the negative E ads indicates favorable sites while the magnitude suggests its strength. We note that the sites near the oxygen of the carbonyl group are relatively stronger. Essentially, within the hybrid, the E ads values reflect the formation of hybrid edge states that favor the adsorption of H 2 . To further corroborate the formation of hybrid, we have investigated the charge difference plots (Figure 6 and Figure S11). In the case of TpPa-1, the H 2 is localized at about ~3 Å above the plane of TpPa-1 (Figure 6a), while it is almost in plane in the hybrid. The distribution of charge is primarily above the plane of TpPa-1 which shifted to the edge and borophene in the hybrid structure (Figure 6b). Regions with positive values (blue) indicate the accumulation when compared to isolated counterpart, indicating bonding regions. Such accumulations can be observed on both TpPa-1 as well as borophene confirming the synergetic effect of the hybrid in the adsorption of H 2 corroborating the enhanced adsorption as observed in the experiment. Table 1. Adsorption energies for selected configurations of TpPa-1, borophene and BNS@TpPa-1 hybrid. The enumerated sites of TpPa-1 and borophene are not equivalent, however, that of TpPa-1 and hybrid are equivalent. 1 -1.829 -10.083 168.294 [i] 2 -18.20 -13.839 -44.686 [e] 3 -1.829 -10.744 -43.341 [e] 4 -1.837 -15.229 -50.687 [e] 5 -1.839 -63.626 -45.870 [e] 6 -1.839 -63.179 -51.578 [e] 7 -1.815 -67.074 -44.686 [e] 8 -1.837 -63.268 -24.265 [e] 9 -1.819 -63.465 -48.789 [e] [i] represent the spatial position of H 2 is at the interface of the hybrid [e] represent the spatial position of H2 is at the edge of the hybrid. In summary, we have designed and synthesized a promising 2D hybrid porous material, BNS@TpPa-1, which has exhibited more efficient performance in H 2 adsorption as compared to the parent COF, TpPa-1. The hybrid has achieved a 1.6-fold increment in H 2 adsorption equivalent to 0.277 weight%. The experimental results, supported by GCMC simulation, reveal that BNS incorporated hybrid BNS-COF demonstrates better adsorption properties due to the enhanced isosteric heat of adsorption from 2.85 kJmol -1 to ~13 kJmol -1 . DFT calculations not only confirm the synergetic effects within hybrid but also identify that the active sites of adsorption are the “edges of TpPa-1” corroborating the enhanced H 2 adsorption as observed in the experiment. The results of this work are of significance in the further elucidation of hydrogen adsorption properties on low-dimensional boron materials and TpPa-1 and could be potentially tapped for overall hydrogen storage materials. This work highlights the potential of a hybrid porous material for physisorptive H 2 storage with enhanced isosteric heat of absorption and may contribute to the realization of advanced hydrogen storage material under near ambient conditions. Declarations AUTHOR INFORMATION Corresponding Authors Dr. R. Medishetty - Department of Chemistry and Department of Materials Science and Metallurgical Engineering, Indian Institute of Technology Bhilai; Orcid ID: 0000-0003-2289-2655. Email: [email protected] Dr. B. Sreenivasulu - Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India, Orcid ID: 0000-0003-3489-5263. E-mail: [email protected] Dr. S. Vempati - Department of Physics, IIT Bhilai, Durg, Chhattisgarh 491001, India. Orcid ID: 0000-0002-0536-7827. Email: [email protected] Authors A. Gogoi - Department of Chemistry, Indian Institute of Technology Bhilai, Durg, Chhattisgarh 491002, India; Orcid ID: 0009-0007-8675-4178. S. Sengupta - Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India. A. Rathore - Department of Physics, IIT Bhilai, Durg, Chhattisgarh 491001, India, Orcid ID: 0009-0000-1044-8325. V.M. Kabilan - Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India, Orcid ID: 0009-0006-2376-0506. S. R. Abothu - Department of Chemistry, Indian Institute of Technology Bhilai, Durg, Chhattisgarh 491002, India, Orcid ID: 0009-0000-7037-7573. M. Bootharajan - Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India. C. V. S. B. Rao - Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India. Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding Sources R. M. acknowledges support from the IBITF under Grant No. IBITF/PRAYAS/Note/2023-24/0009. AG and AR would like to thank IIT Bhilai and Ministry of Education, India (MoE) for the research fellowship. SR would like to thank CSIR (09/1237(19503)/2024-EMR-I) for the research fellowship. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We thank IIT Bhilai for CIF facilities. The authors sincerely thank Dr. V. Jayaraman, Director, MC&MFCG, IGCAR, Kalpakkam, for granting permission to carry out hydrogen sorption experiments at the MC&MFCG facility. References Gomez-Romero, P.; Pokhriyal, A.; Rueda-García, D.; Bengoa, L. N.; González-Gil, R. M. Hybrid Materials: A Metareview. Chem. Mater. 2024 , 36 (1), 8-27. Valentini, C.; Montes-García, V.; Pakulski, D.; Samorì, P.; Ciesielski, A. Covalent Organic Frameworks and 2D Materials Hybrids: Synthesis Strategies, Properties Enhancements, and Future Directions. Small 2025 , 21 (8), 2410544. Pérez-Botella, E.; Valencia, S.; Rey, F. Zeolites in Adsorption Processes: State of the Art and Future Prospects. Chem. Rev. 2022 , 122 (24), 17647-17695. Sam, D. K.; Li, H.; Xu, Y.-T.; Cao, Y. Advances in porous carbon materials for a sustainable future: A review. Adv. Colloid Interface Sci. 2024 , 333 , 103279. 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Enhancement in the hydrogen storage capability of borophene through yttrium doping: A theoretical study. J. Energy Storage 2022 , 55 , 105500. Additional Declarations The authors declare no competing interests. Supplementary Files SupportingInformation.docx Borophene Nanosheets grafted Covalent Organic Framework: A 2D Hybrid Porous Material for Hydrogen Adsorption Studies Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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(b) synthesis of TpPa-1 (i) and BNS@TpPa-1hybrid (ii)\u003c/p\u003e","description":"","filename":"figure1.png","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/b3f90c9b90094a53467f5f68.png"},{"id":105739421,"identity":"2fde18a5-1513-431f-8847-b91489b259a5","added_by":"auto","created_at":"2026-03-30 12:43:37","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":67244160,"visible":true,"origin":"","legend":"\u003cp\u003e(a) HRTEM image of BNS with d spacing (inset refers to the FFT of that image), (b, c) HRTEM image of TpPa-1, (d) FFT of the highlighted region in c, (e, f) HRTEM image of BNS@TpPa-1, (g) FFT of the highlighted region in f, (h) HRTEM image of BNS@TpPa-1 with d spacing (inset refers to the FFT of that image). (i) elemental mapping BNS@TpPa-1.\u003c/p\u003e","description":"","filename":"figure2.png","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/5623c2386c2f322c344b80da.png"},{"id":105739419,"identity":"eacd3e0c-d3c9-4f3c-a111-4cea1b818a8d","added_by":"auto","created_at":"2026-03-30 12:43:34","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1274763,"visible":true,"origin":"","legend":"\u003cp\u003e(a) PXRD, (b) BET isotherm of TpPa-1 and BNS@TpPa-1. (c) Comparison of H2 adsorption capacity in weight % at different pressures for TpPa-1 and BNS@TpPa-1. Comparative high-resolution XPS spectra of (d) B 1s, (e) C 1s, (f) N 1s, and (g) O 1s of TpPa-1, BNS, and BNS@TpPa-1.\u003c/p\u003e","description":"","filename":"figure3.png","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/f4378975b5b642794c125b3d.png"},{"id":105739422,"identity":"e4b7d7e0-2962-4d07-88b8-7bcab70e8c95","added_by":"auto","created_at":"2026-03-30 12:43:37","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":826453,"visible":true,"origin":"","legend":"\u003cp\u003e(a-e) Adsorption kinetics of H\u003csub\u003e2\u003c/sub\u003e on TpPa-1 and BNS@TpPa-1 hybrid at different pressures, (f) graphical representation of adsorption and desorption H\u003csub\u003e2\u003c/sub\u003e weight% at different pressures. Fitting of H\u003csub\u003e2\u003c/sub\u003e adsorption in (g) Freundlich model and (h) Langmuir model.\u003c/p\u003e","description":"","filename":"figure4.png","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/055f93b219d6eec5b760bf55.png"},{"id":105739375,"identity":"c3067355-f7c5-4fe6-8b20-dd16d527453d","added_by":"auto","created_at":"2026-03-30 12:43:25","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":5554000,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Simulated structural model of the BNS@TpPa-1 hybrid, GCMC snapshots of (b) TpPa-1, c) BNS@TpPa-1 with adsorbed H\u003csub\u003e2\u003c/sub\u003e, and comparison of experimental and simulated H\u003csub\u003e2\u003c/sub\u003e\u0026nbsp;adsorption isotherms for (d) TpPa-1 and (e) BNS@TpPa-1 at 77 K.\u003c/p\u003e","description":"","filename":"figure5.png","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/dd20f9962a1f6e5472efbf8e.png"},{"id":105753689,"identity":"e47204cc-3912-4ac0-80bc-4d412988d81c","added_by":"auto","created_at":"2026-03-30 16:11:05","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":2499323,"visible":true,"origin":"","legend":"\u003cp\u003eCharge density difference plots depicting the distribution of charge (a) pristine TpPa-1, isosurface level, 2.58 × 10\u003csup\u003e-5\u003c/sup\u003e eÅ\u003csup\u003e-3\u003c/sup\u003e and (b) BNS@TpPa-1 hybrid; isosurface level 1.69 ×10\u003csup\u003e-5\u003c/sup\u003e eÅ\u003csup\u003e-3\u003c/sup\u003e. Blue and red correspond to positive and negative charge accumulations, respectively.\u003c/p\u003e","description":"","filename":"figure6.png","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/ff8d964efabdd004a7a992a6.png"},{"id":106401653,"identity":"1807f4aa-bed2-4a3e-8893-e8ac6c4a0c3c","added_by":"auto","created_at":"2026-04-08 09:08:46","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":86509021,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/777a823a-3c23-4db5-b30d-7ae72e463015.pdf"},{"id":105739378,"identity":"f3e479d3-8b5e-4476-b3ad-2e28949eed22","added_by":"auto","created_at":"2026-03-30 12:43:25","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4638711,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eBorophene Nanosheets grafted Covalent Organic Framework: A 2D Hybrid Porous Material for Hydrogen Adsorption Studies\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"SupportingInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-9236591/v1/abd74db9c6ffb3186410b86e.docx"}],"financialInterests":"The authors declare no competing interests.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eBorophene Nanosheets grafted Covalent Organic Framework: A 2D Hybrid Porous Material for Hydrogen Adsorption Studies\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"Full Text","content":"\u003cp\u003eTwo-dimensional hybrid porous materials have emerged as potential materials in recent years for advancing gas adsorption strategies, particularly in the field of physisorbed H\u003csub\u003e2\u003c/sub\u003e storage for future energy demand. Owing to their unique features, hybrid porous materials exhibit enhanced induction interactions with H\u003csub\u003e2\u003c/sub\u003e that assist in storing relatively higher gravimetric hydrogen capacities compared to their parent materials. In this study, we report a two-dimensional crystalline hybrid porous material, borophene-TpPa-1, synthesized by integrating borophene nanosheets in a covalent organic framework, TpPa-1. The hybrid remarkably exhibits enhanced hydrogen adsorption at 1.999 bar and 77 K, achieving a 1.6-fold higher uptake relative to TpPa-1. GCMC simulations attribute this observation to the enhanced enthalpy of adsorption (~ 13 kJmol\u003csup\u003e-1\u003c/sup\u003e), reflecting the strengthened interactions between H\u003csub\u003e2\u003c/sub\u003e and the hybrid. Furthermore, the DFT calculation identifies favorable sites of adsorption and confirms the formation of the \u003cem\u003ehybrid\u0026nbsp;\u003c/em\u003estructure. It also validates the enhanced H\u003csub\u003e2\u003c/sub\u003e adsorption in terms of adsorption energies and charge re-distribution. These results reveal that incorporation of borophene in a porous material can significantly enhance hydrogen adsorption.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eHybrid materials exhibit intriguing properties tailored due to the synergistic interactions originated from the intrinsic characteristics of their components.\u003csup\u003e[1]\u003c/sup\u003e These fine-tuned properties impart multifunctionality and establish them in the field of catalysis, optoelectronics, energy storage, gas storage and separation, to name a few.\u003csup\u003e1, 2\u003c/sup\u003e The continuous advancements in porous materials such as zeolites, carbon materials, metal-organic frameworks (MOFs), and covalent-organic frameworks (COFs), have propelled the emergence of a new class of two-dimensional (2D) hybrid porous materials via precise integration and rationally engineered structural designs.\u003csup\u003e3-8\u003c/sup\u003e Owing to their tailored properties, these materials have been explored for hydrogen storage and CO\u003csub\u003e2\u003c/sub\u003e-adsorbents in recent years, compelled by the clean energy demand.\u003csup\u003e7, 9, 10\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eAmid the global transition toward renewable energy, hydrogen is widely regarded as a promising energy source due to its high gravimetric energy density of 33.3 kWhkg\u003csup\u003e-1\u003c/sup\u003e. Nevertheless, its inherently low volumetric energy density causes challenges on efficient storage and the sustainable development of the hydrogen economy.\u003csup\u003e11\u003c/sup\u003e Consequently, to address these challenges material-based hydrogen storage strategies are being explored as an alternative to conventional storage methods. Such materials-based H\u003csub\u003e2\u003c/sub\u003e storage systems are broadly classified into chemisorption and physisorption based on the interactions between H\u003csub\u003e2\u003c/sub\u003e and the material. Chemisorption-based materials including metal hydrides, ammonia-borane, and liquid organic hydrogen carriers (LOHCs) offer viable storage capacities but are often limited by high absorption enthalpies, sluggish kinetics and elevated desorption temperatures.\u003csup\u003e12\u003c/sup\u003e In contrast, physisorption involves weak Van der Waals interactions, enabling rapid adsorption-desorption kinetics and superior reversibility.\u003csup\u003e13\u003c/sup\u003e In particular, hydrogen storage in organic porous materials via non-covalent interactions highlight a potential avenue, where the judicious design of scaffolds and functional groups can yield compact and lightweight storage media with high specific surface areas.\u003csup\u003e13\u003c/sup\u003e\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eAmong porous materials, COFs represent a versatile class of two- and three-dimensional (2D/3D) crystalline organic materials constructed from light elements.\u003csup\u003e6, 14\u003c/sup\u003e With pre-designable structures and distinctive properties, they have been explored for various applications such as catalysis, gas sorption, pollutants degradation, energy storage, to name a few.\u003csup\u003e14-17\u003c/sup\u003e Notably, the high specific surface areas, ordered and tunable pores, and abundant adsorption functional sites render COFs as a promising hydrogen storage material.\u003csup\u003e13\u003c/sup\u003e Over the past decades, numerous theoretical and also experimental studies have been reported highlighting the exceptional H\u003csub\u003e2\u003c/sub\u003e uptake capabilities of COFs under high pressure and cryogenic conditions.\u003csup\u003e13, 18-20\u003c/sup\u003e However, the intrinsically weak interactions between H\u003csub\u003e2\u003c/sub\u003e and the adsorption sites in pristine COFs significantly limit the gravimetric hydrogen storage capacity at low pressure regime. Thus, enhancing the induction interactions between adsorbents and H\u003csub\u003e2\u003c/sub\u003e represents a prospective strategy to achieve better performance in physisorption materials. In this regard, lithium-doped and palladium nanoparticles decorated COFs have been reported to exhibit superior hydrogen adsorption capability compared to their pristine forms due to the imparted stronger interactions.\u003csup\u003e21, 22\u003c/sup\u003e The enhanced isosteric heat of adsorption (Q\u003csub\u003est\u003c/sub\u003e) induced by doping and synergistic effect at the hetero interfaces promotes significant increment in H\u003csub\u003e2\u003c/sub\u003e adsorption in hybrid materials.\u003csup\u003e21, 23, 24\u003c/sup\u003e Nonetheless, incorporation of light-element components without excessive loading is crucial to sustain the specific surface area and the structural integrity while simultaneously inducing stronger interactions that are favorable for enhanced hydrogen adsorption in hybrid materials.\u003c/p\u003e\n\u003cp\u003eIn recent years, borophene emerged as the lightest 2D anisotropic crystalline material with distinctive features and exhibits outstanding mechanical, electrical, and optical properties.\u003csup\u003e25\u003c/sup\u003e These attributes have facilitated the exploration of borophene in diverse fields such as catalysis, sensors, energy storage and many more.\u003csup\u003e26-29\u003c/sup\u003e Within the context of energy storage, borophene has potential avenue for hydrogen storage with theoretical studies predicting high gravimetric densities for metal decorated borophene.\u003csup\u003e29, 30\u003c/sup\u003e However, experimental validation has yet to be realized. As metal-doped borophene can exceptionally enhance H\u003csub\u003e2\u003c/sub\u003e storage capacities (Table S7), due to polarization effect arises from electron depletion and accumulation which generate localized electric field that favor H\u003csub\u003e2\u003c/sub\u003e adsorption. By analogy, it is hypothesized that incorporating borophene with a COF may also induce similar phenomena because of the presence of electron rich nitrogen and oxygen within the framework. Moreover, boron-doped carbon materials were known to exhibit superior H\u003csub\u003e2\u003c/sub\u003e adsorption capacity as compared to their parent materials, underscoring the role of boron-induced effects in enhancing H\u003csub\u003e2\u003c/sub\u003e physisorption.\u003csup\u003e31-33\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eIn the present work, we report a crystalline 2D hybrid porous material, borophene-TpPa-1 where the borophene nanosheets (BNS) are integrated with the stable \u0026beta;-ketoenamine COF, TpPa-1, via a very facile room temperature synthesis. The as-synthesized hybrid material was examined for H\u003csub\u003e2\u003c/sub\u003e adsorption performance at a pressure range 0.667 to 1.999 bar, achieving a 1.6-fold increase in gravimetric H\u003csub\u003e2\u003c/sub\u003e adsorption capacity compared to pristine TpPa-1. GCMC simulation further ascribes this enhancement to the increased isosteric heat of adsorption in the hybrid material while DFT confirms the formation of hybrid and identifies the favorable adsorption-sites.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe synthesis processes for 2D BNS, TpPa-1 and borophene-TpPa-1 hybrid (referred to as BNS@TpPa-1 henceforth) were illustrated in Figure 1. BNS were synthesized from crystalline boron powder via DMF-assisted liquid phase exfoliation approach.\u003csup\u003e34\u003c/sup\u003e Subsequently, the as-synthesized BNS were used to fabricate a 2D hybrid material at room temperature with TpPa-1 (Figure 1b).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe microstructural analysis of BNS, TpPa-1, and BNS@TpPa-1 were conducted using high-resolution transmission electron microscopy (HRTEM) to elucidate their chemical composition, crystallinity, morphology and atomic-level structural properties. Low-resolution TEM micrograph (Figure S2a) showed the formation of few-layered BNS, which validated the successful exfoliation of bulk boron. Further, HRTEM imaging uncovered the atomic arrangement of the exfoliated nanosheets with apparent lattice fringes with a d-spacing of 0.51 nm (Figure 2a), corresponding to the (001) plane of \u0026beta;\u003csub\u003e12\u003c/sub\u003e borophene sheets, which stands out as most stable phase.\u003csup\u003e27, 35\u003c/sup\u003e\u003csup\u003e\u0026nbsp;\u003c/sup\u003eThe presence of distinct interference fringes signified the localized crystalline nature of BNS, though PXRD of the same (Figure S1) resulted in no observation of any diffraction pattern. This may be due to the disruption of the long-range ordered structure of boron powder under the cavitation effect of the probe sonication during the exfoliation process.\u003c/p\u003e\n\u003cp\u003eThe surface morphology of TpPa-1 and BNS@TpPa-1 showed no discernible differences at low-resolution (Figure 2b \u0026amp; e), indicating that integration of BNS did not alter the overall morphology. The HRTEM micrograph (Figure 2f \u0026amp; h) depicted the BNS were well integrated with TpPa-1, showing well-defined lattice fringes with the characteristic d-spacing of \u0026beta;\u003csub\u003e12\u003c/sub\u003e sheets of borophene. This suggests that during the in-situ confinement of BNS in the TpPa-1 framework preserves the phase of BNS. In addition, the fast fourier transform (FFT) carried out in Figure 2c for TpPa-1 exhibited circular rings, a typical observation for \u0026beta;-ketoenamine COFs. The FFT on BNS@TpPa-1 image revealed characteristics of TpPa-1 along with parallel rows of dot patterns (Figure 2g) attributable to BNS indicating the heterostructure interface in the hybrid. Furthermore, EDS mapping revealed the uniform integration of BNS within TpPa-1 framework, suggesting the coexistence of both components in the BNS@TpPa-1 hybrid (Figure 2i). Quantitative EDX analysis further confirmed ~ 5% boron (Figure S3f) content in the hybrid material.\u003c/p\u003e\n\u003cp\u003eThe crystalline and porous nature of the BNS@TpPa-1 hybrid was examined by PXRD and BET analysis. The PXRD of the hybrid material showed the characteristic crystalline nature of the COF, which coincides with the TpPa-1 XRD reflections at 2\u0026theta; = 4.8\u0026deg; (100), 8.5\u0026deg; (200), and 26.6\u0026deg; (001) (Figure 3a).\u003csup\u003e36\u003c/sup\u003e The BET analysis (Figure 3b) of the hybrid exhibited the porous nature of the material, though it exhibited a lower surface area and pore volume than that of TpPa-1. The pristine TpPa-1 possessed a surface area of 849 m\u003csup\u003e2\u0026nbsp;\u003c/sup\u003eg\u003csup\u003e-1\u003c/sup\u003e and a pore volume of 0.778 cc g\u003csup\u003e-1\u003c/sup\u003e, which were decreased to 624 m\u003csup\u003e2\u003c/sup\u003eg\u003csup\u003e-1\u003c/sup\u003e and 0.383 cc g\u003csup\u003e-1\u003c/sup\u003e in the hybrid structure. This is probably due to the obstruction in the pore channels caused by the stacking of BNS upon TpPa-1.\u003c/p\u003e\n\u003cp\u003eFurther, XPS analysis was employed to probe the surface composition and chemical states in the pristine BNS, TpPa-1, and BNS@TpPa-1 hybrid. The high-resolution B\u003cem\u003e1s\u003c/em\u003e spectra of BNS and BNS@TpPa-1 could be resolved into three component peaks corresponding to 186.9 and 188.4 eV for the B-B bond and 191 eV for B-O bond (Figure 3g) in borophene, and a shift of 0.3 eV for B-B bond in the B\u003cem\u003e1s\u0026nbsp;\u003c/em\u003espectra of the hybrid structure was noticed, which may be attributed to gain of electron density from the TpPa-1 framework.\u003csup\u003e37\u003c/sup\u003e Similarly, in the high-resolution spectra of C\u003cem\u003e1s\u0026nbsp;\u003c/em\u003eof TpPa-1, three peaks at 284.1, 285.3 and 286.8 eV corresponding to C=C, C-N and C=O bonds, respectively which were located at 284.2, 285.2 and 288.1 eV for BNS@TpPa-1 (Figure 3d). As for the N\u003cem\u003e1s\u003c/em\u003e, one single peak located at 399.4 eV revealing the C-N-H bond formation in the keto form of TpPa-1 but showed a shift of 0.2 eV in the hybrid (Figure 3e). Likewise, the high-resolution O\u003cem\u003e1s\u003c/em\u003e spectra (Figure 3f) of the pristine TpPa-1 and the hybrid also revealed a change of peak positions. This indicates that there may be interactions between the lone pair electron density of TpPa-1 with the boron of BNS, and consequently, the electron density distribution in the framework may be changed resulting in the changes in the binding energies.\u003c/p\u003e\n\u003cp\u003eThe Raman analysis was also carried out for borophene, TpPa-1, and BNS@TpPa-1 to obtain a better insight into the phase and structural arrangement. BNS exhibited multiple peaks in the lower frequency region (Figure S5a). These peaks confirmed the presence of \u0026beta;\u003csub\u003e12\u003c/sub\u003e polymorphs of 2D borophene which corresponds 1068 cm\u003csup\u003e-1\u003c/sup\u003e for B\u003csub\u003e1g\u003c/sub\u003e\u003csup\u003e1\u003c/sup\u003e mode, 1147 and 911 cm\u003csup\u003e-1\u003c/sup\u003e corresponds to in-plane stretching mode of A\u003csub\u003eg\u003c/sub\u003e\u003csup\u003e1\u003c/sup\u003e and\u003csup\u003e\u0026nbsp;\u003c/sup\u003e(A\u003csub\u003eg\u003c/sub\u003e\u003csup\u003e2\u0026nbsp;\u003c/sup\u003e(S)), 378 cm\u003csup\u003e-1\u003c/sup\u003e ascribed to B\u003csub\u003e1g\u003c/sub\u003e\u003csup\u003e2\u003c/sup\u003e vibration modes of \u0026beta;\u003csub\u003e12\u003c/sub\u003e phase.\u003csup\u003e38\u003c/sup\u003e However, the Raman analysis results for TpPa-1 and BNS@TpPa-1 appeared to be the same, as the vibration modes corresponding to borophene were not discernible in the hybrid, which may be due to the low content of BNS in the TpPa-1 matrix. Despite this, we successfully integrated BNS within TpPa-1 and the porous crystalline 2D hybrid of TpPa-1 was further studied for hydrogen adsorption at low pressures.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eHydrogen adsorption studies were conducted using TpPa-1 and BNS@TpPa-1 to understand the influence of BNS on H\u003csub\u003e2\u003c/sub\u003e uptake in the hybrid. As discussed, heterogeneity and synergetic effects therein improve the hydrogen adsorption performance of porous materials, accordingly, higher efficiency in H\u003csub\u003e2\u003c/sub\u003e uptake was anticipated for BNS@TpPa-1. To validate our hypothesis, we performed the adsorption studies at pressure range (0.667-1.999 bar) using a Sievert apparatus at a temperature of 77 K. First, we measured the pressure drop (\u0026Delta;P) (Table S1) for the empty sample holder at different pressures when the temperature changed from the room temperature (RT) to 77 K. Then, the net pressure difference due to hydrogen adsorption for TpPa-1 and BNS@TpPa-1 was calculated by subtracting the empty cell \u0026Delta;P from the total pressure drop for the samples. The hydrogen adsorption capacity (weight%) was calculated using the equation 1 given below,\u003c/p\u003e\n\u003cp\u003e\u003cimg src=\"https://myfiles.space/user_files/58895_8739fc6c57c1c19a/58895_custom_files/img1774873656.png\" width=\"839\" height=\"85\"\u003e\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eThe pressure difference and H\u003csub\u003e2\u003c/sub\u003e adsorption weight% were summarized in Table S2 for TpPa-1 and BNS@TpPa-1. In both samples, the adsorbed H\u003csub\u003e2\u003c/sub\u003e weight% increased with pressure, consistent with the adsorption behavior of porous materials. It is worth noting that by introducing BNS to the TpPa-1 framework, H\u003csub\u003e2\u003c/sub\u003e adsorption weight% greatly enhanced from 0.175 to 0.277 (Figure 3c), which is 1.6-fold higher than that of pristine TpPa-1 at 1.999 bar and 77 K. Even with lower pore volume and surface area, BNS@TpPa-1 showed greater H\u003csub\u003e2\u003c/sub\u003e adsorption. This observation suggests that BNS may play a significant role in enhancing the H\u003csub\u003e2\u003c/sub\u003e adsorption of BNS@TpPa-1 hybrid material.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe kinetics of H\u003csub\u003e2\u003c/sub\u003e adsorption strongly depends on the operating pressure. As pressure decreased from 1.999 to 0.667 bar, the adsorption profile showed a sharp initial uptake followed by gradual uptake (Figure 4a-e). Due to the highly porous nature of TpPa-1 and BNS@TpPa-1, a rapid H\u003csub\u003e2\u003c/sub\u003e adsorption rate was observed, reaching saturation within 2 minutes at each applied pressure. Along with the adsorption rate, the desorption of H\u003csub\u003e2\u003c/sub\u003e from the materials is crucial to release the gas without much effort. Desorption studies were conducted by recording the pressure increase when the sample temperature changed from 77 K to RT. Both samples desorbed H\u003csub\u003e2\u003c/sub\u003e within 10 minutes, at all the pressures after reaching to RT (Figure S6). The desorbed H\u003csub\u003e2\u003c/sub\u003e weight% were calculated by using equation 2 and was listed in Table S3, and a comparative representation of adsorption-desorption behavior between both samples was shown in Figure 4f. Notably, both samples desorbed almost all adsorbed H\u003csub\u003e2\u003c/sub\u003e indicating the characteristics of physisorption. We also have parameterized the H\u003csub\u003e2\u003c/sub\u003e adsorption isotherms for TpPa-1 and BNS@TpPa-1 according to the Freundlich and Langmuir model. Correlation coefficients (R\u003csup\u003e2\u003c/sup\u003e) obtained for both the fittings were close to 0.99, which suggests that the data were fitted for both the models (Figure 4g \u0026amp; h). This suggests monolayer adsorption in low-pressure regions.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003cimg src=\"https://myfiles.space/user_files/58895_8739fc6c57c1c19a/58895_custom_files/img1774873808.png\" width=\"839\" height=\"118\"\u003e\u003c/p\u003e\n\u003cp\u003eFurther investigation was carried out with Grand Canonical Monte Carlo (GCMC) simulations to understand the adsorption behavior of TpPa-1and BNS@TpPa-1. The hydrogen adsorption capacities of TpPa-1 and BNS@TpPa-1 (Figure 5d \u0026amp; e) were compared across experiment and simulations. Fig. 5b \u0026amp; c presents snapshots from GCMC simulations for both the pristine TpPa-1 and BNS@TpPa-1. It was observed that for both pristine and the hybrid structures, the H\u003csub\u003e2\u003c/sub\u003e uptake (Table S3) increased consistently with increasing pressure, which is in agreement with the experimental results. This trend reflects the typical physisorption behavior dominated by Van der Waals interactions, where higher pressures enhance the adsorbate-adsorbent interaction probability. However, as shown in Figure 5, for the TpPa-1 and BNS@TpPa-1, the GCMC-predicted capacity was consistently higher than the experimental results throughout the pressure range.\u003c/p\u003e\n\u003cp\u003eSeveral factors as discussed in the literature to comprehend the results from GCMC simulations that of experimental measurements. One of the primary reasons is the neglect of quantum effects such as zero-point energy and tunneling in classical GCMC, which leads to overestimation of adsorption, particularly at cryogenic temperatures like 77 K. Additionally, simulations often assume idealized, rigid, and defect-free frameworks, whereas real materials may exhibit structural defects, pore blockage, or flexibility that reduce accessible surface area.\u003csup\u003e39-41\u003c/sup\u003e Also in case of BNS@TpPa-1 , substantial overestimation of hydrogen uptake in the GCMC simulation compared to experiment arises from the idealized interface and uniform stacking of the simulation model in which the TpPa-1 fragment is ideally positioned between two borophene layers. This will create maximum available surface area and potential for stronger interaction via \u0026pi;\u0026ndash;H\u003csub\u003e2\u003c/sub\u003e. In practice, however, the interface of BNS@TpPa-1 will be more disordered with potential aggregation, pore blocking, or limited interfacial exposure leading to lower experimental activity. While discrepancies exist in absolute adsorption values, both theoretical and experimental findings consistently highlight that the incorporation of BNS significantly enhances hydrogen uptake compared to the pristine TpPa-1. This observed trend is of primary importance, highlighting the potential of borophene as a pore-modifying or confinement-enhancing additive.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe isosteric heat of adsorption (Q\u003csub\u003est\u003c/sub\u003e) is a crucial thermodynamic parameter that quantifies the interaction strength between adsorbate molecules and the surface of a porous material. It provides insight into the nature of the adsorption mechanism whether it is dominated by weak Van der Waals forces (physisorption) or stronger chemisorptive interactions. For hydrogen storage applications, an ideal Q\u003csub\u003est\u003c/sub\u003e lies in the moderate range of 4-15 kJmol\u003csup\u003e-1\u003c/sup\u003e, balancing strong enough binding to enable uptake at ambient or cryogenic conditions while avoiding excessive binding that impedes release. In this study, GCMC simulations at 77 K revealed that the pristine TpPa-1 exhibits a relatively low and nearly constant Q\u003csub\u003est\u003c/sub\u003e of about 2.85 kJmol\u003csup\u003e-1\u003c/sup\u003e across a wide pressure range (0.667-1.999 bar), indicative of weak physisorption on homogeneous adsorption sites. Such values are typical of COFs composed purely of organic linkers, where hydrogen interacts primarily via dispersive forces with aromatic surfaces. In contrast, the hybrid material demonstrated a significantly higher Q\u003csub\u003est\u003c/sub\u003e of nearly 13 kJmol\u003csup\u003e-1\u003c/sup\u003e, nearly four times that of the unmodified TpPa-1, which is higher as compared to reported Q\u003csub\u003est\u003c/sub\u003e value for COFs (Table S6). This increase suggests that the incorporation of BNS introduces higher-energy adsorption sites, likely due to a combination of \u0026pi;\u0026ndash;metal interactions, electronic polarization effects, and nanoconfinement between the 2D layers. Borophene, being an electron-deficient, anisotropic material with metallic conductivity can induce polarization effects through electron density distribution with TpPa-1, while the hybrid abled to adsorb hydrogen molecules more effectively than an organic-only framework, thereby enhancing the adsorption enthalpy.\u003csup\u003e20, 42\u003c/sup\u003e The Q\u003csub\u003est\u003c/sub\u003e value of ~13 kJmol\u003csup\u003e-1\u003c/sup\u003e falls within the optimal range reported for advanced porous materials such as MOFs and doped carbons, and is consistent with literature-reported values for hydrogen adsorption on frameworks incorporating conductive or polarizable components.\u003csup\u003e43, 44\u003c/sup\u003e\u003c/p\u003e\n\u003cp\u003eThe observed trend, where the Q\u003csub\u003est\u003c/sub\u003e is less for TpPa-1 and appreciably increases in the hybrid material, reflects the generation of energetically more diverse and stronger binding environments in the hybrid structure. These results confirm that structural modification through 2D material integration is a viable strategy to enhance gas adsorption performance. Furthermore, the moderate increase in Q\u003csub\u003est\u003c/sub\u003e still ensures that hydrogen remains easily desorbable, preserving reversibility, an important criterion for practical storage applications. Thus, the Q\u003csub\u003est\u003c/sub\u003e data not only validates the superior adsorption capacity observed experimentally for the BNS@TpPa-1 hybrid but also highlights the fundamental thermodynamic advantage conferred by hybrid interface engineering.\u003c/p\u003e\n\u003cp\u003eThe overall statistical behavior of TpPa-1/borophene/H\u003csub\u003e2\u003c/sub\u003e system is revealed by the GCMC calculations. To unfold the fundamental, however, the microscopic interaction between the COF, borophene and H\u003csub\u003e2\u003c/sub\u003e molecules, DFT is employed on (i) TpPa-1, (ii) borophene and (iii) BNS@TpPa-1 hybrid. We calculate the site-specific adsorption energies (\u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e) for all three cases (Table S5 \u0026amp; Table1). Active sites of interest have been identified based on the functional groups and the number of bonds for TpPa-1 and borophene, respectively. These sites are enumerated and shown on schematic for TpPa-1 and borophene (Figure S7 and S8, respectively). We considered the active sites for TpPa-1 and hybrid to be the same. We find from the \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e values tabulated in Table S5 that apparently all the selected sites are energetically favorable for both TpPa-1 and borophene. Although the active sites across TpPa-1 and borophene are not chemically equivalent, broadly, \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e for TpPa-1 and borophene vary ~eV and 10s of meV, respectively. This variation is attributed to the presence of functional groups on the TpPa-1 where relatively stronger interactions are expected with H\u003csub\u003e2\u003c/sub\u003e. The adsorption energy values for our structure are very much comparable with the literature for \u003cem\u003e\u0026beta;\u003c/em\u003e\u003csub\u003e12\u003c/sub\u003e and bilayer borophene (Table S8). While \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e values of our borophene are about one order lower compared with the literature on doped (Li, Y, Na, K or Ca) borophene (Table S8).\u003csup\u003e45, 46\u003c/sup\u003e This variation is well justified, since the H\u003csub\u003e2\u003c/sub\u003e is adsorbed on the dopant atom in contrast to that of pristine borophene. \u0026nbsp;Within TpPa-1, the \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e is not site specific indicating similar kind of interaction across the framework. In contrast, for borophene the \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e values vary from -10 to -67 meV while the sites 5, 6, 8 and 9\u003cu\u003e\u0026nbsp;\u003c/u\u003eare comparable. In the case of TpPa-1 (borophene), the corresponding sites of the minimum and maximum \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e are 5(7) and 10(1), respectively. The variation of \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e across the two systems is attributed to the type of interaction that H\u003csub\u003e2\u003c/sub\u003e poses with metallic (semiconducting) borophene (TpPa-1), apart from the active edge atoms of TpPa-1. The typical distance between H\u003csub\u003e2\u003c/sub\u003e and borophene (TpPa-1) is ~ 3.7 \u0026Aring; (~3 \u0026Aring;). H\u003csub\u003e2\u003c/sub\u003e adsorption experiments indicated that the hybrid depicted improved performance. To identify the sites that would possibly host H\u003csub\u003e2\u003c/sub\u003e we have inserted it at the interface of hybrid as well as the edges of TpPa-1. The corresponding \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e values are tabulated in Table 1. Clearly, the positive value of \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e for TpPa-1/H\u003csub\u003e2\u003c/sub\u003e/borophene is not energetically favored for positions 1 and 7. Also, as per the optimized geometry, the borophene layer is significantly deformed in the hybrid due to the presence of H\u003csub\u003e2\u003c/sub\u003e at the interface (Figure S09 and S10) as comprehended from the \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e values (Table 1). In clear contrast, at the edge (configurations 2 to 9), the negative \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e indicates favorable sites while the magnitude suggests its strength. We note that the sites near the oxygen of the carbonyl group are relatively stronger. Essentially, within the hybrid, the \u003cem\u003eE\u003c/em\u003e\u003csub\u003eads\u003c/sub\u003e values reflect the formation of \u003cem\u003ehybrid\u0026nbsp;\u003c/em\u003eedge states that favor the adsorption of H\u003csub\u003e2\u003c/sub\u003e. To further corroborate the formation of hybrid, we have investigated the charge difference plots (Figure 6 and Figure S11). In the case of TpPa-1, the H\u003csub\u003e2\u003c/sub\u003e is localized at about ~3 \u0026Aring; above the plane of TpPa-1 (Figure 6a), while it is almost in plane in the hybrid. The distribution of charge is primarily above the plane of TpPa-1 which shifted to the edge and borophene in the hybrid structure (Figure 6b). \u0026nbsp;Regions with positive values (blue) indicate the accumulation when compared to isolated counterpart, indicating bonding regions. Such accumulations can be observed on both TpPa-1 as well as borophene confirming the synergetic effect of the \u003cem\u003ehybrid\u0026nbsp;\u003c/em\u003ein the adsorption of H\u003csub\u003e2\u003c/sub\u003e corroborating the enhanced adsorption as observed in the experiment.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eTable 1.\u0026nbsp;\u003c/strong\u003eAdsorption energies for selected configurations of TpPa-1, borophene and BNS@TpPa-1 hybrid. The enumerated sites of TpPa-1 and borophene are not equivalent, however, that of TpPa-1 and hybrid are equivalent.\u003c/p\u003e\n\u003ctable border=\"0\" cellspacing=\"0\" cellpadding=\"0\" width=\"100%\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.829\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-10.083\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e168.294\u003csup\u003e[i]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-18.20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-13.839\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-44.686\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.829\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-10.744\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-43.341\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.837\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-15.229\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-50.687\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.839\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-63.626\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-45.870\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.839\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-63.179\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-51.578\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.815\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-67.074\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-44.686\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.837\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-63.268\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-24.265\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-1.819\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 24px;\"\u003e\n \u003cp\u003e-63.465\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\" style=\"width: 25px;\"\u003e\n \u003cp\u003e-48.789\u003csup\u003e[e]\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e[i] represent the spatial position of H\u003csub\u003e2\u003c/sub\u003e is at the interface of the hybrid [e] represent the spatial position of H2 is at the edge of the hybrid.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn summary, we have designed and synthesized a promising 2D hybrid porous material, BNS@TpPa-1, which has exhibited more efficient performance in H\u003csub\u003e2\u003c/sub\u003e adsorption as compared to the parent COF, TpPa-1. The hybrid has achieved a 1.6-fold increment in H\u003csub\u003e2\u003c/sub\u003e adsorption equivalent to 0.277 weight%. The experimental results, supported by GCMC simulation, reveal that BNS incorporated hybrid BNS-COF demonstrates better adsorption properties due to the enhanced isosteric heat of adsorption from 2.85 kJmol\u003csup\u003e-1\u003c/sup\u003e to ~13 kJmol\u003csup\u003e-1\u003c/sup\u003e. DFT calculations not only confirm the synergetic effects within hybrid but also identify that the active sites of adsorption are the \u0026ldquo;edges of TpPa-1\u0026rdquo; corroborating the enhanced H\u003csub\u003e2\u003c/sub\u003e adsorption as observed in the experiment. The results of this work are of significance in the further elucidation of hydrogen adsorption properties on low-dimensional boron materials and TpPa-1 and could be potentially tapped for overall hydrogen storage materials. This work highlights the potential of a hybrid porous material for physisorptive H\u003csub\u003e2\u003c/sub\u003e storage with enhanced isosteric heat of absorption and may contribute to the realization of advanced hydrogen storage material under near ambient conditions.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003eAUTHOR INFORMATION\u003c/p\u003e\n\u003cp\u003eCorresponding Authors\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDr. R. Medishetty\u003c/strong\u003e - Department of Chemistry and Department of Materials Science and Metallurgical Engineering, Indian Institute of Technology Bhilai; Orcid ID: 0000-0003-2289-2655. Email: [email protected]\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDr. B. Sreenivasulu \u003c/strong\u003e- Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India, Orcid ID: 0000-0003-3489-5263. E-mail: [email protected]\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDr. S. Vempati\u003c/strong\u003e - Department of Physics, IIT Bhilai, Durg, Chhattisgarh 491001, India. Orcid ID: 0000-0002-0536-7827. Email: [email protected]\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eA. Gogoi\u003c/strong\u003e - Department of Chemistry, Indian Institute of Technology Bhilai, Durg, Chhattisgarh 491002, India; Orcid ID: 0009-0007-8675-4178.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eS. Sengupta\u003c/strong\u003e - Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eA. Rathore \u003c/strong\u003e- Department of Physics, IIT Bhilai, Durg, Chhattisgarh 491001, India, Orcid ID: 0009-0000-1044-8325.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eV.M. Kabilan \u003c/strong\u003e\u003cstrong\u003e-\u003c/strong\u003e Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India, Orcid ID: 0009-0006-2376-0506.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eS. R. Abothu\u003c/strong\u003e - Department of Chemistry, Indian Institute of Technology Bhilai, Durg, Chhattisgarh 491002, India, Orcid ID: 0009-0000-7037-7573.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eM. Bootharajan \u003c/strong\u003e\u003cstrong\u003e-\u003c/strong\u003e Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eC. V. S. B. Rao\u003c/strong\u003e\u003cem\u003e \u003c/em\u003e\u003cstrong\u003e-\u003c/strong\u003e Materials Chemistry and Metal Fuel Cycle Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu, India, Homi Bhabha National Institure, Training School Complex, Anushakthi Nagar, Mumbai, Maharastra 400094, India.\u003c/p\u003e\n\n\u003cp\u003eAuthor Contributions\u003c/p\u003e\n\u003cp\u003eThe manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.\u003c/p\u003e\n\u003cp\u003eFunding Sources\u003c/p\u003e\n\u003cp\u003eR. M. acknowledges support from the IBITF under Grant No. IBITF/PRAYAS/Note/2023-24/0009. AG and AR would like to thank IIT Bhilai and Ministry of Education, India (MoE) for the research fellowship. SR would like to thank CSIR (09/1237(19503)/2024-EMR-I) for the research fellowship.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eNotes\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing financial interest.\u003c/p\u003e\n\u003cp\u003eACKNOWLEDGMENT\u003c/p\u003e\n\u003cp\u003eWe thank IIT Bhilai for CIF facilities. The authors sincerely thank Dr. V. Jayaraman, Director, MC\u0026amp;MFCG, IGCAR, Kalpakkam, for granting permission to carry out hydrogen sorption experiments at the MC\u0026amp;MFCG facility.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eGomez-Romero, P.; Pokhriyal, A.; Rueda-Garc\u0026iacute;a, D.; Bengoa, L. N.; Gonz\u0026aacute;lez-Gil, R. M. Hybrid Materials: A Metareview. \u003cem\u003eChem. 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Enhancement in the hydrogen storage capability of borophene through yttrium doping: A theoretical study. \u003cem\u003eJ. Energy Storage \u003c/em\u003e\u003cstrong\u003e2022\u003c/strong\u003e, \u003cem\u003e55\u003c/em\u003e, 105500.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"Indian Institute of Technology Bhilai","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"borophene, COF, H2 adsorption, 2D materials, porous materials, hybrid materials","lastPublishedDoi":"10.21203/rs.3.rs-9236591/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9236591/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTwo-dimensional hybrid porous materials have emerged as potential materials in recent years for advancing gas adsorption strategies, particularly in the field of physisorbed H\u003csub\u003e2\u003c/sub\u003e storage for future energy demand. Owing to their unique features, hybrid porous materials exhibit enhanced induction interactions with H\u003csub\u003e2\u003c/sub\u003e that assist in storing relatively higher gravimetric hydrogen capacities compared to their parent materials. In this study, we report a two-dimensional crystalline hybrid porous material, borophene-TpPa-1, synthesized by integrating borophene nanosheets in a covalent organic framework, TpPa-1. The hybrid remarkably exhibits enhanced hydrogen adsorption at 1.999 bar and 77 K, achieving a 1.6-fold higher uptake relative to TpPa-1. GCMC simulations attribute this observation to the enhanced enthalpy of adsorption (~ 13 kJmol\u003csup\u003e-1\u003c/sup\u003e), reflecting the strengthened interactions between H\u003csub\u003e2\u003c/sub\u003e and the hybrid. Furthermore, the DFT calculation identifies favorable sites of adsorption and confirms the formation of the \u003cem\u003ehybrid \u003c/em\u003estructure. It also validates the enhanced H\u003csub\u003e2\u003c/sub\u003e adsorption in terms of adsorption energies and charge re-distribution. These results reveal that incorporation of borophene in a porous material can significantly enhance hydrogen adsorption.\u003c/p\u003e","manuscriptTitle":"Borophene Nanosheets grafted Covalent Organic Framework: A 2D Hybrid Porous Material for Hydrogen Adsorption Studies","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-03-30 12:42:22","doi":"10.21203/rs.3.rs-9236591/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"b9fac170-7539-4a68-81d9-12e4bf8c3e9d","owner":[],"postedDate":"March 30th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":65210510,"name":"Materials Chemistry"},{"id":65210511,"name":"Physical Chemistry"}],"tags":[],"updatedAt":"2026-03-30T12:42:22+00:00","versionOfRecord":[],"versionCreatedAt":"2026-03-30 12:42:22","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9236591","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9236591","identity":"rs-9236591","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}