Leveraging Metal Organic Framework Derived Indium/Zirconium Oxide for Unprecedented Catalytic Performance in CO₂ Hydrogenation to Methanol

Leveraging Metal Organic Framework Derived Indium/Zirconium Oxide for Unprecedented Catalytic Performance in CO₂ Hydrogenation to Methanol | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Leveraging Metal Organic Framework Derived Indium/Zirconium Oxide for Unprecedented Catalytic Performance in CO₂ Hydrogenation to Methanol Suresh Bhargava, Paramita koley, Subhash Shit, Takefumi Yoshida, and 7 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6143390/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 07 Oct, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract The hydrogenation of CO₂ to methanol is a promising route for carbon capture and utilization, but achieving high selectivity and productivity remains a challenge. This study presents a novel catalyst synthesized by pyrolyzing a zirconium-based metal-organic framework (Zr-BDC) impregnated with indium, yielding ultrafine In₂O₃ nanoparticles uniformly embedded within a ZrO₂ and carbon matrix. The resulting In₂O₃/ZrO₂ heterojunction exhibits abundant oxygen vacancies at the interface, which is crucial in enhancing catalytic performance. Under gas-phase conditions, the catalyst achieves an exceptional methanol selectivity of 81% with a record-high productivity of 2.64 gMeOH·gcat⁻¹·h⁻¹, while in liquid-phase hydrogenation, methanol selectivity reaches 96%. Comprehensive structural characterizations confirm that oxygen vacancies and the heterointerface serve as active sites, facilitating CO₂ activation and methanol stabilization. Mechanistic insights from in situ DRIFTS and ATR-IR spectroscopy reveal that methanol formation proceeds via the formate pathway, further supported by in situ ambient-pressure X-ray photoelectron spectroscopy, demonstrating electronic structural modulation and an increased concentration of oxygen vacancies. These findings underscore the critical role of defect engineering in optimizing CO₂ hydrogenation catalysts and provide a pathway for designing highly efficient systems for sustainable methanol production. Physical sciences/Chemistry/Green chemistry/Sustainability Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Rising CO 2 levels in the atmosphere have heightened concerns about global climate change and ocean acidification 1 . Hydrogenating CO 2 into alcohol or hydrocarbons presents a key strategy for recycling atmospheric CO 2 emissions from combustion processes. With growing industrial demand for methanol, significant efforts have focused on converting CO 2 into methanol 2 . Various materials have been tested as catalysts for this conversion, with most industrial processes relying on metal nanoparticles supported on oxide substrates. Cu-based catalysts, often combined with ZnO and/or Al 2 O 3 , have been used for over 50 years 3 . While these catalysts avoid methane production, they show limited activity for CO 2 hydrogenation at low temperatures (T < 500 K), leading to higher hydrogen consumption and reduced methanol yields 4 . Additionally, the presence of water accelerates the sintering of Cu and ZnO, causing catalyst deactivation 5 . Indium-based catalysts have emerged as a promising solution for converting CO 2 into methanol 6 . In 2 O 3 offers up to 100% selectivity for methanol under optimal CO 2 hydrogenation conditions, with exceptional stability due to its oxide-based active phase 7 . While unsupported In 2 O 3 has seen improvements through the addition of active components or promoters to enhance H 2 dissociation, supported In-based catalysts are more suitable for industrial use, requiring less active material and providing greater stability 8 – 11 . Recent research has focused on supported In-based catalysts, with monoclinic zirconia (m-ZrO 2 ) proving to be excellent support, achieving high CO 2 conversion and methanol selectivity 12 . In addition, Tsoukalou et al. 12 and Chen et al. 13 have concentrated on identifying the active phase of the In 2 O 3 /ZrO 2 catalyst used in the methanol synthesis from CO 2 and H 2 . The In-Ov-Zr sites (Ov representing oxygen vacancies) formed by the interaction between In 2 O 3 and ZrO 2 are crucial for maximizing activity and stability in methanol production. The effectiveness of CO 2 reduction to methanol is largely influenced by the size and concentration of In 2 O 3 domains 13 . However, increasing the interfacial area between In 2 O 3 domains and the m-ZrO 2 support remains a key challenge for further enhancing performance. Increasing the interfacial area and oxygen vacancies can be achieved through MOF-derived material synthesis. However, designing heterojunctions with abundant interfaces in complex systems remains challenging 14 . Certain MOFs and MOF composites serve as ideal precursors or templates for producing heterostructured transition metal/metal oxides through a straightforward hydrothermal-calcination method 15 – 18 . These MOF-derived heterostructures typically retain the high porosity and versatile morphologies of MOFs, making them highly promising for catalytic applications 19 – 21 . For example, CoMn-MOF-74-derived Co/MnO heterostructured nanoparticles have shown improved CO 2 adsorption and activation, delivering excellent catalytic performance in low-temperature CO 2 methanation 22 . Building on this success, we developed a ZrO 2 /In 2 O 3 -based heterostructural catalyst using MOF precursors, and we evaluated its efficiency for CO 2 hydrogenation to methanol. In this study, we developed a composite catalyst featuring a heterojunction of In 2 O 3 and ZrO 2 (Deg In-Zr (3:8)), derived from an indium-impregnated Zr-BDC MOF. The Deg In-Zr (3:8) catalyst demonstrated outstanding performance in the selective hydrogenation of CO 2 to methanol in both liquid and gas phases under ambient conditions. To our knowledge, this catalyst achieved the highest reported CH₃OH productivity of 2.64 g MeOH ·g cat −1 .h − 1 in the gas phase. Additionally, the catalyst contains a low indium content (0.6 wt.%), with 2–3 nm In 2 O 3 nanoparticles uniformly dispersed on the surface, making it a cost-effective option for industrial use. The unique In 2 O 3 /ZrO 2 heterointerface provided numerous active sites for enhanced H 2 dissociation and CO 2 activation, confirmed through detailed structural analysis using XAS (XANES and EXAFS). The reaction mechanism responsible for this exceptional performance was investigated using in situ ATR-IR for liquid-phase reactions, in situ DRIFTS for gas-phase reactions, and quantum chemistry modeling. Furthermore, ambient pressure in situ XPS was conducted to gain insights into the active phase during CO 2 hydrogenation to methanol. Synthetic route The Zr-BDC MOF was synthesized by dissolving ZrCl 4 (0.053 g, 0.227 mmol) and 1,4-benzene dicarboxylic acid (H 2 BDC) (0.034 g, 0.227 mmol) in N,N'-dimethylformamide (DMF) at room temperature 23 . The mixture was heated at 120°C for 24 hours to induce crystallization. After cooling, the solid was filtered, washed with DMF and methanol, and dried at 60°C overnight. X-ray diffraction (XRD) confirmed that the synthesized MOF matched the previously reported Zr-BDC structure 24 . Indium was incorporated into the MOF via the incipient wetness impregnation (IWI) method to produce the In-Zr BDC catalyst with various indium-to-zirconium ratios. The mixture was refluxed with indium nitrate in methanol at 70°C, centrifuged, and dried. The XRD pattern confirmed successful indium incorporation. All samples were calcined at 600°C in nitrogen, resulting in the Deg In-Zr catalyst. During calcination, solvent molecules were lost around 150°C, and the H 2 BDC ligand decomposed near 350°C. The Deg In-Zr BDC (3:8) catalyst, containing ZrO 2 and In 2 O 3 phases, exhibited the highest CO 2 conversion to methanol, achieving high efficiency with minimal indium content. Crystalline phase and surface properties The XRD patterns of various samples, including ZrO 2 , In 2 O 3 , In 2 O 3 -ZrO 2 /C, In 2 O 3 -ZrO 2 , Zr-BDC MOF, indium-impregnated Zr-BDC (In-Zr BDC), and degraded In-Zr MOF (Deg In-Zr), are shown in Fig. 1 b. The Zr-BDC MOF displayed sharp peaks, indicating high crystallinity, with a pattern matching previous reports 23 . After thermal degradation at 600°C, the MOF structure collapsed, altering the diffraction pattern and revealing the presence of In 2 O 3 7 and ZrO 2 phases with peak shifts as compared to bare In 2 O 3 and ZrO 2 , suggesting crystal distortion and small crystal domain size. In contrast, the impregnated In 2 O 3 -ZrO 2 and the as-synthesized graphitic carbon-supported In 2 O 3 and ZrO 2 exhibit sharp crystalline peaks, indicating the presence of large crystalline phases. Moreover, the peaks corresponding to In 2 O 3 and ZrO 2 remain unchanged relative to those of pure In 2 O 3 and ZrO 2 . All degraded MOF catalysts with different In and Zr ratio exhibited similar diffraction patterns (Fig. S1 ). Raman spectra of Zr-BDC (Fig. 1 b) show characteristic shifts at 634 and 860 cm⁻¹ (C–H bond vibrations) and at 1140 and 1611 cm⁻¹ (C = C modes of the benzene ring). Peaks at 1434 and 1448 cm⁻¹ correspond to symmetric and asymmetric C–O 2 stretching 25 , 26 . Indium impregnation retained the MOF's structural integrity. After degradation, the Deg In-Zr (3:8) catalyst showed D and G bands at 1316 cm⁻¹ and 1590 cm⁻¹, indicating graphitic carbon formation 27 . Further details are available in the supporting information (page number 19). X-ray Photoelectron Spectroscopy (XPS) was performed to analyze the surface composition and oxidation states of the elements in various catalysts (Fig. 1 (d) to (f), Fig. S2 and S3). The high-resolution XPS spectra for indium (Fig. 1 (d)) reveal distinct peaks corresponding to In 2 O 3 and In(OH) 3 for the as-synthesized metal oxides 28 . In comparison, the Deg In-Zr (3:8) catalyst shows the largest binding energy shift for In 3+ , suggesting a strong electronic interaction between In 2 O 3 and ZrO 2 in this material 10 . This shift indicates significant electronic modulation, as further detailed in the supporting information. For ZrO 2 , (Fig. 1 (e)) the Zr 3d 5/2 and 3d 3/2 peaks appear at 182.01 eV and 184.34 eV 29 , indicating the presence of Zr 4+ . In the Deg In-Zr (3:8) catalyst, these peaks shift to higher binding energies (182.42 eV and 184.40 eV), likely due to surface restructuring and enhanced electronic interaction between ZrO 2 and In 2 O 3 30 . The oxygen 1s XPS spectra of the metal oxide catalysts (Fig. 1 (f)) show three peaks at 529.62 eV, 531.2 eV, and 532.7 eV, corresponding to lattice oxygen (O L ), oxygen vacancies (O V ), and chemically adsorbed oxygen or C–O bond-associated oxygen (O C ), respectively 31 , 32 . The Deg In-Zr (3:8) catalyst exhibits the highest oxygen vacancy concentration, as shown in Fig. 1 (e) and Table S3, compared to other as-synthesized catalysts such as In 2 O 3 , ZrO 2 , In 2 O 3 -ZrO 2 , and In 2 O 3 -ZrO 2 /C. The higher concentration of oxygen vacancies likely contributes to its enhanced activity in CO 2 hydrogenation. A detailed discussion of the varying indium and zirconium ratios in the degraded catalyst is provided in the supporting information (Fig. S3) (page number 21). To gain precise quantitative insights into electronic behavior and coordination environments, X-ray Absorption Spectroscopy (XAS) was employed (Fig. 2 , S5 & S6). The X-ray Absorption Near Edge Structure (XANES) at the In K-edge provided information on the valence state of the absorbing atom, though the low indium density across samples made analysis challenging. All samples showed significant deviations from metallic Zr (Fig. 2 g). In the In-Zr Metal-Organic Frameworks (MOFs), a minor electron transfer from indium to the Zr MOF was observed, with minimal impact on the structural integrity of the Zr framework. However, in the degraded In-Zr MOFs (Deg In-Zr (3:8)), the Zr MOF decomposed into ZrO 2 , displaying differences from monoclinic ZrO 2 and similarities with In-modified ZrO 2 in impregnated In-ZrO 2 samples 33 . We also analyzed the extended X-ray absorption fine structure (EXAFS) spectra at Zr K-edge to investigate the local structure around Zr atoms in the samples. At the Zr K-edge of the Zr MOF, two types of Zr-O bonds and a Zr-Zr bond were detected, indicative of the inherent structure of the Zr MOF (Fig. 2 c). However, the Zr-Zr coordination number was lower than expected, suggesting distortions around Zr atoms within the MOF framework, reducing the coordination number as estimated by EXAFS. EXAFS analysis at the In K-edge for the In-Zr MOF was anticipated, but insufficient signals were obtained, suggesting either lower-than-expected In density (as estimated by ICP) or a distorted and heterogeneous local structure around In atoms, complicating precise EXAFS measurements. Nonetheless, the Zr-Zr coordination number was lower in the In-Zr MOF, indicating increased distortion around Zr atoms due to the incorporation of In into the framework pores. The EXAFS Fourier transform showed a peak at approximately 0.3 nm, shorter than that in Zr MOFs, and the presence of Zr-In bonds improved the fitting analysis. Direct Zr-In bonding at 0.299 nm ± 0.003 was observed, suggesting the formation of Zr-O-In bonds at the interface of the MOF pore walls (Fig. 2 e and i) 12 . At the Zr K-edge, EXAFS analysis of monoclinic ZrO 2 samples revealed Zr-O bonds at 0.215 nm and Zr-Zr bonds at 0.350 nm (Fig. 2 b). In the degraded In-Zr MOF (Deg In-Zr (3:8)), the presence of indium affected the structural parameters (Fig. 2 d and h), showing two distinct Zr-O bonds at 0.214 nm and 0.233 nm, compared to the single Zr-O bond at 0.215 nm in ZrO 2 . Zr-Zr bonding in the degraded In-Zr MOF was observed at 0.362 nm, compared to 0.350 nm in ZrO 2 , while Zr-In bonding at 0.299 nm was also noted, similar to that in the as-synthesized In-Zr MOF. However, the coordination number of Zr-In bonds was low, as detailed in the table below. The R-factor for fitting involving Zr-In bonds (3.5%) was superior to that for Zr-Zr bonds alone (4.6%). Therefore, the ZrO 2 formed from the degradation of In-Zr MOF at 600°C exhibited a different lattice structure compared to ZrO 2 , likely due to the formation of a new mixed In-Zr oxide with Zr-O-In bonds. This mixed oxide likely contains numerous oxygen defects due to the differing valences of Zr 4+ and In 3 + 34 . CO 2 -TPD was performed to assess the CO 2 adsorption behavior of various catalysts. In the CO 2 -TPD profiles (Fig. S9), all catalysts showed a desorption peak between 50–200°C, attributed to bicarbonate formation via physical CO 2 adsorption on surface hydroxyl groups 35 . A second peak, above 200°C, indicated CO 2 chemisorption at oxygen vacancies, critical for CO 2 activation 36 . The Deg In-Zr (3:8) catalyst showed a higher CO 2 chemisorption intensity between 200–450°C compared to bare In 2 O 3 and ZrO 2 , suggesting that the heterointerfaces between In 2 O 3 and ZrO 2 , along with oxygen vacancies, act as key sites for CO 2 adsorption and activation 13 .HCOOH and CH 3 OH temperature-programmed desorption (TPD) experiments were conducted to examine the surface species responsible for high methanol yield during CO 2 hydrogenation (Fig. S7 (c) and (b)). In the Deg In-Zr catalyst, the HCOOH decomposition peak appeared at lower temperatures, indicating reduced stability with increased indium content, leading to its decomposition into CO 2 and H 2 . This suggests that optimizing indium content is key to effectively converting HCOO* intermediates into CH 3 O* species. Similar results by Han et al. showed that lower indium loadings stabilized HCOO species 13 . The CH 3 OH TPD profile revealed that methanol stability decreases with higher indium content, highlighting the importance of reducing indium concentration to improve methanol selectivity in CO 2 hydrogenation. The H 2 -TPR analysis also suggested the formation of the highest amount of oxygen vacancies in the Deg In-Zr (3:8) catalyst which is explained in supporting information (page number 20 and Fig. S8). Morphological and textural properties of the catalysts The morphology of the materials was analyzed using TEM and HRTEM. TEM images of Zr-BDC (Fig. 1 ) reveal a square-like morphology, which is also maintained in the Deg In-Zr (3:8) catalyst, featuring ultrasmall metal oxide nanoparticles ranging from 2 to 3 nm. As shown in Fig. 3 , this catalyst contains both In 2 O 3 and ZrO 2 nanoparticles. The d-spacing of 0.417 nm, observed in In 2 O 3 , is slightly larger than the standard 0.413 nm for the In 2 O 3 (211) 37 lattice plane, likely due to crystal lattice distortion, as supported by XRD data 38 . For ZrO 2 , the HR-TEM images display d-spacing values of 0.497 nm and 0.269 nm, corresponding to the (001) and (200) lattice planes of the monoclinic phase, respectively 39 . This increased d-spacing in the Deg In-Zr (3:8) catalyst compared to bare ZrO 2 indicates crystal distortion. Notably, no tetragonal ZrO 2 phase was observed in the HR-TEM analysis. Previous research by Muller et al. highlighted the high activity of monoclinic ZrO 2 in CO 2 hydrogenation to methanol, a finding supported by the absence of the tetragonal form in EXAFS analysis 12 . The SEAD pattern also confirms the presence of both In 2 O 3 and ZrO 2 , with a diffusive pattern attributed to the ultrasmall nanoparticles in the Deg In-Zr (3:8) catalyst 40 . STEM images (Fig. 3 (d)-(h)) and EDX spectra (Fig. S12) further demonstrate the uniform dispersion of indium and zirconium within the carbonated MOF matrix. Catalytic activity and stability CO 2 catalytic conversion in the gas phase was conducted at 220°C with a feed mixture of (1:3) CO 2 and H 2 , total pressure is 30 bar over various catalysts. As shown in Fig. 4 (a) and (b), the Deg In-Zr BDC (3:8) catalyst demonstrated outstanding methanol productivity (2.64 g MeOH ·g cat −1 ·h − 1 ) after 51 hours, with an exceptional gas hourly space velocity (GHSV) of 78,000 h⁻¹. This superior performance is likely due to the formation of an In 2 O 3 -incorporated ZrO 2 phase, which introduces oxygen vacancies or defective sites that enhance CO 2 activation and methanol production 32 . Previous studies, such as those by Javier et al., suggest that incorporating In 2 O 3 into ZrO 2 induces the formation of a polymorphic ZrO 2 structure, which significantly improves CO 2 adsorption on the catalyst surface 32 . Catalytic tests on bare In 2 O 3 and ZrO 2 revealed that ZrO 2 mainly produced CO with a low CO 2 conversion (0.09%), while In 2 O 3 showed slightly higher activity with 0.9% CO 2 conversion, producing methanol. The performance of the Deg In-Zr (3:8) catalyst was further compared with that of In 2 O 3 -impregnated ZrO 2 (In 2 O 3 -ZrO 2 ) and In 2 O 3 -ZrO 2 /C (impregnated on graphite). These conventional catalysts achieved CO 2 conversion rates of 3.2% and 4.6%, respectively, but were still far less active than Deg In-Zr (3:8), which achieved a 27.8% CO 2 conversion after 51 hours at 220°C and 40 bar pressure. Catalytic activity was also assessed with varying indium content in the MOF-derived catalysts. Figure 4 (b) and (e) show that increasing indium content initially enhanced activity, but beyond a certain threshold, the catalytic performance declined. This is likely due to an optimal balance of In 2 O 3 and ZrO 2 , both of which serve as active sites for CO 2 hydrogenation to methanol 32 , 34 . The time-on-stream profile (Fig. 4 (f) and S13 (a)) indicates that the Deg In-Zr (3:8) catalyst had an induction period of 24 hours, during which methanol selectivity reached 81%, with a productivity of 2.61 g MeOH ·g cat −1 ·h − 1 . Methanol selectivity stabilized at 81.4%, with by-products including formic acid (10.3%) and CO (1.6%). The small amount of CO is likely due to the reverse water-gas shift (RWGS) reaction, which typically requires higher activation energy and occurs at temperatures above 280°C 7 . After 51 hours, the methanol production remained stable at 2.64 g MeOH ·g cat −1 ·h − 1 . Initially, formic acid was a major by-product, but as the reaction progressed, its selectivity decreased while methanol selectivity increased. CO 2 and H 2 are adsorbed onto the catalyst surface, forming surface-bound formate 41 (HCOO − ), which is then reduced to methanol through intermediates like H 2 CO* and H 3 CO* 42 . The oxygen vacancies in the In 2 O 3 species assist in this process by facilitating CO 2 adsorption and activation. As temperature increased, methanol selectivity improved, but ethanol formation began at temperatures above 230°C. The time-on-stream profile for different temperatures is shown in Fig. S13 (b) and (c), where CO selectivity increased with temperature due to the RWGS reaction 33 . For liquid-phase CO 2 hydrogenation, the Deg In-Zr (3:8) catalyst was tested in a high-pressure Parr reactor. The catalyst was highly active in converting CO 2 to methanol, with reaction parameters such as temperature, pressure, and reaction time studied (Fig. 4 (g)-(i)). Before the reaction, the catalyst was reduced at 300°C under 4% H 2 in Ar for 2 hours. As per Fig. 4 (h), at 130°C and 30 bar pressure (3:1 H 2 : CO 2 ratio), the highest methanol selectivity (96.8%) was achieved. Increasing the temperature to 190°C enhanced CO 2 conversion to 35.3%, but ethanol and propanol started to form at higher temperatures, likely due to methanol chain growth via C-C coupling 43 . The effect of pressure on CO 2 conversion and methanol selectivity was also evaluated, with pressure ranging from 20 to 70 bar (Fig. 4 (g)). As pressure increased, CO 2 conversion increased from 23.6–32.2%, but methanol selectivity decreased above 30 bar, leading to the formation of ethanol and propanol. Propanol selectivity reached 15.5% at 70 bar, with ethanol selectivity at 2.3%. The time-on-stream profile in liquid phase over 72h (Fig. S16) revealed that methanol selectivity peaked at 96.8% after 5 hours of reaction, with 26.6% CO 2 conversion. Over extended reaction times, butanol selectivity increased, reaching 25.5% after 72 hours, likely due to C-C coupling reactions 43 . This phenomenon aligns with findings from Wang et al., who observed ethanol formation via C-C coupling over Co catalysts after extended reaction times. The reusability (Fig. 4 (i)) of the Deg In-Zr (3:8) catalyst was tested over five cycles at 130°C, 30 bar total pressure, and 5 hours reaction time. The CO 2 conversion showed only a slight decline from 26.6–25.8%, and methanol selectivity remained high (96.8–95.1%). ICP-MS analysis indicated minimal loss of active metals (In and Zr), confirming the catalyst’s stability in the liquid-phase reaction medium. Characterization of the reused catalyst, including XRD, XPS, and TEM (Fig. S19), confirms that the catalyst maintains its structural integrity after five catalytic cycles. XPS analysis of In and Zr in the reused catalyst reveals oxidation states of + 3 and + 4, respectively, consistent with those observed in the fresh catalyst. Structure performance relationship establishment via in situ AP XPS and Kinetic Study In situ XPS analysis was conducted on various catalysts under different temperatures and hydrogen pressure conditions, as shown in Fig. 5 . The O 1s high-resolution XPS spectra were deconvoluted into three peaks at 529.6 eV, 531.7 eV, and 533.3 eV, corresponding to lattice oxygen, oxygen vacancies, and –OH groups, respectively 44 . As the hydrogen and CO 2 pressure increased from 10 mTorr to 30 mTorr, the number of oxygen vacancies also increased (Fig. 5 (a)). This trend was similarly observed with rising temperature (Fig. 5 (b)), indicating that higher temperatures and pressures promote the generation of oxygen vacancies, which in turn create more active sites for CO 2 adsorption on the catalyst surface 45 . Figure 5 (c) and (d) show a shift in the indium binding energy to higher values under increased pressure and temperature. Conversely, the binding energy of Zr shifted to lower values under the same conditions (Fig. 5 (e) and (f)), suggesting a charge transfer between In and Zr that may lead to the formation of In-Zr bimetallic sites 46 , 47 . The C 1s XPS spectra were deconvoluted into three peaks at 284.3 eV, 285.5 eV, and 288.6 eV, corresponding to C–C, C–O–C, and O–C = O bonds, respectively 48 . A kinetic study was performed using the Deg In-Zr (3:8) catalyst and compared with conventional In 2 O 3 -ZrO 2 and In 2 O 3 -ZrO 2 /C catalysts (Fig. S15(a)-(c)). The activation energy for CO 2 conversion to methanol and the reverse water-gas shift (RWGS) reaction was determined using the Arrhenius equation, plotting the inverse of temperature (1/T) against ln(ri), where ri represents the initial rate constant. CO 2 conversion to methanol was conducted at four different temperatures: 210°C, 220°C, 230°C, and 240°C. Among the catalysts, Deg In-Zr (3:8) exhibited the lowest activation energy (46.2 ± 5 kJ mol⁻¹) for methanol production, significantly lower than the reported activation energy for In 2 O 3 -ZrO 2 catalysts by Frei et al. The activation energy for the RWGS reaction over Deg In-Zr (3:8) was higher, at 98.6 ± 4 kJ mol⁻¹ 32 . Due to its low activation energy barrier for methanol production, Deg In-Zr (3:8) demonstrated superior catalytic activity for CO 2 conversion to methanol. Further details of the structure and activity relationship provided in supporting information (page 22). In situ DRIFT for gas phase and in situ ATR-IR for liquid phase To investigate the reaction mechanism and identify intermediate species in the gas-phase conversion of CO 2 to methanol, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) was conducted on Deg In-Zr (3:8), Deg In-Zr (1:4), and In-Zr BDC catalysts at 220°C and 10 bar with a 25% CO 2 and 75% H 2 feed. At the start of the reaction (Fig. S18), a CO 2 peak at 2350 cm⁻¹ was detected for all catalysts 49 . After 10 minutes, small peaks at 2121 cm⁻¹ (CO) and 1498 cm⁻¹ (monodentate carbonate, CO 3 -2 ) appeared 42 . The formate species (HCOO*) became prominent after 25 minutes over the Deg In-Zr (3:8) catalyst (Fig. S18 (b)), with peaks at 1576 cm⁻¹ (asymmetric OCO stretching) and 1372 cm⁻¹ (symmetric OCO stretching) 50 . Additionally, the bending vibration of CH in HCOO* was detected at 1386 cm⁻¹ after 20 minutes 51 . Peaks corresponding to H 3 CO* species (2830, 2894, and 1040 cm⁻¹) 52 appeared after 30 minutes, with the formate intensity peaking at 35 minutes and declining after 50 minutes, while H 3 CO* intensity increased over time, reaching its maximum after 140 minutes. The decrease in the CO 2 peak at 2350 cm⁻¹ confirmed CO 2 adsorption and conversion into HCOO*, which is subsequently reduced to H 3 CO* and eventually forms CH 3 OH. These findings are consistent with previous studies on In-Zr-based catalysts 42 . DRIFT analysis was also performed on Deg In-Zr (1:4), which showed the appearance of HCOO* peaks after 35 minutes, though no H 3 CO* species were detected, indicating lower activity compared to Deg In-Zr (3:8). For the indium-impregnated ZrBDC catalyst (In-Zr BDC), the formate peak at 1576 cm⁻¹ was weak, confirming its much lower activity (Fig. S18 (a) and (c)). In situ ATR-IR spectroscopy was conducted to further investigate the CO 2 hydrogenation mechanism over Zr-BDC, In-Zr BDC, and Deg In-Zr (3:8) catalysts (Fig. 6 (b), (d) and (f)) within a 0-180 minute time frame. At the start, a doublet for adsorbed CO 2 at 2350 cm⁻¹ was observed for all catalysts 53 , 54 . Over the Deg In-Zr (3:8) catalyst (Fig. 6 (f)), a peak at 1500 cm⁻¹ appeared after 10 minutes, corresponding to surface-bound zirconium bidentate carbonate, consistent with CO 2 reduction studies by Katayama et al 55 . As the reaction progressed, a new peak at 1620 cm⁻¹, associated with adsorbed formate (HCOO ad ), emerged at 20 minutes. CO 2 and H 2 were adsorbed onto the catalyst surface, where oxygen vacancies and active H species likely combined with adsorbed CO 2 to form formate 42 . By 30 minutes, the formate peak intensified 56 , and a peak at 1298 cm⁻¹ (symmetric C = O stretching in bidentate HCOO ad ) appeared 53 . After 40 minutes, a small peak at 1396 cm⁻¹ for OCH 3 adsorbed species (OCH 3ad ) was detected 55 , indicating the hydrogenation of HCOO ad to OCH 3ad , following the reaction pathway CO 2ad → HCOO ad → H 2 CO ad → OCH 3ad , as supported by both DFT calculations and experimental evidence 41 . The OCH 3ad peak increased in intensity over time, reaching its maximum at 180 minutes, while the formate peak steadily declined, confirming its conversion to OCH 3ad and eventually methanol. Additionally, the CO 2 peak at 2350 cm⁻¹ decreased significantly, indicating CO 2 reduction to CH 3 OH. No CO peak was observed, suggesting the absence of the reverse water-gas shift (RWGS) reaction, which typically occurs at higher temperatures 57 . In contrast, the other two catalysts, Zr-BDC (bare MOF) (Fig. 6 (b)) and In-Zr BDC (indium-impregnated Zr MOF) (Fig. 6 (d)), showed no significant peaks except for CO 2 , indicating that they were inactive for CO 2 hydrogenation to methanol during the 0–180-minute reaction window. DFT calculations Building on our previous computational studies on the catalytic activity of metal-organic frameworks (MOFs) for CO 2 conversion 58 – 60 , this work focuses on the support effect of degraded In-Zr MOF (Deg In-Zr) as a catalyst for methanol production. Quantum chemistry calculations were performed to investigate the mechanisms behind the enhanced catalytic performance of the degraded In-Zr MOF, specifically analyzing the role of indium impregnation. Prior research has established that methanol formation follows the formate pathway, where CO 2 binds at oxygen, indium, and zirconium active sites on the catalyst surface 13 , 61 – 64 . Mechanistically, the formation of formate (HCOO) is facilitated when both H 2 and CO 2 absorb energy to form stable intermediates. After degradation, the creation of oxygen vacancies significantly lowers the energy barrier for formate production, stabilizing the HCOO intermediate. In this context, we designed structural models to study the adsorption of CO 2 and H 2 over two different catalyst surfaces—before and after degradation—encompassing Deg In-Zr (degraded MOF with two oxygen vacancy configurations) and In-Zr BDC (containing active indium and zirconium sites within a MOF structure). The Deg In-Zr and In-Zr BDC surface models were based on previously reported structures of In-doped ZrO 2 and indium-impregnated MOFs 11 , 65 , 66 . We optimized the geometries of the catalyst models before and after degradation using density functional theory (DFT) methods, with the optimized atomic coordinates provided in Table S1 67 . To explore the electronic properties and key intramolecular interactions between reactants (CO 2 and H 2 ) and the active sites of these catalyst models, we performed quantum theory of atoms in molecules (QTAIM) calculations 68 on the optimized structures. The QTAIM molecular graphs, including bond critical points (BCPs), ring critical points (RCPs), and bond paths, are presented in Fig. 7 , and the corresponding QTAIM indicators are listed in Table S2. The QTAIM analysis revealed that oxygen vacancies in the degraded catalysts significantly enhance the interaction between the reactants and the active sites, compared to the non-degraded models. This is evident from the formation of In-H BCPs with electron density values around 0.1 in Deg In 2 O 3 -OV1 and Deg In 2 O 3 -OV2, which indicates the interaction of H 2 with indium active sites. In contrast, no such interactions were observed in the non-degraded models. Additionally, the interaction between CO 2 and indium active sites was stronger than with zirconium sites, as shown by the electron density values in the BCPs of O(CO 2 )-In, O(CO 2 )-Zr, and C(CO 2 )-O(catalyst). Furthermore, in the degraded catalyst models (Deg In 2 O 3 -OV1 and Deg In 2 O 3 -OV2), H-H bond dissociation occurred, facilitating C-H bond formation and leading to formic acid production in subsequent reaction steps. This suggests that the presence of oxygen vacancies plays a critical role in promoting the catalytic conversion of CO 2 to methanol. Plausible reaction mechanism and structure and performance relationship Initially, H 2 undergoes heterolytic cleavage on the defective surface of indium oxide, marking the first step in hydrogenating chemisorbed CO 2 at oxygen vacancies (Fig. 6 (a)) 69 , 70 . A plausible pathway for methanol synthesis on the In 2 O 3 (111) surface follows the sequence: *HCOO → H 2 COO* → H 3 CO*. In this study, in situ DRIFTS under realistic conditions reveals that *HCOO is the dominant surface intermediate in the CO 2 hydrogenation process to methanol, consistent with previous reports 51 , 70 . While formate species were previously suggested as bystanders on Cu-based catalysts 71 , in situ DRIFTS confirms the active involvement of *HCOO as a reaction intermediate for the In-Zr catalysts. Increasing indium content enhances H 2 splitting and promotes the formation of *HCOO, as demonstrated by the generation of *HCOO on Deg In-Zr (3:8), Deg In-Zr (1:8), and Deg In-Zr (3:2) catalysts. Indium sites are also likely crucial for the formation of *H 3 CO species 72 . CH 3 OH TPD analysis shows that catalysts with higher indium content exhibit a stronger affinity between the catalyst surface and CH 3 OH. Additionally, HCOOH TPD analysis indicates that bulk In 2 O 3 has a stronger interaction with HCOOH than other catalysts, suggesting that the conversion of HCOOH to CH 3 O* depends on optimal interaction with the catalyst surface, where the correct indium amount is critical for achieving high CH 3 OH selectivity. However, when indium content is too high, the interaction with HCOOH becomes too stable, potentially inhibiting its conversion to CH 3 O*. The well-dispersed In 2 O 3 on ZrO 2 forms a complex interface with the ZrO 2 support. At these interfacial sites, In 2 O 3 dissociates gaseous H 2 into reactive hydrogen atoms, which then interact with adsorbed CO 2 to generate bidentate *HCOO. This intermediate is more likely to undergo hydrogenation, given a delicate balance between the adsorption strengths of *HCOO and *H 3 CO. Meanwhile, the reduced interaction of *HCOO with ZrO 2 inhibits CO formation, as it struggles to bind effectively to the ZrO 2 surface. To clarify the reaction mechanism, HCOOH decomposition was tested over various catalysts in the presence of CO 2 and H 2 . ZrO 2 alone primarily produced CO, while Deg In-Zr catalysts generated CO, CO 2 , and H 2 during steady-state HCOOH decomposition, indicating that ZrO 2 plays a crucial role in CO formation during the catalytic conversion of CO 2 to methanol. Discussion Crystal engineering of MOFs combined with pyrolysis techniques has been used to synthesize ultrafine In 2 O 3 nanoparticles embedded in a ZrO 2 matrix, forming an oxygen vacancy-incorporated heterojunction between the In 2 O 3 and ZrO 2 phases. This catalyst, obtained by pyrolyzing indium-impregnated Zr-BDC MOF with a low indium content of 0.2 wt.%, has been thoroughly characterized using EXAFS, XANES, and HR-TEM, confirming the creation of In 2 O 3 and ZrO 2 heterostructures. XPS analysis further revealed the presence of oxygen vacancies on the catalyst surface, which likely contributes to its exceptional catalytic performance in both liquid and gas-phase CO 2 hydrogenation to methanol. The active site for methanol synthesis is believed to be the interface between ZrO 2 and defective In 2 O 3 , with reaction mechanisms involving the formate pathway. Oxygen vacancies play a key role in activating CO 2 and enhancing methanol stability on the catalyst surface. The catalyst demonstrates remarkable stability in both liquid and gas phase reactions, highlighting its robust performance. In situ DRIFT spectroscopy (gas phase) and in situ ATR-IR spectroscopy (liquid phase) confirmed that methanol synthesis predominantly follows the formate pathway. CH 3 OH TPD and HCOOH TPD experiments showed that an optimal indium content enhances CH 3 OH selectivity. A higher concentration of indium stabilizes formate species on the catalyst surface, reducing their conversion to CH 3 O* species. Conversely, higher ZrO 2 concentrations promote formate decomposition into CO and H 2 O. These TPD studies revealed the active surface species driving the reaction. In situ XPS further explored the relationship between the catalyst’s surface structure and its catalytic performance. The study confirmed that the abundance of oxygen vacancies and electronic modulation between In 2 O 3 and ZrO 2 are key factors driving the high catalytic activity. Previous work by Kumari et al. also highlighted that oxygen vacancies play a critical role in CO 2 activation by lowering the reaction barriers for CO 2 dissociation. DFT calculations in this study reinforced these findings 73 . This research presents a systematic atomic-level approach for designing multi-metal catalysts with enhanced active sites for CO 2 hydrogenation to methanol. The method of optimizing indium content and controlling oxygen vacancies can be applied to other catalytic systems, providing a cost-effective and efficient route to catalyst synthesis, with indium loading as low as 0.2 wt.%. This approach offers significant potential for industrial-scale methanol production through CO 2 hydrogenation. Future work will involve operando EXAFS studies to monitor structural changes in the catalyst during reactions in real time. These studies will provide deeper insights into the reaction mechanism, helping to develop even more effective catalysts for CO 2 hydrogenation. Methods Chemicals ZrCl 4 , benzene dicarboxylic acid, Indium (III) nitrate hydrate (In(NO 3 ) 3 · xH 2 O), N,N-Dimethylformamide, methanol and ZrO 2 are purchased from Sigma Aldrich. Catalyst preparation : Zr BDC MOF has been prepared by following literature reported method by involving the dissolution of ZrCl 4 (0.053 g, 0.227 mmol) and 1,4-benzene dicarboxylic acid (H 2 BDC) (0.034 g, 0.227 mmol) in N, N'-dimethylformamide (DMF) (24.9 g, 340 mmol) at room temperature 23 . The mixture was then heated in an oven at 120°C for 24 hours, allowing crystallization to occur under static conditions. After cooling to room temperature in air, the solid product was filtered, washed multiple times with DMF and methanol, and dried in an oven at 60°C overnight (14 hours). Indium was impregnated into the Zr-BDC MOF using the incipient wetness impregnation (IWI) technique to synthesize the In-Zr BDC catalyst. Various indium-to-zirconium molar ratios (3:2, 3:4, 3:8, 1:2, 1:4, and 1:8) were applied to produce the indium-impregnated Zr BDC MOF. The corresponding amount of indium nitrate was added to 1 g of Zr BDC MOF in a methanol solution. The resulting solution was then refluxed at 70°C for 24 hours. Following this, the solution was centrifuged, and the solid (In-Zr BDC) was dried in an oven at 60°C overnight. All of the In-Zr BDC was thermally treated in a 600 ℃ tubular furnace under an N 2 atmosphere for 4h at a 2 ℃/min heating rate. This is denoted as Deg In-Zr. Catalyst characterization: All the detailed catalyst characterizations are depicted in Supplementary Information. DFT calculations: The details of the DFT calculations are shown in the Supplementary Information. Catalyst evaluation (Gas Phase & Liquid Phase): The catalytic activity was assessed in a fixed-bed reactor that was 300 mm long and 7 mm in diameter, constructed from stainless steel. The bed comprised 0.4 g of catalyst (with a mesh size distribution of 20–40) and 2 g of quartz particles, arranged between two layers of silica wool. Initially, the reactor pressure was raised to 3.0 MPa with N 2 flow, and the temperature was increased to 300°C. Subsequently, the catalyst was reduced and activated using a stream of diluted hydrogen (10 vol % H 2 /N 2 ) at 350°C for 1 hour. The catalytic activity for methanol synthesis was evaluated under the following conditions: H 2 /CO 2 = 3 and a flow rate of 10 mL/min (30 bar pressure). At the outlet of the reactor, the gases were depressurized to atmospheric pressure, and the reaction products were analyzed using an online gas chromatograph (GC, Agilent 7890A) equipped with two detectors. A flame ionization detector, along with an HP-FFAP column and H 2 as the carrier gas, was used to detect CO, CH 4 , and CH 3 OH. A thermal conductivity detector equipped with MS-5A and Hayesep Q columns, utilizing He as the carrier gas, was used to identify other gaseous products (including H 2 , CO 2 , N 2 , and CO). The carbon balance was found to exceed 95% in all experiments. The calculations for CO 2 conversion, selectivity of C-containing products, and product yield were carried out as follows CO 2 Conversion (%) = \(\:(\frac{{F}_{{CO}_{2\:IN}}-{F}_{{CO}_{2\:OUT}}}{{F}_{{CO}_{2\:IN}}}\) ) \(\:\times\:100\) Selectivity (%) = \(\:\left(\frac{N\%}{\sum\:\left(\left(N\%\right)\right)}\right)\times\:100\) $$\:\text{Y}\text{i}\text{e}\text{l}\text{d}\:\left(\text{%}\right)\hspace{0.17em}=\hspace{0.17em}\text{s}\text{e}\text{l}\text{e}\text{c}\text{t}\text{i}\text{v}\text{i}\text{t}\text{y}\:\times\:\:\text{c}\text{o}\text{n}\text{v}\text{e}\text{r}\text{s}\text{i}\text{o}\text{n}\:\times\:100$$ Here, N denotes the carbon-containing species in the products, which include CO, CH 4 , and CH 3 OH. The results were obtained once the reaction reached a steady state. All the reactions of CO 2 hydrogenation were performed in a 250 ml stainless steel Parr autoclave inbuilt with a pressure gauge setup. 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Electro-Communications","correspondingAuthor":false,"prefix":"","firstName":"Hiroko","middleName":"","lastName":"Miwa","suffix":""},{"id":428270349,"identity":"26baf45c-aa2a-4cb4-b411-75fd134030f0","order_by":5,"name":"Tomoya Uruga","email":"","orcid":"","institution":"Japan Synchrotron Radiation Research Institute","correspondingAuthor":false,"prefix":"","firstName":"Tomoya","middleName":"","lastName":"Uruga","suffix":""},{"id":428270350,"identity":"605640b7-68dd-4aab-8f9d-29ee9b27f342","order_by":6,"name":"Tayebeh Hosseinnejad","email":"","orcid":"","institution":"RMIT University","correspondingAuthor":false,"prefix":"","firstName":"Tayebeh","middleName":"","lastName":"Hosseinnejad","suffix":""},{"id":428270351,"identity":"4971b057-c239-44fe-be7e-16df17c95517","order_by":7,"name":"Selvakannan Periasamy","email":"","orcid":"","institution":"RMIT","correspondingAuthor":false,"prefix":"","firstName":"Selvakannan","middleName":"","lastName":"Periasamy","suffix":""},{"id":428270352,"identity":"8606de66-3f1b-4bca-8195-c7aa9869d06e","order_by":8,"name":"Deshetti Jampaiah","email":"","orcid":"","institution":"RMIT University","correspondingAuthor":false,"prefix":"","firstName":"Deshetti","middleName":"","lastName":"Jampaiah","suffix":""},{"id":428270353,"identity":"c4facd26-0483-4024-b869-9faa16aa5c77","order_by":9,"name":"Ravindra Gudi","email":"","orcid":"","institution":"Indian Institute of Technology Bombay","correspondingAuthor":false,"prefix":"","firstName":"Ravindra","middleName":"","lastName":"Gudi","suffix":""},{"id":428270354,"identity":"911fcc99-7185-4213-a80f-14815ff76fe1","order_by":10,"name":"Yasuhiro Iwasawa","email":"","orcid":"https://orcid.org/0000-0002-5222-5418","institution":"University of Electro-Communications","correspondingAuthor":false,"prefix":"","firstName":"Yasuhiro","middleName":"","lastName":"Iwasawa","suffix":""}],"badges":[],"createdAt":"2025-03-03 06:55:32","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6143390/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6143390/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-025-63932-y","type":"published","date":"2025-10-07T04:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":78727769,"identity":"b63f59db-6fc1-4a96-8ba2-75869f1d7435","added_by":"auto","created_at":"2025-03-18 06:43:28","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":497681,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eStructural Characterization of the catalysts.\u003c/strong\u003e (a) catalyst synthesis scheme, (b) XRD of different catalysts, (c) Raman spectra of various catalysts, (d) In XPS, (e) Zr XPS and (f) O XPS of different catalysts\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/11e266129668ec2775472c89.jpeg"},{"id":78728116,"identity":"2cba78c7-ff3e-46d4-84d9-7cd161c9c123","added_by":"auto","created_at":"2025-03-18 06:51:28","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":413374,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eEXAFS of various catalysts.\u003c/strong\u003e Curve fitting results of the k\u003csup\u003e3\u003c/sup\u003e-weighted EXAFS data at Zr K-edge for Fourier transform (a) Zr foil (b) ZrO\u003csub\u003e2\u003c/sub\u003e (c) Zr BDC MOF (d) Deg In-Zr MOF (Deg In-Zr (3:8) ) (e) In-Zr MOF and (f) In-ZrO\u003csub\u003e2\u003c/sub\u003e (impregnated indium in ZrO\u003csub\u003e2\u003c/sub\u003e) Red circles: observed; Red solid line: fitted; Blue circles: imaginary part; Blue solid line: fitted. (g) XANES of Zr K-edge (h) WT of Deg In-Zr (3:8) and (i) In-Zr BDC\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/89ced58ac88127a83d066482.jpeg"},{"id":78728801,"identity":"0b3b63b5-3881-463a-a8a9-7b179ff578e7","added_by":"auto","created_at":"2025-03-18 06:59:28","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1460429,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eMorphological characterization of the catalysts.\u003c/strong\u003e(a)-(c) HR-TEM of Deg In-Zr (3:8) and (d)-(h) HADDF-STEM images and corresponding elemental mapping of Deg In-Zr (3:8)\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/6a857d400af7bf329a44f380.png"},{"id":78728118,"identity":"1dc7fba3-78df-4f8d-ba93-690bf09ce3d7","added_by":"auto","created_at":"2025-03-18 06:51:28","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":532400,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCatalytic activity gas and liquid phases.\u003c/strong\u003e (a)-(f) gas phase reaction and (g)-(i) liquid phase reaction.\u003c/p\u003e","description":"","filename":"floatimage4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/63b887dcc07ff73ceef9dfb7.jpeg"},{"id":78727775,"identity":"0e8a79d5-30fe-480a-aed5-8d294ad6feb4","added_by":"auto","created_at":"2025-03-18 06:43:28","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":514932,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003eIn situ\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e Ambient Pressure XPS.\u003c/strong\u003e(a)-(b) O 1s XPS, (c)-(d) In 3d XPS, (e)-(f) Zr 3d XPS and (g)-(h) C 1s\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/9624ecf0414d145a966c98a4.png"},{"id":78728123,"identity":"4f7ded3f-9e0b-4fe9-a511-f70eea3bc679","added_by":"auto","created_at":"2025-03-18 06:51:28","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":524679,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eReaction Mechanistic and \u003c/strong\u003e\u003cem\u003e\u003cstrong\u003ein situ\u003c/strong\u003e\u003c/em\u003e\u003cstrong\u003e ATR-IR in Liquid phase\u003c/strong\u003e. (a) Reaction mechanism over Deg In-Zr (3:8) catalyst, (b), (d) and (f) time dependent in situ ATR-IR of Zr-BDC, In-Zr BDC and Deg In-Zr (3:8) respectively; (c), (e) and (g) ATR-IR of the catalysts in different gaseous environment for Zr-BDC, In-Zr BDC and Deg In-Zr (3:8) respectively in liquid phase.\u003c/p\u003e","description":"","filename":"floatimage6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/2edc6c402acfe587910a98b6.jpeg"},{"id":78727777,"identity":"0901c39e-6d11-4e10-aa98-15020e8637a9","added_by":"auto","created_at":"2025-03-18 06:43:28","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":149890,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eDFT calculations.\u003c/strong\u003e QTAIM graphs of Deg In2O3-OV1, Deg In2O3-OV2, nonDeg In2O3-1, nonDeg In2O3-2, and nonDeg Zr BDC MOF catalyst models, obtained by the analysis of PBE0/6-31G* electron density functions. Bond Critical Points: Green circles; Ring Critical Points: Blue circles; Bond Paths: Gray solid and dashed lines.\u003c/p\u003e","description":"","filename":"floatimage72.png","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/4ce19caf0afafda7486445f0.png"},{"id":93009020,"identity":"1ca5db8b-55bb-4a3b-ba2a-8878b73c493a","added_by":"auto","created_at":"2025-10-08 07:06:06","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4933648,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6143390/v1/f805f584-e39c-4286-bdfe-a4b8ad0f7042.pdf"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Leveraging Metal Organic Framework Derived Indium/Zirconium Oxide for Unprecedented Catalytic Performance in CO₂ Hydrogenation to Methanol","fulltext":[{"header":"Introduction","content":"\u003cp\u003eRising CO\u003csub\u003e2\u003c/sub\u003e levels in the atmosphere have heightened concerns about global climate change and ocean acidification\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u003c/sup\u003e. Hydrogenating CO\u003csub\u003e2\u003c/sub\u003e into alcohol or hydrocarbons presents a key strategy for recycling atmospheric CO\u003csub\u003e2\u003c/sub\u003e emissions from combustion processes. With growing industrial demand for methanol, significant efforts have focused on converting CO\u003csub\u003e2\u003c/sub\u003e into methanol\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. Various materials have been tested as catalysts for this conversion, with most industrial processes relying on metal nanoparticles supported on oxide substrates. Cu-based catalysts, often combined with ZnO and/or Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, have been used for over 50 years\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. While these catalysts avoid methane production, they show limited activity for CO\u003csub\u003e2\u003c/sub\u003e hydrogenation at low temperatures (T \u0026lt; 500 K), leading to higher hydrogen consumption and reduced methanol yields\u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e. Additionally, the presence of water accelerates the sintering of Cu and ZnO, causing catalyst deactivation\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIndium-based catalysts have emerged as a promising solution for converting CO\u003csub\u003e2\u003c/sub\u003e into methanol\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e. In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e offers up to 100% selectivity for methanol under optimal CO\u003csub\u003e2\u003c/sub\u003e hydrogenation conditions, with exceptional stability due to its oxide-based active phase\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e. While unsupported In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e has seen improvements through the addition of active components or promoters to enhance H\u003csub\u003e2\u003c/sub\u003e dissociation, supported In-based catalysts are more suitable for industrial use, requiring less active material and providing greater stability\u003csup\u003e\u003cspan additionalcitationids=\"CR9 CR10\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e–\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u003c/sup\u003e. Recent research has focused on supported In-based catalysts, with monoclinic zirconia (m-ZrO\u003csub\u003e2\u003c/sub\u003e) proving to be excellent support, achieving high CO\u003csub\u003e2\u003c/sub\u003e conversion and methanol selectivity\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. In addition, Tsoukalou et al.\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e and Chen et al.\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e have concentrated on identifying the active phase of the In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/ZrO\u003csub\u003e2\u003c/sub\u003e catalyst used in the methanol synthesis from CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e. The In-Ov-Zr sites (Ov representing oxygen vacancies) formed by the interaction between In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e are crucial for maximizing activity and stability in methanol production. The effectiveness of CO\u003csub\u003e2\u003c/sub\u003e reduction to methanol is largely influenced by the size and concentration of In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e domains\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e. However, increasing the interfacial area between In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e domains and the m-ZrO\u003csub\u003e2\u003c/sub\u003e support remains a key challenge for further enhancing performance.\u003c/p\u003e \u003cp\u003eIncreasing the interfacial area and oxygen vacancies can be achieved through MOF-derived material synthesis. However, designing heterojunctions with abundant interfaces in complex systems remains challenging\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e. Certain MOFs and MOF composites serve as ideal precursors or templates for producing heterostructured transition metal/metal oxides through a straightforward hydrothermal-calcination method\u003csup\u003e\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e–\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e. These MOF-derived heterostructures typically retain the high porosity and versatile morphologies of MOFs, making them highly promising for catalytic applications\u003csup\u003e\u003cspan additionalcitationids=\"CR20\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e–\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e. For example, CoMn-MOF-74-derived Co/MnO heterostructured nanoparticles have shown improved CO\u003csub\u003e2\u003c/sub\u003e adsorption and activation, delivering excellent catalytic performance in low-temperature CO\u003csub\u003e2\u003c/sub\u003e methanation\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. Building on this success, we developed a ZrO\u003csub\u003e2\u003c/sub\u003e/In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-based heterostructural catalyst using MOF precursors, and we evaluated its efficiency for CO\u003csub\u003e2\u003c/sub\u003e hydrogenation to methanol.\u003c/p\u003e \u003cp\u003eIn this study, we developed a composite catalyst featuring a heterojunction of In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e (Deg In-Zr (3:8)), derived from an indium-impregnated Zr-BDC MOF. The Deg In-Zr (3:8) catalyst demonstrated outstanding performance in the selective hydrogenation of CO\u003csub\u003e2\u003c/sub\u003e to methanol in both liquid and gas phases under ambient conditions. To our knowledge, this catalyst achieved the highest reported CH₃OH productivity of 2.64 g\u003csub\u003eMeOH\u003c/sub\u003e·g\u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e.h\u003csup\u003e− 1\u003c/sup\u003e in the gas phase. Additionally, the catalyst contains a low indium content (0.6 wt.%), with 2–3 nm In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e nanoparticles uniformly dispersed on the surface, making it a cost-effective option for industrial use. The unique In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/ZrO\u003csub\u003e2\u003c/sub\u003e heterointerface provided numerous active sites for enhanced H\u003csub\u003e2\u003c/sub\u003e dissociation and CO\u003csub\u003e2\u003c/sub\u003e activation, confirmed through detailed structural analysis using XAS (XANES and EXAFS). The reaction mechanism responsible for this exceptional performance was investigated using in situ ATR-IR for liquid-phase reactions, in situ DRIFTS for gas-phase reactions, and quantum chemistry modeling. Furthermore, ambient pressure in situ XPS was conducted to gain insights into the active phase during CO\u003csub\u003e2\u003c/sub\u003e hydrogenation to methanol.\u003c/p\u003e\n\u003ch3\u003eSynthetic route\u003c/h3\u003e\n\u003cp\u003eThe Zr-BDC MOF was synthesized by dissolving ZrCl\u003csub\u003e4\u003c/sub\u003e (0.053 g, 0.227 mmol) and 1,4-benzene dicarboxylic acid (H\u003csub\u003e2\u003c/sub\u003eBDC) (0.034 g, 0.227 mmol) in N,N'-dimethylformamide (DMF) at room temperature\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e. The mixture was heated at 120°C for 24 hours to induce crystallization. After cooling, the solid was filtered, washed with DMF and methanol, and dried at 60°C overnight. X-ray diffraction (XRD) confirmed that the synthesized MOF matched the previously reported Zr-BDC structure\u003csup\u003e\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. Indium was incorporated into the MOF via the incipient wetness impregnation (IWI) method to produce the In-Zr BDC catalyst with various indium-to-zirconium ratios. The mixture was refluxed with indium nitrate in methanol at 70°C, centrifuged, and dried. The XRD pattern confirmed successful indium incorporation. All samples were calcined at 600°C in nitrogen, resulting in the Deg In-Zr catalyst. During calcination, solvent molecules were lost around 150°C, and the H\u003csub\u003e2\u003c/sub\u003eBDC ligand decomposed near 350°C. The Deg In-Zr BDC (3:8) catalyst, containing ZrO\u003csub\u003e2\u003c/sub\u003e and In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e phases, exhibited the highest CO\u003csub\u003e2\u003c/sub\u003e conversion to methanol, achieving high efficiency with minimal indium content.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eCrystalline phase and surface properties\u003c/h2\u003e \u003cp\u003eThe XRD patterns of various samples, including ZrO\u003csub\u003e2\u003c/sub\u003e, In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e/C, In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e, Zr-BDC MOF, indium-impregnated Zr-BDC (In-Zr BDC), and degraded In-Zr MOF (Deg In-Zr), are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb. The Zr-BDC MOF displayed sharp peaks, indicating high crystallinity, with a pattern matching previous reports\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e. After thermal degradation at 600°C, the MOF structure collapsed, altering the diffraction pattern and revealing the presence of In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e \u003csup\u003e7\u003c/sup\u003eand ZrO\u003csub\u003e2\u003c/sub\u003e phases with peak shifts as compared to bare In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e, suggesting crystal distortion and small crystal domain size. In contrast, the impregnated In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e and the as-synthesized graphitic carbon-supported In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e exhibit sharp crystalline peaks, indicating the presence of large crystalline phases. Moreover, the peaks corresponding to In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e remain unchanged relative to those of pure In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e. All degraded MOF catalysts with different In and Zr ratio exhibited similar diffraction patterns (Fig. \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). Raman spectra of Zr-BDC (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb) show characteristic shifts at 634 and 860 cm⁻¹ (C–H bond vibrations) and at 1140 and 1611 cm⁻¹ (C = C modes of the benzene ring). Peaks at 1434 and 1448 cm⁻¹ correspond to symmetric and asymmetric C–O\u003csub\u003e2\u003c/sub\u003e stretching\u003csup\u003e\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e,\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e. Indium impregnation retained the MOF's structural integrity. After degradation, the Deg In-Zr (3:8) catalyst showed D and G bands at 1316 cm⁻¹ and 1590 cm⁻¹, indicating graphitic carbon formation\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e. Further details are available in the supporting information (page number 19).\u003c/p\u003e \u003cp\u003eX-ray Photoelectron Spectroscopy (XPS) was performed to analyze the surface composition and oxidation states of the elements in various catalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e (d) to (f), Fig. S2 and S3). The high-resolution XPS spectra for indium (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e(d)) reveal distinct peaks corresponding to In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and In(OH)\u003csub\u003e3\u003c/sub\u003e for the as-synthesized metal oxides\u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. In comparison, the Deg In-Zr (3:8) catalyst shows the largest binding energy shift for In\u003csup\u003e3+\u003c/sup\u003e, suggesting a strong electronic interaction between In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e in this material\u003csup\u003e\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u003c/sup\u003e. This shift indicates significant electronic modulation, as further detailed in the supporting information. For ZrO\u003csub\u003e2\u003c/sub\u003e, (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e (e)) the Zr 3d\u003csub\u003e5/2\u003c/sub\u003e and 3d\u003csub\u003e3/2\u003c/sub\u003e peaks appear at 182.01 eV and 184.34 eV\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e, indicating the presence of Zr\u003csup\u003e4+\u003c/sup\u003e. In the Deg In-Zr (3:8) catalyst, these peaks shift to higher binding energies (182.42 eV and 184.40 eV), likely due to surface restructuring and enhanced electronic interaction between ZrO\u003csub\u003e2\u003c/sub\u003e and In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e30\u003c/sup\u003e. The oxygen 1s XPS spectra of the metal oxide catalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e(f)) show three peaks at 529.62 eV, 531.2 eV, and 532.7 eV, corresponding to lattice oxygen (O\u003csub\u003eL\u003c/sub\u003e), oxygen vacancies (O\u003csub\u003eV\u003c/sub\u003e), and chemically adsorbed oxygen or C–O bond-associated oxygen (O\u003csub\u003eC\u003c/sub\u003e), respectively\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e,\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. The Deg In-Zr (3:8) catalyst exhibits the highest oxygen vacancy concentration, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e(e) and Table S3, compared to other as-synthesized catalysts such as In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, ZrO\u003csub\u003e2\u003c/sub\u003e, In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e, and In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e/C. The higher concentration of oxygen vacancies likely contributes to its enhanced activity in CO\u003csub\u003e2\u003c/sub\u003e hydrogenation. A detailed discussion of the varying indium and zirconium ratios in the degraded catalyst is provided in the supporting information (Fig. S3) (page number 21).\u003c/p\u003e \u003cp\u003eTo gain precise quantitative insights into electronic behavior and coordination environments, X-ray Absorption Spectroscopy (XAS) was employed (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, S5 \u0026amp; S6). The X-ray Absorption Near Edge Structure (XANES) at the In K-edge provided information on the valence state of the absorbing atom, though the low indium density across samples made analysis challenging. All samples showed significant deviations from metallic Zr (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eg). In the In-Zr Metal-Organic Frameworks (MOFs), a minor electron transfer from indium to the Zr MOF was observed, with minimal impact on the structural integrity of the Zr framework. However, in the degraded In-Zr MOFs (Deg In-Zr (3:8)), the Zr MOF decomposed into ZrO\u003csub\u003e2\u003c/sub\u003e, displaying differences from monoclinic ZrO\u003csub\u003e2\u003c/sub\u003e and similarities with In-modified ZrO\u003csub\u003e2\u003c/sub\u003e in impregnated In-ZrO\u003csub\u003e2\u003c/sub\u003e samples\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eWe also analyzed the extended X-ray absorption fine structure (EXAFS) spectra at Zr K-edge to investigate the local structure around Zr atoms in the samples. At the Zr K-edge of the Zr MOF, two types of Zr-O bonds and a Zr-Zr bond were detected, indicative of the inherent structure of the Zr MOF (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec). However, the Zr-Zr coordination number was lower than expected, suggesting distortions around Zr atoms within the MOF framework, reducing the coordination number as estimated by EXAFS.\u003c/p\u003e \u003cp\u003eEXAFS analysis at the In K-edge for the In-Zr MOF was anticipated, but insufficient signals were obtained, suggesting either lower-than-expected In density (as estimated by ICP) or a distorted and heterogeneous local structure around In atoms, complicating precise EXAFS measurements. Nonetheless, the Zr-Zr coordination number was lower in the In-Zr MOF, indicating increased distortion around Zr atoms due to the incorporation of In into the framework pores. The EXAFS Fourier transform showed a peak at approximately 0.3 nm, shorter than that in Zr MOFs, and the presence of Zr-In bonds improved the fitting analysis. Direct Zr-In bonding at 0.299 nm ± 0.003 was observed, suggesting the formation of Zr-O-In bonds at the interface of the MOF pore walls (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ee and i)\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eAt the Zr K-edge, EXAFS analysis of monoclinic ZrO\u003csub\u003e2\u003c/sub\u003e samples revealed Zr-O bonds at 0.215 nm and Zr-Zr bonds at 0.350 nm (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb). In the degraded In-Zr MOF (Deg In-Zr (3:8)), the presence of indium affected the structural parameters (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed and h), showing two distinct Zr-O bonds at 0.214 nm and 0.233 nm, compared to the single Zr-O bond at 0.215 nm in ZrO\u003csub\u003e2\u003c/sub\u003e. Zr-Zr bonding in the degraded In-Zr MOF was observed at 0.362 nm, compared to 0.350 nm in ZrO\u003csub\u003e2\u003c/sub\u003e, while Zr-In bonding at 0.299 nm was also noted, similar to that in the as-synthesized In-Zr MOF. However, the coordination number of Zr-In bonds was low, as detailed in the table below. The R-factor for fitting involving Zr-In bonds (3.5%) was superior to that for Zr-Zr bonds alone (4.6%). Therefore, the ZrO\u003csub\u003e2\u003c/sub\u003e formed from the degradation of In-Zr MOF at 600°C exhibited a different lattice structure compared to ZrO\u003csub\u003e2\u003c/sub\u003e, likely due to the formation of a new mixed In-Zr oxide with Zr-O-In bonds. This mixed oxide likely contains numerous oxygen defects due to the differing valences of Zr\u003csup\u003e4+\u003c/sup\u003e and In\u003csup\u003e3 + 34\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eCO\u003csub\u003e2\u003c/sub\u003e-TPD was performed to assess the CO\u003csub\u003e2\u003c/sub\u003e adsorption behavior of various catalysts. In the CO\u003csub\u003e2\u003c/sub\u003e-TPD profiles (Fig. S9), all catalysts showed a desorption peak between 50–200°C, attributed to bicarbonate formation via physical CO\u003csub\u003e2\u003c/sub\u003e adsorption on surface hydroxyl groups\u003csup\u003e\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e. A second peak, above 200°C, indicated CO\u003csub\u003e2\u003c/sub\u003e chemisorption at oxygen vacancies, critical for CO\u003csub\u003e2\u003c/sub\u003e activation\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e. The Deg In-Zr (3:8) catalyst showed a higher CO\u003csub\u003e2\u003c/sub\u003e chemisorption intensity between 200–450°C compared to bare In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e, suggesting that the heterointerfaces between In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e, along with oxygen vacancies, act as key sites for CO\u003csub\u003e2\u003c/sub\u003e adsorption and activation\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e.HCOOH and CH\u003csub\u003e3\u003c/sub\u003eOH temperature-programmed desorption (TPD) experiments were conducted to examine the surface species responsible for high methanol yield during CO\u003csub\u003e2\u003c/sub\u003e hydrogenation (Fig. S7 (c) and (b)). In the Deg In-Zr catalyst, the HCOOH decomposition peak appeared at lower temperatures, indicating reduced stability with increased indium content, leading to its decomposition into CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e. This suggests that optimizing indium content is key to effectively converting HCOO* intermediates into CH\u003csub\u003e3\u003c/sub\u003eO* species. Similar results by Han et al. showed that lower indium loadings stabilized HCOO species\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e. The CH\u003csub\u003e3\u003c/sub\u003eOH TPD profile revealed that methanol stability decreases with higher indium content, highlighting the importance of reducing indium concentration to improve methanol selectivity in CO\u003csub\u003e2\u003c/sub\u003e hydrogenation. The H\u003csub\u003e2\u003c/sub\u003e-TPR analysis also suggested the formation of the highest amount of oxygen vacancies in the Deg In-Zr (3:8) catalyst which is explained in supporting information (page number 20 and Fig. S8).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eMorphological and textural properties of the catalysts\u003c/h3\u003e\n\u003cp\u003eThe morphology of the materials was analyzed using TEM and HRTEM. TEM images of Zr-BDC (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) reveal a square-like morphology, which is also maintained in the Deg In-Zr (3:8) catalyst, featuring ultrasmall metal oxide nanoparticles ranging from 2 to 3 nm. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e, this catalyst contains both In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e nanoparticles. The d-spacing of 0.417 nm, observed in In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, is slightly larger than the standard 0.413 nm for the In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (211)\u003csup\u003e\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e lattice plane, likely due to crystal lattice distortion, as supported by XRD data\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. For ZrO\u003csub\u003e2\u003c/sub\u003e, the HR-TEM images display d-spacing values of 0.497 nm and 0.269 nm, corresponding to the (001) and (200) lattice planes of the monoclinic phase, respectively\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e. This increased d-spacing in the Deg In-Zr (3:8) catalyst compared to bare ZrO\u003csub\u003e2\u003c/sub\u003e indicates crystal distortion. Notably, no tetragonal ZrO\u003csub\u003e2\u003c/sub\u003e phase was observed in the HR-TEM analysis. Previous research by Muller et al. highlighted the high activity of monoclinic ZrO\u003csub\u003e2\u003c/sub\u003e in CO\u003csub\u003e2\u003c/sub\u003e hydrogenation to methanol, a finding supported by the absence of the tetragonal form in EXAFS analysis\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. The SEAD pattern also confirms the presence of both In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e, with a diffusive pattern attributed to the ultrasmall nanoparticles in the Deg In-Zr (3:8) catalyst\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e. STEM images (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e(d)-(h)) and EDX spectra (Fig. S12) further demonstrate the uniform dispersion of indium and zirconium within the carbonated MOF matrix.\u003c/p\u003e\n\u003ch3\u003eCatalytic activity and stability\u003c/h3\u003e\n\u003cp\u003eCO\u003csub\u003e2\u003c/sub\u003e catalytic conversion in the gas phase was conducted at 220°C with a feed mixture of (1:3) CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e, total pressure is 30 bar over various catalysts. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(a) and (b), the Deg In-Zr BDC (3:8) catalyst demonstrated outstanding methanol productivity (2.64 g\u003csub\u003eMeOH\u003c/sub\u003e·g\u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e·h\u003csup\u003e− 1\u003c/sup\u003e) after 51 hours, with an exceptional gas hourly space velocity (GHSV) of 78,000 h⁻¹. This superior performance is likely due to the formation of an In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-incorporated ZrO\u003csub\u003e2\u003c/sub\u003e phase, which introduces oxygen vacancies or defective sites that enhance CO\u003csub\u003e2\u003c/sub\u003e activation and methanol production\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. Previous studies, such as those by Javier et al., suggest that incorporating In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e into ZrO\u003csub\u003e2\u003c/sub\u003e induces the formation of a polymorphic ZrO\u003csub\u003e2\u003c/sub\u003e structure, which significantly improves CO\u003csub\u003e2\u003c/sub\u003e adsorption on the catalyst surface\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. Catalytic tests on bare In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e revealed that ZrO\u003csub\u003e2\u003c/sub\u003e mainly produced CO with a low CO\u003csub\u003e2\u003c/sub\u003e conversion (0.09%), while In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e showed slightly higher activity with 0.9% CO\u003csub\u003e2\u003c/sub\u003e conversion, producing methanol. The performance of the Deg In-Zr (3:8) catalyst was further compared with that of In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-impregnated ZrO\u003csub\u003e2\u003c/sub\u003e (In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e) and In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e/C (impregnated on graphite). These conventional catalysts achieved CO\u003csub\u003e2\u003c/sub\u003e conversion rates of 3.2% and 4.6%, respectively, but were still far less active than Deg In-Zr (3:8), which achieved a 27.8% CO\u003csub\u003e2\u003c/sub\u003e conversion after 51 hours at 220°C and 40 bar pressure. Catalytic activity was also assessed with varying indium content in the MOF-derived catalysts. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(b) and (e) show that increasing indium content initially enhanced activity, but beyond a certain threshold, the catalytic performance declined. This is likely due to an optimal balance of In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e, both of which serve as active sites for CO\u003csub\u003e2\u003c/sub\u003e hydrogenation to methanol\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e,\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe time-on-stream profile (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(f) and S13 (a)) indicates that the Deg In-Zr (3:8) catalyst had an induction period of 24 hours, during which methanol selectivity reached 81%, with a productivity of 2.61 g\u003csub\u003eMeOH\u003c/sub\u003e·g\u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e·h\u003csup\u003e− 1\u003c/sup\u003e. Methanol selectivity stabilized at 81.4%, with by-products including formic acid (10.3%) and CO (1.6%). The small amount of CO is likely due to the reverse water-gas shift (RWGS) reaction, which typically requires higher activation energy and occurs at temperatures above 280°C\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e. After 51 hours, the methanol production remained stable at 2.64 g\u003csub\u003eMeOH\u003c/sub\u003e·g\u003csub\u003ecat\u003c/sub\u003e\u003csup\u003e−1\u003c/sup\u003e·h\u003csup\u003e− 1\u003c/sup\u003e. Initially, formic acid was a major by-product, but as the reaction progressed, its selectivity decreased while methanol selectivity increased. CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e are adsorbed onto the catalyst surface, forming surface-bound formate\u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e (HCOO\u003csup\u003e−\u003c/sup\u003e), which is then reduced to methanol through intermediates like H\u003csub\u003e2\u003c/sub\u003eCO* and H\u003csub\u003e3\u003c/sub\u003eCO*\u003csup\u003e42\u003c/sup\u003e. The oxygen vacancies in the In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e species assist in this process by facilitating CO\u003csub\u003e2\u003c/sub\u003e adsorption and activation. As temperature increased, methanol selectivity improved, but ethanol formation began at temperatures above 230°C. The time-on-stream profile for different temperatures is shown in Fig. S13 (b) and (c), where CO selectivity increased with temperature due to the RWGS reaction\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eFor liquid-phase CO\u003csub\u003e2\u003c/sub\u003e hydrogenation, the Deg In-Zr (3:8) catalyst was tested in a high-pressure Parr reactor. The catalyst was highly active in converting CO\u003csub\u003e2\u003c/sub\u003e to methanol, with reaction parameters such as temperature, pressure, and reaction time studied (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(g)-(i)). Before the reaction, the catalyst was reduced at 300°C under 4% H\u003csub\u003e2\u003c/sub\u003e in Ar for 2 hours. As per Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e (h), at 130°C and 30 bar pressure (3:1 H\u003csub\u003e2\u003c/sub\u003e: CO\u003csub\u003e2\u003c/sub\u003e ratio), the highest methanol selectivity (96.8%) was achieved. Increasing the temperature to 190°C enhanced CO\u003csub\u003e2\u003c/sub\u003e conversion to 35.3%, but ethanol and propanol started to form at higher temperatures, likely due to methanol chain growth via C-C coupling\u003csup\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. The effect of pressure on CO\u003csub\u003e2\u003c/sub\u003e conversion and methanol selectivity was also evaluated, with pressure ranging from 20 to 70 bar (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(g)). As pressure increased, CO\u003csub\u003e2\u003c/sub\u003e conversion increased from 23.6–32.2%, but methanol selectivity decreased above 30 bar, leading to the formation of ethanol and propanol. Propanol selectivity reached 15.5% at 70 bar, with ethanol selectivity at 2.3%. The time-on-stream profile in liquid phase over 72h (Fig. S16) revealed that methanol selectivity peaked at 96.8% after 5 hours of reaction, with 26.6% CO\u003csub\u003e2\u003c/sub\u003e conversion. Over extended reaction times, butanol selectivity increased, reaching 25.5% after 72 hours, likely due to C-C coupling reactions\u003csup\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e. This phenomenon aligns with findings from Wang et al., who observed ethanol formation via C-C coupling over Co catalysts after extended reaction times. The reusability (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e(i)) of the Deg In-Zr (3:8) catalyst was tested over five cycles at 130°C, 30 bar total pressure, and 5 hours reaction time. The CO\u003csub\u003e2\u003c/sub\u003e conversion showed only a slight decline from 26.6–25.8%, and methanol selectivity remained high (96.8–95.1%). ICP-MS analysis indicated minimal loss of active metals (In and Zr), confirming the catalyst’s stability in the liquid-phase reaction medium. Characterization of the reused catalyst, including XRD, XPS, and TEM (Fig. S19), confirms that the catalyst maintains its structural integrity after five catalytic cycles. XPS analysis of In and Zr in the reused catalyst reveals oxidation states of + 3 and + 4, respectively, consistent with those observed in the fresh catalyst.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eStructure performance relationship establishment via in situ AP XPS and Kinetic Study\u003c/h3\u003e\n\u003cp\u003e \u003cem\u003eIn situ\u003c/em\u003e XPS analysis was conducted on various catalysts under different temperatures and hydrogen pressure conditions, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e. The O 1s high-resolution XPS spectra were deconvoluted into three peaks at 529.6 eV, 531.7 eV, and 533.3 eV, corresponding to lattice oxygen, oxygen vacancies, and –OH groups, respectively\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e. As the hydrogen and CO\u003csub\u003e2\u003c/sub\u003e pressure increased from 10 mTorr to 30 mTorr, the number of oxygen vacancies also increased (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(a)). This trend was similarly observed with rising temperature (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(b)), indicating that higher temperatures and pressures promote the generation of oxygen vacancies, which in turn create more active sites for CO\u003csub\u003e2\u003c/sub\u003e adsorption on the catalyst surface\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(c) and (d) show a shift in the indium binding energy to higher values under increased pressure and temperature. Conversely, the binding energy of Zr shifted to lower values under the same conditions (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e(e) and (f)), suggesting a charge transfer between In and Zr that may lead to the formation of In-Zr bimetallic sites\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e,\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e. The C 1s XPS spectra were deconvoluted into three peaks at 284.3 eV, 285.5 eV, and 288.6 eV, corresponding to C–C, C–O–C, and O–C = O bonds, respectively\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eA kinetic study was performed using the Deg In-Zr (3:8) catalyst and compared with conventional In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e and In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e/C catalysts (Fig. S15(a)-(c)). The activation energy for CO\u003csub\u003e2\u003c/sub\u003e conversion to methanol and the reverse water-gas shift (RWGS) reaction was determined using the Arrhenius equation, plotting the inverse of temperature (1/T) against ln(ri), where ri represents the initial rate constant. CO\u003csub\u003e2\u003c/sub\u003e conversion to methanol was conducted at four different temperatures: 210°C, 220°C, 230°C, and 240°C. Among the catalysts, Deg In-Zr (3:8) exhibited the lowest activation energy (46.2 ± 5 kJ mol⁻¹) for methanol production, significantly lower than the reported activation energy for In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-ZrO\u003csub\u003e2\u003c/sub\u003e catalysts by Frei et al. The activation energy for the RWGS reaction over Deg In-Zr (3:8) was higher, at 98.6 ± 4 kJ mol⁻¹\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. Due to its low activation energy barrier for methanol production, Deg In-Zr (3:8) demonstrated superior catalytic activity for CO\u003csub\u003e2\u003c/sub\u003e conversion to methanol. Further details of the structure and activity relationship provided in supporting information (page 22).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eIn situ DRIFT for gas phase and in situ ATR-IR for liquid phase\u003c/h3\u003e\n\u003cp\u003eTo investigate the reaction mechanism and identify intermediate species in the gas-phase conversion of CO\u003csub\u003e2\u003c/sub\u003e to methanol, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) was conducted on Deg In-Zr (3:8), Deg In-Zr (1:4), and In-Zr BDC catalysts at 220°C and 10 bar with a 25% CO\u003csub\u003e2\u003c/sub\u003e and 75% H\u003csub\u003e2\u003c/sub\u003e feed. At the start of the reaction (Fig. S18), a CO\u003csub\u003e2\u003c/sub\u003e peak at 2350 cm⁻¹ was detected for all catalysts\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e. After 10 minutes, small peaks at 2121 cm⁻¹ (CO) and 1498 cm⁻¹ (monodentate carbonate, CO\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e-2\u003c/sup\u003e) appeared\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e. The formate species (HCOO*) became prominent after 25 minutes over the Deg In-Zr (3:8) catalyst (Fig. S18 (b)), with peaks at 1576 cm⁻¹ (asymmetric OCO stretching) and 1372 cm⁻¹ (symmetric OCO stretching)\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e. Additionally, the bending vibration of CH in HCOO* was detected at 1386 cm⁻¹ after 20 minutes\u003csup\u003e\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e\u003c/sup\u003e. Peaks corresponding to H\u003csub\u003e3\u003c/sub\u003eCO* species (2830, 2894, and 1040 cm⁻¹)\u003csup\u003e\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e appeared after 30 minutes, with the formate intensity peaking at 35 minutes and declining after 50 minutes, while H\u003csub\u003e3\u003c/sub\u003eCO* intensity increased over time, reaching its maximum after 140 minutes. The decrease in the CO\u003csub\u003e2\u003c/sub\u003e peak at 2350 cm⁻¹ confirmed CO\u003csub\u003e2\u003c/sub\u003e adsorption and conversion into HCOO*, which is subsequently reduced to H\u003csub\u003e3\u003c/sub\u003eCO* and eventually forms CH\u003csub\u003e3\u003c/sub\u003eOH. These findings are consistent with previous studies on In-Zr-based catalysts\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e. DRIFT analysis was also performed on Deg In-Zr (1:4), which showed the appearance of HCOO* peaks after 35 minutes, though no H\u003csub\u003e3\u003c/sub\u003eCO* species were detected, indicating lower activity compared to Deg In-Zr (3:8). For the indium-impregnated ZrBDC catalyst (In-Zr BDC), the formate peak at 1576 cm⁻¹ was weak, confirming its much lower activity (Fig. S18 (a) and (c)).\u003c/p\u003e \u003cp\u003eIn situ ATR-IR spectroscopy was conducted to further investigate the CO\u003csub\u003e2\u003c/sub\u003e hydrogenation mechanism over Zr-BDC, In-Zr BDC, and Deg In-Zr (3:8) catalysts (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(b), (d) and (f)) within a 0-180 minute time frame. At the start, a doublet for adsorbed CO\u003csub\u003e2\u003c/sub\u003e at 2350 cm⁻¹ was observed for all catalysts\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e,\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e. Over the Deg In-Zr (3:8) catalyst (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e (f)), a peak at 1500 cm⁻¹ appeared after 10 minutes, corresponding to surface-bound zirconium bidentate carbonate, consistent with CO\u003csub\u003e2\u003c/sub\u003e reduction studies by Katayama et al\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e. As the reaction progressed, a new peak at 1620 cm⁻¹, associated with adsorbed formate (HCOO\u003csub\u003ead\u003c/sub\u003e), emerged at 20 minutes. CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e were adsorbed onto the catalyst surface, where oxygen vacancies and active H species likely combined with adsorbed CO\u003csub\u003e2\u003c/sub\u003e to form formate\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e. By 30 minutes, the formate peak intensified\u003csup\u003e\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e, and a peak at 1298 cm⁻¹ (symmetric C = O stretching in bidentate HCOO\u003csub\u003ead\u003c/sub\u003e) appeared\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e. After 40 minutes, a small peak at 1396 cm⁻¹ for OCH\u003csub\u003e3\u003c/sub\u003e adsorbed species (OCH\u003csub\u003e3ad\u003c/sub\u003e) was detected\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e, indicating the hydrogenation of HCOO\u003csub\u003ead\u003c/sub\u003e to OCH\u003csub\u003e3ad\u003c/sub\u003e, following the reaction pathway CO\u003csub\u003e2ad\u003c/sub\u003e → HCOO\u003csub\u003ead\u003c/sub\u003e → H\u003csub\u003e2\u003c/sub\u003eCO\u003csub\u003ead\u003c/sub\u003e → OCH\u003csub\u003e3ad\u003c/sub\u003e, as supported by both DFT calculations and experimental evidence\u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e. The OCH\u003csub\u003e3ad\u003c/sub\u003e peak increased in intensity over time, reaching its maximum at 180 minutes, while the formate peak steadily declined, confirming its conversion to OCH\u003csub\u003e3ad\u003c/sub\u003e and eventually methanol. Additionally, the CO\u003csub\u003e2\u003c/sub\u003e peak at 2350 cm⁻¹ decreased significantly, indicating CO\u003csub\u003e2\u003c/sub\u003e reduction to CH\u003csub\u003e3\u003c/sub\u003eOH. No CO peak was observed, suggesting the absence of the reverse water-gas shift (RWGS) reaction, which typically occurs at higher temperatures\u003csup\u003e\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eIn contrast, the other two catalysts, Zr-BDC (bare MOF) (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e (b)) and In-Zr BDC (indium-impregnated Zr MOF) (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e (d)), showed no significant peaks except for CO\u003csub\u003e2\u003c/sub\u003e, indicating that they were inactive for CO\u003csub\u003e2\u003c/sub\u003e hydrogenation to methanol during the 0–180-minute reaction window.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eDFT calculations\u003c/h2\u003e \u003cp\u003eBuilding on our previous computational studies on the catalytic activity of metal-organic frameworks (MOFs) for CO\u003csub\u003e2\u003c/sub\u003e conversion\u003csup\u003e\u003cspan additionalcitationids=\"CR59\" citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e–\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e\u003c/sup\u003e, this work focuses on the support effect of degraded In-Zr MOF (Deg In-Zr) as a catalyst for methanol production. Quantum chemistry calculations were performed to investigate the mechanisms behind the enhanced catalytic performance of the degraded In-Zr MOF, specifically analyzing the role of indium impregnation. Prior research has established that methanol formation follows the formate pathway, where CO\u003csub\u003e2\u003c/sub\u003e binds at oxygen, indium, and zirconium active sites on the catalyst surface\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e,\u003cspan additionalcitationids=\"CR62 CR63\" citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e–\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e\u003c/sup\u003e. Mechanistically, the formation of formate (HCOO) is facilitated when both H\u003csub\u003e2\u003c/sub\u003e and CO\u003csub\u003e2\u003c/sub\u003e absorb energy to form stable intermediates. After degradation, the creation of oxygen vacancies significantly lowers the energy barrier for formate production, stabilizing the HCOO intermediate. In this context, we designed structural models to study the adsorption of CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e over two different catalyst surfaces—before and after degradation—encompassing Deg In-Zr (degraded MOF with two oxygen vacancy configurations) and In-Zr BDC (containing active indium and zirconium sites within a MOF structure). The Deg In-Zr and In-Zr BDC surface models were based on previously reported structures of In-doped ZrO\u003csub\u003e2\u003c/sub\u003e and indium-impregnated MOFs\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e,\u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e,\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e\u003c/sup\u003e. We optimized the geometries of the catalyst models before and after degradation using density functional theory (DFT) methods, with the optimized atomic coordinates provided in Table S1\u003csup\u003e67\u003c/sup\u003e. To explore the electronic properties and key intramolecular interactions between reactants (CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e) and the active sites of these catalyst models, we performed quantum theory of atoms in molecules (QTAIM) calculations\u003csup\u003e\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e\u003c/sup\u003e on the optimized structures. The QTAIM molecular graphs, including bond critical points (BCPs), ring critical points (RCPs), and bond paths, are presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e, and the corresponding QTAIM indicators are listed in Table S2. The QTAIM analysis revealed that oxygen vacancies in the degraded catalysts significantly enhance the interaction between the reactants and the active sites, compared to the non-degraded models. This is evident from the formation of In-H BCPs with electron density values around 0.1 in Deg In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-OV1 and Deg In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-OV2, which indicates the interaction of H\u003csub\u003e2\u003c/sub\u003e with indium active sites. In contrast, no such interactions were observed in the non-degraded models. Additionally, the interaction between CO\u003csub\u003e2\u003c/sub\u003e and indium active sites was stronger than with zirconium sites, as shown by the electron density values in the BCPs of O(CO\u003csub\u003e2\u003c/sub\u003e)-In, O(CO\u003csub\u003e2\u003c/sub\u003e)-Zr, and C(CO\u003csub\u003e2\u003c/sub\u003e)-O(catalyst). Furthermore, in the degraded catalyst models (Deg In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-OV1 and Deg In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-OV2), H-H bond dissociation occurred, facilitating C-H bond formation and leading to formic acid production in subsequent reaction steps. This suggests that the presence of oxygen vacancies plays a critical role in promoting the catalytic conversion of CO\u003csub\u003e2\u003c/sub\u003e to methanol.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003ePlausible reaction mechanism and structure and performance relationship\u003c/h3\u003e\n\u003cp\u003eInitially, H\u003csub\u003e2\u003c/sub\u003e undergoes heterolytic cleavage on the defective surface of indium oxide, marking the first step in hydrogenating chemisorbed CO\u003csub\u003e2\u003c/sub\u003e at oxygen vacancies (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(a))\u003csup\u003e\u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e69\u003c/span\u003e,\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e. A plausible pathway for methanol synthesis on the In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e(111) surface follows the sequence: *HCOO → H\u003csub\u003e2\u003c/sub\u003eCOO* → H\u003csub\u003e3\u003c/sub\u003eCO*. In this study, in situ DRIFTS under realistic conditions reveals that *HCOO is the dominant surface intermediate in the CO\u003csub\u003e2\u003c/sub\u003e hydrogenation process to methanol, consistent with previous reports\u003csup\u003e\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e,\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e. While formate species were previously suggested as bystanders on Cu-based catalysts\u003csup\u003e\u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e\u003c/sup\u003e, in situ DRIFTS confirms the active involvement of *HCOO as a reaction intermediate for the In-Zr catalysts. Increasing indium content enhances H\u003csub\u003e2\u003c/sub\u003e splitting and promotes the formation of *HCOO, as demonstrated by the generation of *HCOO on Deg In-Zr (3:8), Deg In-Zr (1:8), and Deg In-Zr (3:2) catalysts. Indium sites are also likely crucial for the formation of *H\u003csub\u003e3\u003c/sub\u003eCO species\u003csup\u003e\u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e72\u003c/span\u003e\u003c/sup\u003e. CH\u003csub\u003e3\u003c/sub\u003eOH TPD analysis shows that catalysts with higher indium content exhibit a stronger affinity between the catalyst surface and CH\u003csub\u003e3\u003c/sub\u003eOH. Additionally, HCOOH TPD analysis indicates that bulk In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e has a stronger interaction with HCOOH than other catalysts, suggesting that the conversion of HCOOH to CH\u003csub\u003e3\u003c/sub\u003eO* depends on optimal interaction with the catalyst surface, where the correct indium amount is critical for achieving high CH\u003csub\u003e3\u003c/sub\u003eOH selectivity. However, when indium content is too high, the interaction with HCOOH becomes too stable, potentially inhibiting its conversion to CH\u003csub\u003e3\u003c/sub\u003eO*. The well-dispersed In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e on ZrO\u003csub\u003e2\u003c/sub\u003e forms a complex interface with the ZrO\u003csub\u003e2\u003c/sub\u003e support. At these interfacial sites, In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e dissociates gaseous H\u003csub\u003e2\u003c/sub\u003e into reactive hydrogen atoms, which then interact with adsorbed CO\u003csub\u003e2\u003c/sub\u003e to generate bidentate *HCOO. This intermediate is more likely to undergo hydrogenation, given a delicate balance between the adsorption strengths of *HCOO and *H\u003csub\u003e3\u003c/sub\u003eCO. Meanwhile, the reduced interaction of *HCOO with ZrO\u003csub\u003e2\u003c/sub\u003e inhibits CO formation, as it struggles to bind effectively to the ZrO\u003csub\u003e2\u003c/sub\u003e surface. To clarify the reaction mechanism, HCOOH decomposition was tested over various catalysts in the presence of CO\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003e. ZrO\u003csub\u003e2\u003c/sub\u003e alone primarily produced CO, while Deg In-Zr catalysts generated CO, CO\u003csub\u003e2\u003c/sub\u003e, and H\u003csub\u003e2\u003c/sub\u003e during steady-state HCOOH decomposition, indicating that ZrO\u003csub\u003e2\u003c/sub\u003e plays a crucial role in CO formation during the catalytic conversion of CO\u003csub\u003e2\u003c/sub\u003e to methanol.\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eCrystal engineering of MOFs combined with pyrolysis techniques has been used to synthesize ultrafine In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e nanoparticles embedded in a ZrO\u003csub\u003e2\u003c/sub\u003e matrix, forming an oxygen vacancy-incorporated heterojunction between the In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e phases. This catalyst, obtained by pyrolyzing indium-impregnated Zr-BDC MOF with a low indium content of 0.2 wt.%, has been thoroughly characterized using EXAFS, XANES, and HR-TEM, confirming the creation of In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e heterostructures. XPS analysis further revealed the presence of oxygen vacancies on the catalyst surface, which likely contributes to its exceptional catalytic performance in both liquid and gas-phase CO\u003csub\u003e2\u003c/sub\u003e hydrogenation to methanol. The active site for methanol synthesis is believed to be the interface between ZrO\u003csub\u003e2\u003c/sub\u003e and defective In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, with reaction mechanisms involving the formate pathway. Oxygen vacancies play a key role in activating CO\u003csub\u003e2\u003c/sub\u003e and enhancing methanol stability on the catalyst surface. The catalyst demonstrates remarkable stability in both liquid and gas phase reactions, highlighting its robust performance. In situ DRIFT spectroscopy (gas phase) and in situ ATR-IR spectroscopy (liquid phase) confirmed that methanol synthesis predominantly follows the formate pathway. CH\u003csub\u003e3\u003c/sub\u003eOH TPD and HCOOH TPD experiments showed that an optimal indium content enhances CH\u003csub\u003e3\u003c/sub\u003eOH selectivity. A higher concentration of indium stabilizes formate species on the catalyst surface, reducing their conversion to CH\u003csub\u003e3\u003c/sub\u003eO* species. Conversely, higher ZrO\u003csub\u003e2\u003c/sub\u003e concentrations promote formate decomposition into CO and H\u003csub\u003e2\u003c/sub\u003eO. These TPD studies revealed the active surface species driving the reaction. In situ XPS further explored the relationship between the catalyst’s surface structure and its catalytic performance. The study confirmed that the abundance of oxygen vacancies and electronic modulation between In\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e are key factors driving the high catalytic activity. Previous work by Kumari et al. also highlighted that oxygen vacancies play a critical role in CO\u003csub\u003e2\u003c/sub\u003e activation by lowering the reaction barriers for CO\u003csub\u003e2\u003c/sub\u003e dissociation. DFT calculations in this study reinforced these findings\u003csup\u003e\u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e73\u003c/span\u003e\u003c/sup\u003e. This research presents a systematic atomic-level approach for designing multi-metal catalysts with enhanced active sites for CO\u003csub\u003e2\u003c/sub\u003e hydrogenation to methanol. The method of optimizing indium content and controlling oxygen vacancies can be applied to other catalytic systems, providing a cost-effective and efficient route to catalyst synthesis, with indium loading as low as 0.2 wt.%. This approach offers significant potential for industrial-scale methanol production through CO\u003csub\u003e2\u003c/sub\u003e hydrogenation. Future work will involve operando EXAFS studies to monitor structural changes in the catalyst during reactions in real time. These studies will provide deeper insights into the reaction mechanism, helping to develop even more effective catalysts for CO\u003csub\u003e2\u003c/sub\u003e hydrogenation.\u003c/p\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/div\u003e"},{"header":"Methods","content":"\u003cp\u003e \u003cstrong\u003eChemicals\u003c/strong\u003e \u003c/p\u003e\u003cp\u003eZrCl\u003csub\u003e4\u003c/sub\u003e, benzene dicarboxylic acid, Indium (III) nitrate hydrate (In(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e · xH\u003csub\u003e2\u003c/sub\u003eO), N,N-Dimethylformamide, methanol and ZrO\u003csub\u003e2\u003c/sub\u003e are purchased from Sigma Aldrich.\u003c/p\u003e\u003cp\u003e \u003cem\u003eCatalyst preparation\u003c/em\u003e: Zr BDC MOF has been prepared by following literature reported method by involving the dissolution of ZrCl\u003csub\u003e4\u003c/sub\u003e (0.053 g, 0.227 mmol) and 1,4-benzene dicarboxylic acid (H\u003csub\u003e2\u003c/sub\u003eBDC) (0.034 g, 0.227 mmol) in N, N'-dimethylformamide (DMF) (24.9 g, 340 mmol) at room temperature\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e. The mixture was then heated in an oven at 120°C for 24 hours, allowing crystallization to occur under static conditions. After cooling to room temperature in air, the solid product was filtered, washed multiple times with DMF and methanol, and dried in an oven at 60°C overnight (14 hours). Indium was impregnated into the Zr-BDC MOF using the incipient wetness impregnation (IWI) technique to synthesize the In-Zr BDC catalyst. Various indium-to-zirconium molar ratios (3:2, 3:4, 3:8, 1:2, 1:4, and 1:8) were applied to produce the indium-impregnated Zr BDC MOF. The corresponding amount of indium nitrate was added to 1 g of Zr BDC MOF in a methanol solution. The resulting solution was then refluxed at 70°C for 24 hours. Following this, the solution was centrifuged, and the solid (In-Zr BDC) was dried in an oven at 60°C overnight. All of the In-Zr BDC was thermally treated in a 600 ℃ tubular furnace under an N\u003csub\u003e2\u003c/sub\u003e atmosphere for 4h at a 2 ℃/min heating rate. This is denoted as Deg In-Zr.\u003c/p\u003e\u003ch2\u003eCatalyst characterization:\u003c/h2\u003e\u003cp\u003eAll the detailed catalyst characterizations are depicted in Supplementary Information.\u003c/p\u003e\u003ch2\u003eDFT calculations:\u003c/h2\u003e\u003cp\u003eThe details of the DFT calculations are shown in the Supplementary Information.\u003c/p\u003e\u003ch2\u003eCatalyst evaluation (Gas Phase \u0026amp; Liquid Phase):\u003c/h2\u003e\u003cp\u003eThe catalytic activity was assessed in a fixed-bed reactor that was 300 mm long and 7 mm in diameter, constructed from stainless steel. The bed comprised 0.4 g of catalyst (with a mesh size distribution of 20–40) and 2 g of quartz particles, arranged between two layers of silica wool. Initially, the reactor pressure was raised to 3.0 MPa with N\u003csub\u003e2\u003c/sub\u003e flow, and the temperature was increased to 300°C. Subsequently, the catalyst was reduced and activated using a stream of diluted hydrogen (10 vol % H\u003csub\u003e2\u003c/sub\u003e/N\u003csub\u003e2\u003c/sub\u003e) at 350°C for 1 hour. The catalytic activity for methanol synthesis was evaluated under the following conditions: H\u003csub\u003e2\u003c/sub\u003e/CO\u003csub\u003e2\u003c/sub\u003e = 3 and a flow rate of 10 mL/min (30 bar pressure). At the outlet of the reactor, the gases were depressurized to atmospheric pressure, and the reaction products were analyzed using an online gas chromatograph (GC, Agilent 7890A) equipped with two detectors. A flame ionization detector, along with an HP-FFAP column and H\u003csub\u003e2\u003c/sub\u003e as the carrier gas, was used to detect CO, CH\u003csub\u003e4\u003c/sub\u003e, and CH\u003csub\u003e3\u003c/sub\u003eOH. A thermal conductivity detector equipped with MS-5A and Hayesep Q columns, utilizing He as the carrier gas, was used to identify other gaseous products (including H\u003csub\u003e2\u003c/sub\u003e, CO\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003e, and CO). The carbon balance was found to exceed 95% in all experiments. The calculations for CO\u003csub\u003e2\u003c/sub\u003e conversion, selectivity of C-containing products, and product yield were carried out as follows\u003c/p\u003e\u003cp\u003eCO\u003csub\u003e2\u003c/sub\u003e Conversion (%) = \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:(\\frac{{F}_{{CO}_{2\\:IN}}-{F}_{{CO}_{2\\:OUT}}}{{F}_{{CO}_{2\\:IN}}}\\)\u003c/span\u003e\u003c/span\u003e)\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\times\\:100\\)\u003c/span\u003e\u003c/span\u003e\u003c/p\u003e\u003cp\u003eSelectivity (%) = \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\left(\\frac{N\\%}{\\sum\\:\\left(\\left(N\\%\\right)\\right)}\\right)\\times\\:100\\)\u003c/span\u003e\u003c/span\u003e\u003c/p\u003e\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$$\\:\\text{Y}\\text{i}\\text{e}\\text{l}\\text{d}\\:\\left(\\text{%}\\right)\\hspace{0.17em}=\\hspace{0.17em}\\text{s}\\text{e}\\text{l}\\text{e}\\text{c}\\text{t}\\text{i}\\text{v}\\text{i}\\text{t}\\text{y}\\:\\times\\:\\:\\text{c}\\text{o}\\text{n}\\text{v}\\text{e}\\text{r}\\text{s}\\text{i}\\text{o}\\text{n}\\:\\times\\:100$$\u003c/div\u003e\u003c/div\u003e\u003cp\u003eHere, N denotes the carbon-containing species in the products, which include CO, CH\u003csub\u003e4\u003c/sub\u003e, and CH\u003csub\u003e3\u003c/sub\u003eOH. The results were obtained once the reaction reached a steady state.\u003c/p\u003e\u003cp\u003eAll the reactions of CO\u003csub\u003e2\u003c/sub\u003e hydrogenation were performed in a 250 ml stainless steel Parr autoclave inbuilt with a pressure gauge setup. The typical hydrogenation reaction conditions were temperature, 130°C; 60 ml water; 40 mg of catalyst; oxygen pressure, 30 bar (3:1 H\u003csub\u003e2\u003c/sub\u003e: CO\u003csub\u003e2\u003c/sub\u003e); reaction time, 5 h. After the completion of the reaction, the reaction mixture was collected, filtered, and analyzed by HPLC. C-18 column, in combination with milli Q water as mobile phase.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAresta M (2010) Carbon dioxide as chemical feedstock. Wiley\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJadhav SG, Vaidya PD, Bhanage BM, Joshi JB (2014) Catalytic carbon dioxide hydrogenation to methanol: A review of recent studies. 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J Phys Chem C 120:16626\u0026ndash;16635\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":false,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-6143390/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6143390/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe hydrogenation of CO₂ to methanol is a promising route for carbon capture and utilization, but achieving high selectivity and productivity remains a challenge. This study presents a novel catalyst synthesized by pyrolyzing a zirconium-based metal-organic framework (Zr-BDC) impregnated with indium, yielding ultrafine In₂O₃ nanoparticles uniformly embedded within a ZrO₂ and carbon matrix. The resulting In₂O₃/ZrO₂ heterojunction exhibits abundant oxygen vacancies at the interface, which is crucial in enhancing catalytic performance. Under gas-phase conditions, the catalyst achieves an exceptional methanol selectivity of 81% with a record-high productivity of 2.64 gMeOH\u0026middot;gcat⁻\u0026sup1;\u0026middot;h⁻\u0026sup1;, while in liquid-phase hydrogenation, methanol selectivity reaches 96%. Comprehensive structural characterizations confirm that oxygen vacancies and the heterointerface serve as active sites, facilitating CO₂ activation and methanol stabilization. Mechanistic insights from in situ DRIFTS and ATR-IR spectroscopy reveal that methanol formation proceeds via the formate pathway, further supported by in situ ambient-pressure X-ray photoelectron spectroscopy, demonstrating electronic structural modulation and an increased concentration of oxygen vacancies. These findings underscore the critical role of defect engineering in optimizing CO₂ hydrogenation catalysts and provide a pathway for designing highly efficient systems for sustainable methanol production.\u003c/p\u003e","manuscriptTitle":"Leveraging Metal Organic Framework Derived Indium/Zirconium Oxide for Unprecedented Catalytic Performance in CO₂ Hydrogenation to Methanol","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-03-18 06:43:23","doi":"10.21203/rs.3.rs-6143390/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"03d03fa6-24d2-4eda-b177-75e00fc24a9a","owner":[],"postedDate":"March 18th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":45627479,"name":"Physical sciences/Chemistry/Green chemistry/Sustainability"},{"id":45627480,"name":"Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis"}],"tags":[],"updatedAt":"2025-10-08T07:05:58+00:00","versionOfRecord":{"articleIdentity":"rs-6143390","link":"https://doi.org/10.1038/s41467-025-63932-y","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2025-10-07 04:00:00","publishedOnDateReadable":"October 7th, 2025"},"versionCreatedAt":"2025-03-18 06:43:23","video":"","vorDoi":"10.1038/s41467-025-63932-y","vorDoiUrl":"https://doi.org/10.1038/s41467-025-63932-y","workflowStages":[]},"version":"v1","identity":"rs-6143390","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6143390","identity":"rs-6143390","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}