Coke Resistance Research Articles

Boosting Dry Reforming of Methane Over NiCo/CeO2 Catalysts Treated by Hydrogen Plasma

ABSTRACTNickel (Ni)‐based catalysts are prospective materials for dry reforming of methane (DRM) reaction, but suffer from coke formation and limited activity for CO2 conversion. To improve the reactivity of Ni‐based catalysts, a promising strategy is introducing cobalt (Co) metal. Here, we construct highly efficient NiCo sites on CeO2 support by H2 plasma, which enables the catalyst to obtain a remarkable increase in DRM reaction than the samples treated by conventional H2 reduction. H2 plasma treatment results in the formation of highly dispersed NiCo alloy nanoparticles and high‐concentration oxygen vacancy. These features create large numbers of highly active sites to boost the activation of CH4 and especially CO2 and their catalytic reactions, resulting in strong coke resistance in the DRM reaction.

Enhancing coke resistance of Ni-based spinel-type oxides by tuning the configurational entropy

The reforming of CH4 and CO2 into syngas is a highly relevant technology for energy conservation and reducing greenhouse gas emissions, attracting widespread attention in the industry. Inspired by this, this work proposes a general criterion for coke-resistant nickel-based catalysts. By leveraging the high-entropy effect and the lattice distortion of the structure, a high-entropy (NiCaMgZnCo)Al10Ox catalyst was synthesized. The high-entropy oxide exhibited good activity and stability during the DRM reaction over 100 h at 800°C and 650°C, producing only a minimal amount of easily removable carbon deposition. O2-TPO, CO2-TPD, CH4-TPSR, CO2-TPSR, DFT and in situ DRIFT were employed to investigate the mechanism of carbon deposition elimination on the surface of the high-entropy catalyst. Then, a high-entropy strategy for designing coke-resistant catalysts was proposed. This strategy may soon inspire the development of catalysts with enhanced stability and anti-coke deposition properties for various catalytic applications.

Modification of chemical vapor-phase deposition and coking resistance over HZSM-5 catalysts for toluene disproportionation

Abstract To achieve higher catalytic activity of toluene disproportionation and improve the p-xylene selectivity and stability of coking resistance on HZSM-5 catalysts, tetrabutyl titanate, ethyl orthosilicate and diethyl phosphite were used for chemical gas-phase deposition modification on HZSM-5 catalysts. The properties of acid sites on catalysts were characterized by infrared spectroscopy (IR) and temperature-programmed desorption of pyridine (TPD), respectively. The experimental results showed that the type of acid sites and density of weaker acid sites over HZSM-5 zeolites deposited by oxides containing Ti, Si and P in chemical vapor coating did not change while the density of stronger acid sites decreased, in which acid intensity on HZSM-5 zeolite deposited by oxides containing P enhanced obviously. Using HZSM-5 zeolites modified as catalysts of toluene disproportionation, HZSM-5 catalysts deposited by oxides containing Si and P can greatly improve both catalytic activity and coking resistance on catalysts.

Enhanced coking resistance of alumina-supported cobalt nitride catalyst via doping of phosphorus for dry reforming of methane

A novel P-doped Co4N/γ-Al2O3 catalyst was firstly designed for dry reforming of methane (DRM). It was found that the use of P doping Co4N/γ-Al2O3 can enhance its coking resistance, which might be due to a decrease in CH4 dissociation ability and an increase in CO2 dissociation ability, as well as the increase of cobalt species capable of interacting with alumina.

Effective CO2 Thermocatalytic Hydrogenation with High Coke Resistance on Ni-CZ/Attapulgite Composite

Converting CO2 into methane is considered a promising and economically viable technology for global transportation and utilization of this greenhouse gas. This study involves the preparation of a Ni-CZ (CeO2-ZrO2)/ATP (attapulgite) catalyst through the co-precipitation and impregnation methods. XRD, SEM, TEM, N2 absorption-desorption isotherms, XPS, H2-TPR, CO2-TPD, TG/DSC, and Raman were adapted to characterize the obtained samples. Real-time GC was used to measure the catalytic performances and to intensively study the impact of Ni loading content and ATP to CZ ratio on the catalytic performance of the products. DRIFTs was used to monitor the interstitial radicals in the catalytic reactions and to deduce the catalytic mechanisms. The results indicate that the composite catalytic matrix composed of CZ assembled on ATP demonstrated higher CO2 methanation stability and better carbon deposition resistance ability than the single CZ or ATP as the carrier, which should be attributed to the improved specific surface area and pore volume of the ATP assembled matrix and the enhanced dispersibility of the CZ and Ni species. The adoption of CZ solid solutions improves the oxygen storage capability of the catalyst, thereby providing continued mobile O2− in the matrix and accelerating the molecular exchange rate in the catalytic reactions. The ideal loading quantity of nickel contents on the CZA matrix is 15%, as the CO2 conversion decreases at elevated temperatures when the Ni loading content reaches 20%. Among the tested samples, the 15Ni-0.8CZA sample showed the best catalytic performance of 75% CO2 conversion and 100% CH4 selectivity at 400 °C. After 50 h of stability tests, the CO2 conversion rate still remained 70.84%, and the CH4 selectivity obtained 97.46%. No obvious coke was detected according to the Raman spectra of the used catalyst. The in situ DRIFTS experiment showed that formate is the main intermediate of the CO2 hydrogenation reaction on the 15Ni-0.8CZA catalyst.

Hydrodeoxygenation of Isoeugenol-derived Model Compound over Carbon-supported Pt and Pt-SnS Catalysts for the Production of Sustainable Jet Fuel.

This study focuses on the sustainable production of bio-jet fuel through the catalytic hydrodeoxygenation (HDO) of isoeugenol (IE). Properties of two spraying synthesis methods (in situ and ex situ metal doping) with different platinum (Pt) loading percentages. The catalyst was characterised using various techniques such as XAS, X-ray photoelectron spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), field-emission scanning electron microscopy (FESEM) and thermogravimetric analysis. The HRTEM and FESEM results show the successful preparation of a spherical nanoparticle doped over activated carbon, and Pt was dispersed on the outer shell of the particles. The catalytic HDO of IE showed a high yield and conversion as follows: IE conversion of 100%, liquid-phase mass balance of 95.92%, dihydroeugenol conversion of 99.32%, propylcyclohexane yield of 88.94% and HYD yield of 76.19%. Moreover, the catalyst exhibited high reusability with low metal leaching and high coke resistance for 10 cycles. The catalyst was evaluated in a continuous flow reactor for 100 h at different reaction temperatures, and interestingly, the catalyst showed low deactivation with a high half-time.

Exploring the superior mild temperature performance of nickel-infused fibrous titania silica for enhanced dry reforming of methane

Carbon (IV) oxide (CO2) and methane (CH4) contribute significantly to greenhouse gas emissions and global warming. One potential approach for reducing their environmental impact is transforming these gases into synthesis gas (CO + H2). This study illustrates the advancement of catalysts supported by fibrous titania silica (FTS), which have nickel loadings of 1%, 3%, and 5%. The FTS support, a modified variant of silica-titania, has a distinct fibrous structure and exhibits mesoporous material properties such as a type IV isotherm and an H1 hysteresis loop. After 72 h of operation, the 1Ni/FTS catalyst converted over 80% of CH4 and CO2 with low coke deposition, outperforming other catalysts. The bare FTS support had reduced CH4 conversion at 600°C, CO2 conversion at 650°C, and H2/CO ratio at 700°C. However, the 5Ni/FTS and 3Ni/FTS catalysts showed consistent increases in CH4 conversion at 600°C. The 1Ni/FTS catalyst, with a pore size of 7.39 nm, had strong metal-support interaction and moderate basicity sites, which helped with reactant dissociation and coke gasification. Despite the slightly higher CH4 conversion of the 3Ni/FTS catalyst and the high basicity of the 5Ni/FTS catalyst, the 1Ni/FTS catalyst demonstrated superior thermal stability and coking resistance, as evidenced by negligible weight loss during TGA analysis. Raman shifts revealed the presence of carbon synthesis and the buildup of disordered amorphous carbon. The Id/Ig ratios of FTS, 1Ni/FTS, 3Ni/FTS, and 5Ni/FTS were 1.01, 0.98, 1.01, and 1.01, respectively. The lower Id/Ig ratio of 1Ni/FTS suggests less disorder. The FTS support promises mild-temperature, carbon-neutral CH4 reforming with long-term catalytic applications. This study demonstrates the efficacy of FTS-supported catalysts in constructing long-term and efficient systems for converting greenhouse gasses.

Tailoring and Visualizing Macropores of the Zeolite Monolith to Reveal the Coke Resistance Performance for Bio-oil Hydrodeoxygenation

Tailoring and Visualizing Macropores of the Zeolite Monolith to Reveal the Coke Resistance Performance for Bio-oil Hydrodeoxygenation

High coke resistance Ni-based CH4/CO2 reforming catalysts with strong spatial confinement effect: Effect of CeO2 shell thickness

Ni-based catalysts show promise as candidates for the dry reforming of methane (DRM), yet the susceptibility to sintering and carbon deposition is a major obstacle to industrialization. This work demonstrates a mesoporous Ni-based catalyst with a thickness-tailorable CeO2 shell for enhanced spatial confinement effect for the DRM. The Ni-MCM-41@xCeO2 catalysts are prepared at various CeO2 shell thickness through a two-step hydrothermal reaction. The kinetic studies have shown that the Ni-MCM-41@2CeO2 catalyst has the lowest activation energy, producing a high conversion of CH4 and CO2 as high as around 80 % at 700 °C. Our characterizations reveal that the Ni core is tightly confined in the mesoporous skeleton of MCM-41 and within a CeO2 shell. The Ni-MCM-41@2CeO2 catalyst is able to sustain high activity for more than 10 h of operation, with a remarkably reduced carbon deposition (0.28 %) as compared with a conventional Ni-Ce/MCM-41 catalyst (8.77 %). Furthermore, the density functional theory (DFT) calculation supports that the CeO2 shell layer significantly reduces dissociation potential barrier for CH4 and CO2, hence enhancing the catalytic activity of the DRM.

Anchoring nickel sites on ceria-coated silica to enhance the catalytic stability for the vapor phase levulinic acid hydrogenation

The preparation of the binary metal NiCe-based catalysts involved a 2-step protocol, the ceria was first coated on SiO2 which was then utilized to disperse Ni nanoparticles. Various techniques including N2 adsorption/desorption, ICP-OES, XRD, HRTEM, XPS, H2-chemisorption, H2-TPR, NH3-TPD, and TG etc. were performed to study the microstructure, redox, acid property and deactivation. The results revealed that CeO2 and metallic Ni were well dispersed on the support surface, the synergistic effect between the two metal species was conserved well. The content of CeO2 had considerable effects on redox and metallic properties rather than the acidic property. The dispersion of metallic Ni played a dominant role in promoting the catalytic activity. The levulinic acid conversion attained 84.0 % with a γ-valerolactone selectivity of 98.8 % on Ni/SiO2@2CeO2 sample with the highest dispersion of 9.8 %. The amorphous CeO2 suppressed the sintering of metallic Ni nanoparticles and improved the coke resistance, leading to better catalytic activity within 20 h time on stream.

Dry reforming of model-biogas over ceria-supported nickel catalyst: the effect of charge enhanced dry impregnation on the catalytic performance and coke resistance

In this study, we investigated the effectiveness of charge charge-enhanced dry impregnation (CEDI) method on a ceria-supported nickel-based catalyst (10Ni/CeO2) used to produce synthesis (syngas) under biogas dry reforming conditions. The CEDI method was used to enhance the electrostatic adsorption of nickel precursor onto the ceria support during dry impregnation (DI), hence charge-enhanced dry impregnation. The other ceria-supported nickel-based catalyst (labelled 10Ni/CeO2-DI) was prepared by the commonly used DI method and used as the reference catalyst. The catalysts were then tested for stability and catalytic performance (biogas conversion and syngas yield) under biogas reforming conditions using CatLab-QGA equipment supplied by Hidden Analytical. The characterisation studies: X-ray diffraction (XRD), N2 adsorption/desorption, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), oxygen temperature programmed oxidation (O2-TPO), temperature programmed reduction (TPR), and H2-chemisorption were performed on the fresh and spent catalysts to gain insight into the influence of the CEDI method on dispersion, nanoparticles size of the active phase, metal-support interaction, bulk composition, and phase composition. The results showed that enhancing electrostatic attraction during the DI method produced 10Ni/CeO2-CEDI with smaller nanoparticles (3.33 nm), improved nickel dispersion from 1.40 to 5.04% and improved metal-support interaction inferred from TPR values increased from 290 to 340 °C. These favourable physicochemical properties had a positive correlation with the improvement in the conversion of model biogas feed and the least coke formation.

Highly dispersed Ni nanoparticles confined in mesoporous SBA-15 for methane dry reforming with improved coke resistance and stability

Methane dry reforming (DRM) is a promising route for sustainable syngas production, in which Ni-based catalysts face challenges of metal sintering and coke formation. In this work, highly dispersed Ni nanoparticles (NPs) embedded in the mesopores of SBA-15 were prepared using a simple solid-state impregnation (SSI) method. TEM and cross-section HRTEM results clearly indicated that ultra-small Ni NPs (3–4 nm) were orderly dispersed within the mesopores of the SBA-15 support. Compared with the conventional wetness impregnation (WI) method, the Ni/SBA-15 catalyst prepared by solid-state impregnation method possessed much better catalytic activity, stability, and coke resistance in DRM. In-situ DRIFTS and semi-in-situ XRD were used to elucidate the dispersion and encapsulation mechanism of Ni within the mesopores of SBA-15 during the sample preparation process. Specifically, WI formed large NiO particles, while SSI formed smaller NiO NPs with stronger interaction between metal and support (SIMS) via forming Ni-O-Si species which is beneficial for the DRM reactivity. This work establishes relationships among catalyst preparation, structure, and DRM performance, paving the way for general template-assisted methods to prepare nanometallic catalysts for various applications.

The impact of surface-impregnated versus support-dispersed Fe in Fe–Ni/γ-Al2O3 catalysts for partial oxidation of methane: Insights into the effect of Fe incorporation method on coking and on the reaction mechanism

Two sets of Fe-modified Ni/γ-Al2O3 catalysts were prepared and tested in partial oxidation of methane. In one set, Fe was co-impregnated on the surface (NiFe) and in the other set Fe was incorporated in the support bulk (Ni/Fe). The two types showed significantly different coking resistance and performance. While Fe well dispersed in the support bulk significantly enhanced coking resistance, Fe co-impregnated with Ni on the surface enhanced the rate of coke deposition on the catalysts’ surfaces. The impact of Fe in the Ni/Fe catalysts is referred to its partially reduced ions (Fe2+) in redox reactions, and to the Ni-support strong interaction retarding the coke formation pathways. On the contrary, carbon formation on the NiFe catalysts is referred to the formation of Ni–Fe alloy particles which may block Ni active sites and can promote cracking of methane as well as CO molecules resulting in higher rates of coking.

Boron doped Mo/HMCM-22 catalyst for improving coke resistance in methane dehydroaromatization

Mo/HMCM-22 is one of the candidate catalysts for methane dehydroaromatization (MDA) reaction. However, serious coke deposition would deactivate the catalyst, resulting in a rapid decrease of aromatics yield. Here, we adjusted the acidity of MCM-22 zeolite by doping boron into the framework. Boron species replace some of framework aluminum and prompt aluminum to locate in sinusoidal channel. It optimizes the ratio of strong/weak Brønsted acid, as well as enhances the interaction between molybdenum and HMCM-22 to facilitate the dispersion of molybdenum species. After 10 h of MDA reaction, the yield of aromatics over Mo/H[B]MCM-22 (SBR 30) is 3.5 times higher than that of Mo/H[B]MCM-22 (SBR 5). It decreases by only 4.8 % in comparison to the initial yield. Meanwhile, Mo/H[B]MCM-22 (SBR 30) shows significantly better resistance to coke deposition. Therefore, the established structure–activity relationships provide valuable insights for future research on the modification of zeolite acidity in methane dehydroaromatization reaction.

Coking and deactivation behavior study of Ce-modified Cs-Nb/Al2O3 in aldol condensation of methyl propionate with formaldehyde

Coke deposition during the aldol condensation of methyl propionate (MP) and formaldehyde (FA) to produce methyl methacrylate (MMA) is a critical factor limiting the long-term stability of catalysts. In this work, Ce-modified Cs-Nb/Al2O3 catalysts with superior catalytic activity and robust coke resistance were achieved during the reaction by enhancing the oxygen vacancy (OV) ratio. With optimal Ce loading of 1 %, the MP conversion of 35.4 % and MMA selectivity of 90.3 % can be achieved. Meanwhile, the coke content of the modified catalyst significantly reduced from the original 10.49 wt% to 5.44 wt%. It was discovered that higher water content in the reaction feedstock promotes the hydrolysis reaction, resulting in a decrease in MMA selectivity. Furthermore, the presence of water can promote the conversion of Lewis acid sites to Brønsted acid sites, while an excess of Brønsted acid sites can accelerate the coke formation. Various characterization techniques confirmed that the coke species on the used catalysts consisted basically of polycyclic aromatic hydrocarbons and aliphatic compounds. Ultimately, the kinetics of coke deposition on Cs-Nb/Al2O3 and Cs-Nb-1Ce/Al2O3 were established using the modified Voorhies equation, offering a reliable method to predict coke accumulation under specific conditions. The higher apparent activation energy of coke formation observed on Cs-Nb-1Ce/Al2O3 is responsible for its robust coke resistance.

Geometrically effective NiAl2O4 formation over macroporous Ni/Al2O3 catalysts and coking resistance in dry reforming of methane

This study aimed to investigate the geometrical effect of macroporosity on the performance of Ni-based catalysts in the dry reforming of methane (DRM). For this, macroporous Ni/Al2O3 catalysts with different Ni contents were synthesized. Characterization experiments on the macroporous Ni/Al2O3 catalysts revealed that the macroporous Al2O3 structure enhanced NiAl2O4 formation by facilitating efficient interactions between the Ni species and accessible Al2O3 sites on the macroporous wall surface during calcination. In a subsequent reduction step, Ni exsolution from the NiAl2O4 structure generated highly dispersed Ni nanoclusters over the macroporous Al2O3. Conversely, non-macroporous Ni/Al2O3 catalysts presented substantial amounts of large isolated Ni nanoparticles at an Ni content of 20 wt%, owing to limited NiAl2O4 formation caused by the lack of accessible Al2O3 sites. The highly dispersed Ni nanoclusters surrounded by oxygen vacancies on the macroporous Ni/Al2O3 catalysts significantly enhanced their catalytic performance in the DRM, evidenced by their high CO2 and CH4 conversions and strong resistance to coking. Moreover, the superior coke resistance ability of the macroporous Ni/Al2O3 catalysts was attributed to the gasification of the coke precursor on Ni nanoclusters surrounded by oxygen vacancies during the DRM.

Enhancement of Ni-NiO-CeO2 Interaction on Ni-CeO2/Al2O3-MgO Catalyst by Ammonia Vapor Diffusion Impregnation for CO2 Reforming of CH4.

Ni-based catalysts have been widely used for the CO2 reforming of methane (CRM) process, but deactivation is their main problem. This study created an alternative electronic Ni-NiO-CeO2 interaction on the surface of 5 wt% Ni-5 wt% CeO2/Al2O3-MgO (5Ni5Ce(xh)/MA) catalysts to enhance catalytic potential simultaneously with coke resistance for the CRM process. The Ni-NiO-CeO2 network was developed on Al2O3-MgO through layered double hydroxide synthesis via our ammonia vapor diffusion impregnation method. The physical properties of the fresh catalysts were analyzed employing FESEM, N2 physisorption, and XRD. The chemical properties on the catalyst surface were analyzed employing H2-TPR, XPS, H2-TPD, CO2-TPD, and O2-TPD. The CRM performances of reduced catalysts were evaluated at 600 °C under ambient pressure. Carbon deposits on spent catalysts were determined quantitatively and qualitatively by TPO, FESEM, and XRD. Compared to 5 wt% Ni-5 wt% CeO2/Al2O3-MgO prepared by the traditional impregnation method, the electronic interaction of the Ni-NiO-CeO2 network with the Al2O3-MgO support was constructed along the time of ammonia diffusion treatment. The electronic interaction in the Ni-NiO-CeO2 nanostructure of the treated catalyst develops surface hydroxyl sites with an efficient pathway of OH* and O* transfer that improves catalytic activities and coke oxidation.

Unraveling the function of monolayer shell structure over Pt-based alloy catalysts in tuning ethane dehydrogenation reactivity and coking resistance

Ethane direct dehydrogenation (EDH) operated at high temperature easily leads to coke formation. The new core–shell catalysts with monolayer shell exhibited better catalytic performance, and the function of monolayer shell structure is of great importance. This work fully investigated catalytic performance of EDH over six types of core–shell Pt3M@Pt and Pt@Pt3M (M = Fe, Co, and Ni) catalysts with Pt3M and Pt monolayer shell under the experimental conditions. Here, density functional theory (DFT) calculations with kinetic Monte Carlo (kMC) simulations were employed. The results show that the metal M over Pt3M@Pt surface decreases coordination number of Pt-Pt and restricts deep dehydrogenation reactions. The Pt3M@Pt catalysts with d-band center close to Fermi level exhibit higher C2H4(g) formation activity than Pt@Pt3M catalysts at 873.15 K. H2(g) co-feeding significantly decreases the coverage of coking C*+CC* species. The screened Pt3Ni@Pt catalyst presents the highest C2H4(g) formation activity and 100 % selectivity at the H2(g) partial pressure of 0.1 bar and reaction temperature 873.15 K, which is superior to previously reported Pt, Pt3Sn, 1Pt3Sn@4Pt, Pd1-NDG, Pt2/Al2O3 and Rh/ZrO2 catalysts. H* adsorption energy is proposed as a descriptor to quickly evaluate C2H4(g) formation activity. This work provides a useful strategy for designing alkane dehydrogenation catalysts by tuning monolayer shell structure and coordination environment of active site.

Dry reforming of methane over embedded Ni nanoparticles in CeZrO2: Effect of Ce/Zr ratio and H2O addition

Biogas has emerged as renewable source of CH4 towards energy decarbonization in recent years. Among the biogas valorization routes, the dry reforming of methane (DRM) process is particularly interesting for H2 production. However, the development of new catalysts with high metal dispersion and coke resistance is a significant challenge, particularly under industrial condition. Therefore, this work studies the performance of Ni@CexZr1-xO2 catalysts with different Ce/Zr molar ratios for the dry reforming and bi-reforming of methane reactions. The addition of Zr promotes the Ni dispersion and the oxygen mobility of the support, leading to enhanced resistance to coke formation. Additionally, H2O suppresses coke formation under high CH4/CO2 molar ratio, but catalyst deactivation is still observed. Finally, an optimal Ce/Zr molar ratio (i.e., 4.0) is achieved, demonstrating remarkable resistance to coke formation and high CH4 and CO2 conversion rates through the control of Ni particle size and the promotion of oxygen mobility.

Surface engineered sustainable nanocatalyst with improved coke resistance for dry methane reforming to produce hydrogen

The ever-growing carbon-based economy has led to alarming increases in greenhouse gas (GHG) emissions, particularly methane (CH4) and carbon dioxide (CO2). These emissions accelerate global warming, pollution and environmental challenges. Methane Dry Reforming (DRM) offers a promising technology to address this issue by converting CH4 and CO2 into a valuable syngas (CO + H2) mixture, which is a valuable fuel and a building block for many important chemical reactions (Fischer-Tropsch process). However, finding affordable and environmentally friendly catalysts for large-scale applications remains a critical hurdle. This study delves into the development of stable nickel-zirconia catalysts prepared via impregnation method. The weight percentage of nickel and zirconia was varied to optimize the catalyst's activity by controlling deactivation phenomenon that is a major challenge at higher temperatures during DRM. Various characterization techniques (XRD, FT-IR, SEM-EDX, TGA, TEM and BET) were employed to evaluate synthesized catalysts physio-chemical properties. Additionally, catalytic performance was assessed at temperatures ranging from 550 to 750 °C and a gas hourly space velocity (GHSV) of 72,000 mL/h.gcat. Among tested catalysts, 15% Ni/ZrO2 displayed remarkable conversion values for both CH4 (62.9%) and CO2 (64.9%). Importantly, it exhibited significantly lower weight loss (ca. 15.42%) compared to other variants, indicating better resilience against coke deposition. This enhanced stability can be attributed to synergistic interplay between nickel and zirconia support, effectively suppressing carbon formation. These findings demonstrate potential of 15% Ni/ZrO2 as a promising catalyst for experimental DRM application. With the obvious high activity and stability, 15% Ni/ZrO2 candidate serves as an eco-friendly candidate for greenhouse gas conversion into green fuel energy, contributing to a sustainable economy and clean environment.