3D Hierarchical MOF-Derived Defect-Rich NiFe Spinel Ferrite as a Highly Efficient Electrocatalyst for Oxygen Redox Reactions in Zinc-Air Batteries.

The strategy of defect engineering is increasingly recognized for its pivotal role in modulating the electronic structure, thereby significantly improving the electrocatalytic performance of materials. In this study, we present defect-enriched nickel and iron oxides as highly active and cost-effective electrocatalysts, denoted as Ni0.6Fe2.4O4@NC, derived from NiFe-based metal-organic frameworks (MOFs) for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER). XANES and EXAFS confirm that the crystals have a distorted structure and metal vacancies. The cation defect-rich Ni0.6Fe2.4O4@NC electrocatalyst exhibits exceptional ORR and OER activities (ΔE = 0.68 V). Mechanistic pathways of electrochemical reactions are studied by DFT calculations. Furthermore, a rechargeable zinc-air battery (RZAB) using the Ni0.6Fe2.4O4@NC catalyst demonstrates a peak power density of 187 mW cm-2 and remarkable long-term cycling stability. The flexible solid-state ZAB using the Ni0.6Fe2.4O4@NC catalyst exhibits a power density of 66 mW cm-2. The proposed structural design strategy allows for the rational design of electronic delocalization of cation defect-rich NiFe spinel ferrite attached to ultrathin N-doped graphitic carbon sheets in order to enhance active site availability and facilitate mass and electron transport.

Pd-loaded hierarchical titanosilicalite-1 catalysts on CO2 cycloaddition with epoxides: Experimental and DFT investigations.

This work presents the synthesis of Pd-loaded microporous titanosilicalite-1 (Pd/TS-1) and Pd-loaded hierarchical titanosilicalite-1 (Pd/HTS-1) with abundant mesopores (2-30 nm) inside the framework via hydrothermal method using polydiallydimethyl ammonium chloride as the non-surfactant mesopore template. XRD, N2 sorption, FT-IR, FESEM-EDX, TEM, XPS, and DR-UV techniques were used to characterize the morphological and physicochemical properties of the synthesized materials. These materials were tested as heterogeneous catalysts, along with tetrapropylammonium bromide as co-catalyst, for cycloaddition reactions of CO2 with epoxides to produce cyclic carbonates. It was found that the epoxide conversions were influenced by acidity and pore accessibility of the catalysts. Using Pd/HTS-1 facilitated bulky substrates to access active sites, resulting in higher conversions than Pd/TS-1. Over 85 % conversions were achieved for at least five consecutive cycles without significant loss in catalytic activity. The interaction between the Pd active surfaces and epichlorohydrin (ECH) was further studied by DFT calculations. The existence of Pd(200) was more influential on adsorbing epichlorohydrin (ECH) and subsequent formation of dissociated ECH (DECH) intermediate than Pd(111) surface. However, Pd(111) was dominant in enhancing the activity of DECH species for capturing CO2. Therefore, the co-existence of Pd(200) and Pd(111) surfaces was needed for cycloaddition of CO2 with ECH.

Renovated FeCoP-NC nanospheres wrapped by CoP-NC nanopetals: As a tremendously effectual and robust MOF-assisted electrocatalyst for hydrogen energy production.

The future of energy technology is significantly influenced by hydrogen (H2) energy. However, hydrogen energy production through water-splitting entirely depends on the catalyst's performance. Modifying the morphological structure and increasing the number of active sites by changing the metal composition are pivotal factors in enhancing the catalytic activity for the hydrogen evolution reaction (HER). In this context, we introduce the impact of metal-organic framework (MOF) strategies for decorating CoP petals onto α-Fe2O3 and FeCoP-NC (NC-nitrogen-doped carbon) nanoflowers. This method results in an excellent electrocatalyst for HER. The study demonstrated the influence of different MOF precursors, the impact of calcination temperatures, and the importance of composition percentages in Fe1-xCoxP-NC. As a result, FeCoP-NC shows excellent electrochemical performance potential (η) of 57 mV, a rapid kinetic Tafel value of 61 mV/dec, and remarkable electrochemical stability of around 2000 cycles and 20 h in stand potential. Additionally, the composite has numerous active surfaces at 4.7 mF/cm2 during the electrochemical reactions. This work concludes that MOF-assisted FeCoP-NC nanoflowers are an ideal electrocatalyst for HER in an alkaline medium.

Strategic Design and Insights into Lanthanum and Strontium Perovskite Oxides for Oxygen Reduction and Oxygen Evolution Reactions.

Perovskite oxides exhibit bifunctional activity for both oxygen reduction (ORR) and oxygen evolution reactions (OER), making them prime candidates for energy conversion in applications like fuel cells and metal-air batteries. Their intrinsic catalytic prowess, combined with low-cost, abundance, and diversity, positions them as compelling alternatives to noble metal and metal oxides catalysts. This review encapsulates the nuances of perovskite oxide structures and synthesis techniques, providing insight into pivotal active sites that underscore their bifunctional behavior. The focus centers on the breakthroughs surrounding lanthanum (La) and strontium (Sr)-based perovskite oxides, specifically their roles in zinc-air batteries (ZABs). An introduction to the mechanisms of ORR and OER is provided. Moreover, the light is shed on strategies and determinants central to optimizing the bifunctional performance of La and Sr-based perovskite oxides.

The Underlying Catalytic Role of Oxygen Vacancies in Fatty Acid Methyl Esters Ketonization over TiOx Catalysts.

Recently, interest in converting bio-derived fatty acid methyl esters (FAMEs) into added-value products has significantly increased. The selectivity of ketonization reaction in the conversion of the FAMEs has significantly hampered the efficiency of this process. Herein, this work reports the preparation of catalysts with different levels of oxygen vacancies while the crystal phase remained unchanged. The catalyst with the highest level of oxygen vacancy exhibited the maximum selectivity. The density functional theory (DFT) simulation showed an increase in interatomic distances leading to the formation of frustrated Lewis pairs (FLPs) upon the creation of oxygen vacancies. The surface measurements, type and density of acid sites of the catalysts, showed that the Lewis acid sites enhanced the selectivity for ketone production; while Bronsted acid sites increased the formation of by-products. Moreover, the ketone formation rate was directly proportional to acid density. The findings of this research provide a different approach for catalyst design, based on defects engineering and their effect on the surface activity, which could be used for enhancing the catalytic performance of novel metal oxides.

Photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction to methane with simultaneous H2 production.

This study assessed the photoactivity of amorphous and crystalline TiO2 nanotube arrays (TNA) films in gas phase CO2 reduction. The TNA photocatalysts were fabricated by titanium anodization and submitted to an annealing treatment for crystallization and/or cathodic reduction to introduce Ti3+ and oxygen vacancies into the TiO2 structure. The cathodic reduction demonstrated a significant effect on the generated photocurrent. The photoactivity of the four TNA catalysts in CO2 reduction with water vapor was evaluated under UV irradiation for 3 h, where CH4 and H2 were detected as products. The annealed sample exhibited the best performance towards methane with a production rate of 78 µmol gcat-1 h-1, followed by the amorphous film, which also exhibited an impressive formation rate of 64 µmol gcat-1 h-1. The amorphous and reduced-amorphous films exhibited outstanding photoactivity regarding H2 production (142 and 144 µmol gcat-1 h-1, respectively). The annealed catalyst also revealed a good performance for H2 production (132 µmol gcat-1 h-1) and high stability up to five reaction cycles. Molecular dynamic simulations demonstrated the changes in the band structure by introducing oxygen vacancies. The topics covered in this study contribute to the Sustainable Development Goals (SDG), involving affordable and clean energy (SDG#7) and industry, innovation, and infrastructure (SDG#9).

Hierarchical Porous Activated Carbon from Wheat Bran Agro-Waste: Applications in Carbon Dioxide Capture, Dye Removal, Oxygen and Hydrogen Evolution Reactions.

This work reports an efficient method for facile synthesis of hierarchically porous carbon (WB-AC) utilizing wheat bran waste. Obtained carbon showed 2.47 mmol g-1 CO2 capture capacity with good CO2 /N2 selectivity and 27.35 to 29.90 kJ mol-1 isosteric heat of adsorption. Rapid removal of MO dye was observed with a capacity of ~555 mg g-1 . Moreover, WB-AC demonstrated a good OER activity with 0.35 V low overpotential at 5 mA cm-2 and a Tafel slope of 115 mV dec-1 . It also exhibited high electrocatalytic HER activity with 57 mV overpotential at 10 mA cm-2 and a Tafel slope of 82.6 mV dec-1 . The large SSA (757 m2 g-1 ) and total pore volume (0.3696 cm3 g-1 ) result from N2 activation contributing to selective CO2 uptake, high and rapid dye removal capacity and superior electrochemical activity (OER/HER), suggesting the use of WB-AC as cost effective adsorbent and metal free electrocatalyst.

Evaluation of the hydrogenation reaction on the electrocatalytic nitrobenzene degradation over (FeCoNiCuZn)xOy high entropy oxides (HEOs).

Environmental pollution is one of the main challenges currently faced by mankind; especially industrial waste-waters treatment and remediation using energy-efficient methodologies. This research focused on the electrochemical degradation of the hazardous nitrobenzene (NB) in aqueous solutions, using novel high-entropy oxide (HEO) electrodes to elucidate the influence of the electrochemical reduction step on the degradation process. The effect of solution pH, dissolved oxygen concentration, anodic applied potential, and cell configurations on NB hydrogenation reaction were evaluated. A synergistic effect between the hydrogenation of nitrobenzene and the degradation was found to drastically enhance the conversion rates. The presence of dissolved oxygen promoted the oxidation reactions, reaching more than 90% nitrobenzene removal at 1.7 V and pH 14. The degradation of the organic by-products was attributed to the formation of the superoxide radical (O2*-) as the main oxidant species. A degradation mechanism was proposed based on the detected intermediates and the decoupling of electrochemical surface reactions observed by EIS at different solution pH.

A density functional theory study on how γ-Al2O3 - Boehmite transformation affects carbon evolution during aqueous-phase reaction.

Gamma-alumina (γ-Al2O3), one of the most common materials, is commercially used in many catalytic applications, including the active catalyst and support. However, the problem of fast deactivation makes the utilization of the γ-Al2O3 challenging. This work elucidates the mechanism of coke formation consisting of coke deposition and evolution on γ-Al2O3(110) surfaces in differential conditions, including; clean and hydroxylation γ-Al2O3(110) in terms of partial and fully hydroxylation of OH/γ-Al2O3(110) and AlOOH(010), respectively. We demonstrated that the γ-Al2O3(110) surface is proper for atomic coke deposition and dimerization in the initial state, where the presence of OH species promotes the coke evolution to higher coke, Cn (where n ≥ 3). Also, the higher coke formation thermodynamically preferred the cyclic form to the aliphatic one. The electron transfer from substrates to adsorbed coke illustrates the role of the electron donor of catalyst surfaces corresponding to the electron acceptor of adsorbed cokes.

Noble metals (Pd, Ag, Pt, and Au) doped bismuth oxybromide photocatalysts for improved visible light-driven catalytic activity for the degradation of phenol.

The doping of noble metals onto the semiconductor metal oxides has a great impact on the intrinsic properties of the materials. This present work reports the synthesis of noble metals doped BiOBr microsphere by a solvothermal method. The various characteristic findings reveal the effective incorporation of Pd, Ag, Pt, and Au onto the BiOBr and the performance of synthesized samples was test for the degradation of phenol over visible light. The Pd-doped BiOBr material showed enhanced phenol degradation efficacy, which is ∼4-fold greater than pure BiOBr. This improved activity was on reason of good photon absorption, lower recombination rate, and higher surface area facilitated by surface plasmon resonance. Moreover, Pd-doped BiOBr sample displayed good reusability and stability after 3 cycles of run. A plausible charge transfer mechanism for phenol degradation is disclosed in detail over Pd-doped BiOBr sample. Our findings disclose that the incorporation of noble metal as the electron trap is a feasible approach to enhance visible light activity of BiOBr photocatalyst used in phenol degradation. This work represents new vision interested in the outline and development of noble metal doped semiconductor metal oxides as a visible light material for the elimination of colorless toxins from untreated wastewater.

First-principles-driven catalyst design protocol of 2D/2D heterostructures for electro- and photocatalytic nitrogen reduction reaction.

Ammonia synthesis from nitrogen is a vital process and a necessity in a variety of applications including energy, pharmaceutical, agricultural, and chemical applications. The electro- and photocatalytic nitrogen reduction reactions (NRRs) are promising sustainable processes operated under milder conditions than the conventional Haber-Bosch process. However, the main pain points of these catalytic processes are their low selectivity and low efficiency. This perspective presents the recent status and the design protocols for developing promising 2D/2D heterojunction catalysts for the NRR, using the first-principles approach. The current theoretical studies are briefly discussed, and available methods are suggested for the development and design of new potential 2D/2D heterojunctions as efficient electro- and photo-NRR catalysts.

High-throughput materials screening algorithm based on first-principles density functional theory and artificial neural network for high-entropy alloys.

This work introduced the high-throughput phase prediction of PtPd-based high-entropy alloys via the algorithm based on a combined Korringa-Kohn-Rostoker coherent potential approximation (KKR-CPA) and artificial neural network (ANN) technique. As the first step, the KKR-CPA was employed to generate 2,720 data of formation energy and lattice parameters in the framework of the first-principles density functional theory. Following the data generation, 15 features were selected and verified for all HEA systems in each phase (FCC and BCC) via ANN. The algorithm exhibited high accuracy for all four prediction models on 36,556 data from 9139 HEA systems with 137,085 features, verified by R2 closed to unity and the mean relative error (MRE) within 5%. From this dataset comprising 5002 and 4137 systems of FCC and BCC phases, it can be realized based on the highest tendency of HEA phase formation that (1) Sc, Co, Cu, Zn, Y, Ru, Cd, Os, Ir, Hg, Al, Si, P, As, and Tl favor FCC phase, (2) Hf, Ga, In, Sn, Pb, and Bi favor BCC phase, and (3) Ti, V, Cr, Mn, Fe, Ni, Zr, Nb, Mo, Tc, Rh, Ag, Ta, W, Re, Au, Ge, and Sb can be found in both FCC and BCC phases with comparable tendency, where all predictions are in good agreement with the data from the literature. Thus, the combination of KKR-CPA and ANN can reduce the computational cost for the screening of PtPd-based HEA and accurately predict the structure, i.e., FCC, BCC, etc.

Controlling the Fe2O3-SiO2 interaction: The effect on the H2S selective catalytic oxidation and catalyst deactivation.

Biogas utilization is one of the most promising options for reducing the consumption of fossil fuels for energy production, but the presence of H2S represents a serious industrial and environmental problem. In this work, two different synthesis methods (sol-gel and incipient wetness impregnation) were used to synthesize iron oxide supported on silica catalysts (Fe2O3/SiO2) with metal loadings ranging from 0.5 to 10 %wt. The catalysts were tested for the selective oxidation of H2S, changing the operating conditions like O2/H2S (0.5-2.5), temperature (170-250°C), and water content (0-50%). The optimum condition was O2/H2S = 0.5 and no water at 230 °C with the conversion of approximately 100%, the selectivity of 97%, and the deactivation of 0.6%. A detailed characterization of the fresh and spent catalysts' surface revealed the presence of four deactivation mechanisms: metal surface reduction, oxygen vacancy loss, pore plugging, and sintering. Among the observed deactivation mechanisms, the sintering showed the highest impact on catalytic activity and deactivation. The sol-gel catalysts (SG) showed the highest metal-oxide/support interaction, which reduced the metal-oxide nanoparticles sintering compared with the incipient wetness impregnation method (IWI), reporting a lower sintering, higher activity, and selectivity, lower deactivation rates and lower sensitivity to the operating conditions. A catalytic cycle representing the possible surface intermediate states of the catalyst is proposed based on the performance and characterization results obtained.

Synthesis of novel graphene aerogel encapsulated bismuth oxyiodide composite towards effective removal of methyl orange azo-dye under visible light.

Development of novel and eco-friendly composite photocatalysts for the efficient removal of contaminants from wastewater is the need of the hour. In this study, visible light responsive novel graphene aerogel/bismuth oxyiodide (GA/BiOI) composite was synthesized via low-temperature solvothermal method. The synthesized GA/BiOI composite was tested for methyl orange (MO) azo-dye degradation under visible light. The graphene aerogel nanosheets were wrapped onto the surface of the each individual BiOI microsphere, which encourages the interconnection charge transfer process. The light absorption properties of GA/BiOI composite were increased with the addition of graphene aerogel. The optimal 5%-GA/BiOI composite displayed higher MO removal efficiency, which is ∼2 fold more than the bare BiOI photocatalyst. This enhanced photocatalytic activity was on account of lower recombination rate of charge carriers, improved light absorption, and the high surface area. In addition, the 5%-GA/BiOI composite showed good stability until 3 cycles without deactivation. The plausible MO degradation mechanism was also proposed over GA/BiOI under visible light. This work provides a new perspective on the design and synthesis of graphene aerogel-based composite for environmental applications.

A review on sensitivity of operating parameters on biogas catalysts for selective oxidation of Hydrogen Sulfide to elemental sulfur.

Hydrogen sulfide (H2S) is a critical problem for biogas applications, such as electricity and heat generation, or the production of different chemical compounds, due to corrosion and toxic effluent gases. The selective catalytic oxidation of H2S to S is the most promising way to eliminate H2S from biogas due to the lack of effluents, therefore can be considered a green technology. The most extensively used catalysts for H2S selective oxidation can be classified in two groups: metal oxide-based catalysts, including vanadium and iron oxides, and carbon-based catalysts. Numerous studies have been devoted to studying their different catalytic performances. For industrial applications, the most suitable catalysts should be less sensitive to the operating parameters like the temperature, O2/H2S ratio, and H2O content. More specifically, for metal oxides and carbon-based catalysts, the temperature and O2/H2S ratio have a similar effect on the conversion and selectivity, but carbon-based catalysts are less sensitive to water in all operating conditions.

Rational La-doped hematite as an anode and hydrous cobalt phosphate as a battery-type electrode for a hybrid supercapacitor.

In recent years, modern appliances require high energy density with a burst power supply. Hybrid supercapacitors show high performance based on high energy density without compromising power density and stability over thousands of charge-discharge cycles. In this work, the optimized hybrid electrodes using lanthanum-doped hematite (lanthanum-doped iron oxide) noted as 7.5%La-HMT as a negative electrode and hydrous cobalt phosphate (CoPO) as a battery-type positive electrode have been successfully fabricated via a simple hydrothermal method and a facile co-precipitation method, respectively. The 7.5%La-HMT showed excellent electrochemical performance due to doping of rare-earth La3+ metal ions, resulting in improvised active sites and reduction in the equivalent resistance. The 7.5%La-HMT operated at a high potential window (0 to -1.2 V) with an ultra-high specific capacitance (Sp) of 1226.7 F g-1 at 1 A g-1 with capacitance retention of 89.3% over 1000 cycles. CoPO could be operated at a high working window (0 to 0.45 V) with a specific capacity of 121.7 mA h g-1 at a current density of 2 A g-1 with capacitance retention of 85.4% over 1000 cycles. The configured CoPO//KOH//10%La-HMT aqueous hybrid capacitor device (Aq-HSC) could be operated at a potential window of 1.6 V and delivered a maximum energy density (E.D) of 83.6 W h kg-1 at a power density (P.D) of 3.2 kW kg-1 with Sp of 235.0 F g-1 at 2 A g-1 and 89.0% Sp retention over 5000 cycles. The simplicity of the synthesis methods for CoPO and 7.5%La-HMT along with their superior super-capacitive properties make them suitable for advanced electrical devices and hybrid vehicles.

On a high photocatalytic activity of high-noble alloys Au-Ag/TiO2 catalysts during oxygen evolution reaction of water oxidation.

The analysis via density functional theory was employed to understand high photocatalytic activity found on the Au-Ag high-noble alloys catalysts supported on rutile TiO2 during the oxygen evolution of water oxidation reaction (OER). It was indicated that the most thermodynamically stable location of the Au-Ag bimetal-support interface is the bridging row oxygen vacancy site. On the active region of the Au-Ag catalyst, the Au site is the most active for OER catalyzing the reaction with an overpotential of 0.60 V. Whereas the photocatalytic activity of other active sites follows the trend of Au > Ag > Ti. This finding evident from the projected density of states revealed the formation of the trap state that reduces the band gap of the catalyst promoting activity. In addition, the Bader charge analysis revealed the electron relocation from Ag to Au to be the reason behind the activity of the bimetallic that exceeds its monometallic counterparts.

Single-step fabrication of highly stable amorphous TiO2 nanotubes arrays (am-TNTA) for stimulating gas-phase photoreduction of CO2 to methane.

This study investigates the facile fabrication of interfacial defects assisted amorphous TiO2 nanotubes arrays (am-TNTA) for promoting gas-phase CO2 photoreduction to methane. The am-TNTA catalyst was fabricated via a one-step synthesis, without heat treatment, by anodization of Titanium in Ethylene glycol-based electrolyte in a shorter anodizing time. The samples presented a TiO2 nanostructured array with a nanotubular diameter of 100 ± 10 nm, a wall thickness of 26 ± 5 nm, and length of 3.7 ± 0.3 µm, resulting in a specific surface of 0.75 m2 g. The am-TNTA presented prolonged chemical stability, a high exposed surface area, and a large number of surface traps that can reduce the recombination of the charge carriers. The am-TNTA showed promising photoactivity when tested in the CO2 reduction reaction with water under UV irradiation with a methane production rate of 14.0 µmol gcat-1 h-1 for a pure TiO2 material without any modification procedure. This enhanced photocatalytic activity can be explained in terms of surface defects of the amorphous structure, mainly OH groups that can act as electron traps for increasing the electron lifetime. The CO2 interacts directly with those traps, forming carbonate species, which favors the catalytic conversion to methane. The am-TNTA also exhibited a high stability during six reaction cycles. The photocatalytic activity, the significantly reduced time for synthesis, and high stability for continuous CH4 production make this nanomaterial a potential candidate for a sustainable CO2 reduction process and can be employed for other energy applications.

Recent developments on bismuth oxyhalides (BiOX; X = Cl, Br, I) based ternary nanocomposite photocatalysts for environmental applications.

Photocatalytic treatment of organic pollutants present in wastewater using semiconductor nanomaterials under light irradiation is one of the efficient advanced oxidation processes. Stable metal oxide (e.g. TiO2) based semiconductor photocatalytic systems have been mainly investigated for this purpose. Nevertheless, their large band gap (~3.2 eV) makes them inefficient in utilization of visible light portion of solar light leading to a lower degradation efficiency. Investigations have focused on the development of visible light responsive bismuth oxyhalides (BiOX; X = Cl, Br, I), one of the potential nanomaterials with unique layered structure, for efficient absorption of solar light for the degradation of pollutants. However, the rapid recombination rate of photogenerated charge carriers limits their practical applicability. To overcome such drawbacks, the development of BiOX based ternary nanocomposites received significant attention because of their unique structural and electronic properties, improved visible light response and increased separation and transfer rate of photogenerated charge carriers. This review aims to provide a comprehensive overview of the recent developments on bismuth oxyhalides-based ternary nanocomposites for enhanced environmental pollutants decomposition under visible light irradiation. The principles of photocatalysis, synthetic methodologies of bismuth oxyhalides and their characteristics such as heterojunctions formation, improved visible light response and separation rate of charge carriers and the mechanisms for enhanced visible light photocatalytic activity are discussed. In addition, the future prospects on the improvement in the photocatalytic activity of bismuth oxyhalides-based ternary nanocomposites are also discussed. This review could be beneficial for designing new ternary nanocomposites with superior visible light photocatalytic efficiency.

Comparative study on the effect of different copper loading on catalytic behaviors and activity of Cu/ZnO/Al2O3 catalysts toward CO and CO2 hydrogenation.

The ternary Cu/ZnO/Al2O3 (CZA) catalysts having different Cu loading were prepared by the co-precipitation method. Then, they were used in CO and CO2 hydrogenation to produce methanol under atmospheric pressure at 250 °C. The high Cu loading CZA catalyst (CZA-H) resulted in the enhancement of structural features and textural properties (e.g., BET surface area and the crystallite size of copper species). Furthermore, the conversion of CO and CO2 over CZA-H catalyst was apparently higher than that of the CZA-L (low Cu loading) catalyst. The major product of CO hydrogenation obtained from both catalysts was methanol, whereas in CO2 hydrogenation, the main product was CO. Deactivation of catalysts was also crucial during CO and CO2 hydrogenation. Therefore, the spent catalysts were determined to identify the nature of carbon formation. It revealed that amorphous and graphitic cokes were present. These cokes have different mechanisms in the elimination from the surface leading to influencing the deactivation process. The spent CZA-L was found to have higher carbon content, which was around 2.3% and 3.1% for CO and CO2 hydrogenation, respectively. Besides the amorphous coke, the graphitic coke was also observed in CZA-L after time on stream for 5 h.