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Catalytic hydrogenation of CO2 to value-added fuels and chemicals is of great importance to carbon neutrality but suffers from an activity-selectivity trade-off, leading to limited catalytic performance. Herein, the ZnFeAlO4 + SAPO-34 composite catalyst was designed, which can simultaneously achieve a CO2 conversion of 42%, a CO selectivity of 50%, and a C2-C4= selectivity of 83%, resulting in a C2-C4= yield of almost 18%. This superior catalytic performance was found to be from the presence of unconventional electron-deficient tetrahedral Fe sites and electron-enriched octahedral Zn sites in the ZnFeAlO4 spinel, which were active for the CO2 deoxygenation to CO via the reverse water gas shift reaction, and CO hydrogenation to CH3OH, respectively, leading to a route for CO2 hydrogenation to C2-C4=, where the kinetics of CO2 activation can be improved, the mass transfer of CO hydrogenation can be minimized, and the C2-C4= selectivity can be enhanced via modifying the acid density of SAPO-34. Moreover, the spinel structure of ZnFeAlO4 possessed a strong ability to stabilize the active Fe and Zn sites even at elevated temperatures, resulting in long-term stability of over 450 h for this process, exhibiting great potential for large-scale applications.

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Typical cracking catalysts, called equilibrium catalyst (E-Cat) are ultra-stable Y (USY) zeolite often used with 15% commercial ZSM-5 zeolite additive (ZSM-5(COM)) to boost olefin yield. In this study, similar additive zeolites with different pore sizes and acidic character were synthesized by rapid ageing of precursor solution and used in the co-cracking of low-density polyethylene (LDPE) and heavy vacuum gas oil (HVGO). Three ZSM-5 zeolites additives with Si/Al ratio 25 (ZSM-5(25)), 50 (ZSM-5(50)) and 75 (ZSM-5(75)) were synthesized and combined with E-Cat to form E-Cat/ZSM-5(25), E-Cat/ZSM-5(50) and E-Cat/ZSM-5(75) respectively. The E-Cat/ZSM-5(50) has slightly better endothermic conversion (cracking) of a mixture of dissolved LDPE and HVGO into H2, C1 to C4 gases and C2-C4 light olefins (total conversion of E-Cat 80.0%, E-Cat/ZSM-5(COM) 75.0% and E-Cat/ZSM-5(50) 83.7% respectively), with different gas, liquid and coke distributions. The E-Cat/ZSM-5(75) has 81% conversion, and highest yield of light olefins (38.4%). Structural (surface area, pore size) and chemical (acid sites) characteristics of the synthetized ZSM-5(75) zeolite explain the observed higher light olefin selectivity by different and competing catalytic routes. The ZSM-5(75) has demonstrated to be a good zeolite additive for converting dissolved plastic in HVGO into light olefins.

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Naphtha, as the primary raw material in the production of light olefins, could well accommodate their increasing demand through the energy-efficient process of catalytic cracking with ZSM-5. In the current work, different amounts of lanthanum and phosphorous were loaded on ZSM-5 using the wet impregnation method to tune the acidic properties of ZSM-5 for selective catalytic cracking of n-hexane to produce light olefins. Various characterization techniques such as X-ray diffraction (XRD), Al nuclear magnetic resonance (NMR), temperature-programmed desorption of NH3 (NH3-TPD), Py-Fourier transform infra-red (Py-FTIR), inductively coupled plasma optical emission spectroscopy (ICP-OES), N2 adsorption-desorption, X-ray photoelectron spectra (XPS), and scanning electron microscopy were adopted to investigate the modified zeolites. It was found that adding La to ZSM-5 (0.25 wt% to 1 wt%) improved the catalytic life and increased the n-hexane conversion (to 99.7%), while the further addition had a negative impact, reducing the conversion rate and deviating the product selectivity towards a substantial, undesired benzene, toluene, and xylene (BTX) fraction (33%). On the other hand, a 64% selectivity for light olefins was achieved on phosphorous-doped ZSM-5 (at a loading amount of 1 wt%) while reducing the BTX fraction (2.3%) and converting 69% of the n-hexane. A dual metal-modified ZSM-5 with optimal loading amount, 1P0.25LaZ5 (phosphorus 1 wt% and La 0.25 wt%), helped boost the light olefin selectivity to 62% in the tuned Lewis acid sites at an n-hexane conversion of about 77% while decreasing the undesired BTX selectivity to 3% by reducing the number of Brønsted sites. Thus, the current study reveals that tuning the acidic sites of ZMS-5 by dual metal augmentation with P.La is an effective way of controlling the amount of undesirable BTX produced at a stable n-hexane conversion rate and substantial olefin selectivity.

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We proposed a new strategy for CO2 hydrogenation to prepare light olefins by introducing Zn into GaZrOx to construct ZnGaZrOx ternary oxides, which was combined with SAPO-34 to prepare a high-performance ZnGaZrOx/SAPO-34 tandem catalyst for CO2 hydrogenation to light olefins. By optimizing the Zn doping content, the ratio and mode of the two-phase composite, and the process conditions, the 3.5 %ZnGaZrOx/SAPO-34 tandem catalyst showed excellent catalytic performance and good high-temperature inhibition of the reverse water-gas shift (RWGS) reaction. The catalyst achieved 26.6 % CO2 conversion, 82.1 % C2 =-C4 = selectivity and 11.8 % light olefins yield. The ZnGaZrOx formed by introducing an appropriate amount of Zn into GaZrOx significantly enhanced the spillover H2 effect and also induced the generation of abundant oxygen vacancies to effectively promote the activation of CO2. Importantly, the RWGS reaction was also significantly suppressed at high temperatures, with the CO selectivity being only 46.1 % at 390 °C.

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Prolonging the lifetime of SAPO-34 catalysts and enhancing their olefin selectivity in methanol-to-olefin (MTO) reactions are critical yet challenging objectives. Here, a series of hierarchical SAPO-34 catalysts were synthesized using a straightforward recrystallization method. The incorporation of triethylamine into the recrystallization mother liquor facilitated the formation of mesopores, achieving a high solid yield of up to 90%. Notably, the addition of phosphoric acid and ammonium polyvinyl phosphate alcohol during the recrystallization process significantly enhanced the crystallinity and regularity of the hierarchical SAPO-34 crystals, consequently increasing the mesopore size. Due to the substantially improved mass transfer efficiency and moderated acidity, the SP34-0.14P-0.06R catalysts exhibited a prolonged lifetime of 344 min and 80.3% selectivity for ethylene and propylene at a weight hourly space velocity (WHSV) of 2 h-1. This performance markedly surpasses that of the parent SP34 catalyst, which demonstrated a lifetime of 136 min and a selectivity of 78.0%. Remarkably, the SP34-0.14P-0.06R maintained a lifetime of 166 min even at a high WHSV of 10 h-1, which is more than 5-fold greater than that of the original microporous SP34. This research offers valuable insights into the design and development of hierarchically porous zeolites with high yields, enhancing the efficiency of MTO reactions and other applications.

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Reducing CO2 emissions is an urgent global priority. In this context, several mitigation strategies, including CO2 tax and stringent legislation, have been adopted to halt the deterioration of the natural environment. Also, carbon recycling procedures undoubtedly help reduce net emissions into the atmosphere, enhancing sustainability. Utilizing Earth's abundant CO2 to produce high-potential green chemicals and light fuels opens new avenues for the chemical industry. In this context, many attempts have been devoted to converting CO2 as a feedstock into various value-added chemicals, such as CH4, lower methanol, light olefins, gasoline, and higher hydrocarbons, for numerous applications involving various catalytic reactions. Although several CO2-conversion methods have been used, including electrochemical, photochemical, and biological approaches, the hydrogenation method allows the reaction to be tuned to produce the targeted compound without significantly altering infrastructure. This review discusses the numerous hydrogenation routes and their challenges, such as catalyst design, operation, and the combined art of structure-activity relationships for the various product formations.

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Converting CO2 to olefins is an ideal route to achieve carbon neutrality. However, selective hydrogenation to light olefins, especially single-component olefin, while reducing CH4 formation remains a great challenge. Herein, we developed ZnZrOx /SSZ-13 tandem catalyst for the highly selective hydrogenation of CO2 to light olefins. This catalyst shows C2 = -C4 = and propylene selectivity up to 89.4 % and 52 %, respectively, while CH4 is suppressed down to 2 %, and there is no obvious deactivation. It is demonstrated that the isolated moderate Brønsted acid sites (BAS) of SSZ-13 promotes the rapid conversion of intermediate species derived from ZnZrOx , thereby enhancing the kinetic coupling of the reactions and inhibit the formation of alkanes and improve the light olefins selectivity. Besides, the weaker BAS of SSZ-13 promote the conversion of intermediates into aromatics with 4-6 methyl groups, which is conducive to the aromatics cycle. Accordingly, more propene can be obtained by elevating the Si/Al ratio of SSZ-13. This provides an efficient strategy for CO2 hydrogenation to light olefins with high selectivity.

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Owing to the ever-increasing generation of plastic waste, the need to develop environmentally friendly disposal methods has increased. This study explored the potential of waste plastic straw to generate valuable light olefins and monocyclic aromatic hydrocarbons (MAHs) via catalytic pyrolysis using high-silica zeolite-based catalysts. HZSM-5 (SiO2/Al2O3:200) exhibited superior performance, yielding more light olefins (49.8 wt%) and a higher MAH content than Hbeta (300). This was attributed to the increased acidity and proper shape selectivity. HZSM-5 displayed better coking resistance (0.7 wt%) than Hbeta (4.4 wt%) by impeding secondary reactions, limiting coke precursor formation. The use of HZSM-5 (80) resulted in higher MAHs and lower light olefins than HZSM-5 (200) because of its higher acidity. Incorporation of Co into HZSM-5 (200) marginally lowered light olefin yield (to 44.0 wt%) while notably enhancing MAH production and boosting propene selectivity within the olefin composition. These observations are attributed to the well-balanced coexistence of Lewis and Brønsted acid sites, which stimulated the carbonium ion mechanism and induced H-transfer, cyclization, Diels-alder, and dehydrogenation reactions. The catalytic pyrolysis of plastic straw over high-silica and metal-loaded HZSM-5 catalysts has been suggested as an efficient and sustainable method for transforming plastic waste materials into valuable light olefins and MAHs.

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As a nonpetroleum process, photodriven Fischer-Tropsch synthesis provides a practical approach for the synthesis of light olefins. However, maximizing the solar-energy conversion efficiency based on the design of the composite catalyst and understanding the catalytic mechanism remain challenging. Herein, a novel carbon-coated CoMn-based catalyst, a C-coated mixture of Co and MnO, is designed for the efficient conversion of syngas to light olefins under light irradiation. The CoMnC-450 catalyst exhibits a CO conversion of 12.6% with a selectivity to light olefins of 36.5% under light irradiation, showing 5.5-fold the activity of thermocatalysis. Experimental characterizations as certain the CoMnC-450 catalyst can be excited to generate photogenerated carriers under light irradiation and then the electron transfer to metallic Co to form electron-rich active sites with carbon mediation, thereby enhancing the catalytic performance. In situ Fourier transform infrared spectroscopy and theoretical calculation based on density functional theory reveal the unique roles of photogenerated carriers in promoting the adsorption and activation of CO molecules. This study demonstrates a feasible catalyst model to efficiently utilize full-spectral solar light to produce the value-added chemical.

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Light olefins (LOs) such as ethylene and propylene are critical feedstocks for many vital chemicals that support our economy and daily life. LOs are currently mass produced via steam cracking of hydrocarbons, which is highly energy intensive and carbon polluting. Efficient, low-emission, and LO-selective conversion technologies are highly desirable. Electrochemical oxidative dehydrogenation of alkanes in oxide-ion-conducting solid oxide fuel cell (SOFC) reactors has been reported in recent years as a promising approach to produce LOs with high efficiency and yield while generating electricity. We report here an electrocatalyst that excels in the co-production. The efficient catalyst is NiFe alloy nanoparticles (NPs) exsolved from a Pr- and Ni-doped double perovskite Sr2Fe1.5Mo0.5O6 (Pr0.8Sr1.2Ni0.2Fe1.3Mo0.5O6-δ, PSNFM) matrix during SOFC operation. We show evidence that Ni is first exsolved, which triggers the following Fe-exsolution, forming the NiFe NP alloy. At the same time as the NiFe exsolution, abundant oxygen vacancies are created at the NiFe/PSNFM interface, which promotes the oxygen mobility for oxidative dehydrogenation of propane (ODHP), coking resistance, and power generation. At 750 °C, the SOFC reactor with the PSNFM catalyst reaches a propane conversion of 71.40% and LO yield of 70.91% under a current density of 0.3 A cm-2 without coking. This level of performance is unmatchable by the current thermal catalytic reactors, demonstrating the great potential of electrochemical reactors for direct hydrocarbon conversion into value-added products.

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The oxide-zeolite (OXZEO) catalyst design concept has been demonstrated in an increasing number of studies as an alternative avenue for direct syngas conversion to light olefins. We report that face-centered cubic (FCC) MnGaOx -Spinel gives 40 % CO conversion, 81 % light olefins selectivity, and a 0.17 g gcat -1 h-1 space-time yield of light olefins in combination with SAPO-18. In comparison, solid solution MnGaOx (characterized by Mn-doped hexagonal close-packed (HCP) Ga2 O3 ) with a similar chemical composition gives a much inferior activity, i.e., the specific surface activity is one order of magnitude lower than the spinel oxide. Photoluminescence (PL), in situ Fourier-transform infrared (FT-IR), and density functional theory (DFT) calculations indicate that the superior activity of MnGaOx -Spinel can be attributed to its higher reducibility (higher concentration of oxygen vacancies) and the presence of coordinatively unsaturated Ga3+ sites, which facilitates the dissociation of the C-O bond via a more efficient ketene-acetate pathway to light olefins.

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Solar-driven CO2 hydrogenation into multi-carbon products is a highly desirable, but challenging reaction. The bottleneck of this reaction lies in the C-C coupling of C1 intermediates. Herein, we construct the C-C coupling centre for C1 intermediates via the in situ formation of Co0 -Coδ+ interface double sites on MgAl2 O4 (Co-CoOx /MAO). Our experimental and theoretical prediction results confirmed the effective adsorption and activation of CO2 by the Co0 site to produce C1 intermediates, while the introduction of the electron-deficient state of Coδ+ can effectively reduce the energy barrier of the key CHCH* intermediates. Consequently, Co-CoOx /MAO exhibited a high C2-4 hydrocarbons production rate of 1303 µmol g-1 h-1 ; the total organic carbon selectivity of C2-4 hydrocarbons is 62.5 % under light irradiation with a high ratio (≈11) of olefin to paraffin. This study provides a new approach toward the design of photocatalysts used for CO2 conversion into C2+ products.

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Direct production of light olefins, building blocks of chemical industry, can be attained by developing efficient catalysts for Fischer-Tropsch synthesis (FTS). The nature of FTS complicates the catalyst development process as the product distribution is affected by the components and the preparation methods of the catalyst. In this work, high-throughput (HT) methodology is employed to overcome this problem by testing many different catalyst formulations. Fast performance screening of 40 different α-Al2O3 supported Fe-Mn based catalysts promoted with Cu, K and Ni, using different impregnation agents, was performed in a HT test system at atmospheric pressure. Promising catalyst candidates identified by HT analysis were further subjected to high pressure FTS in a conventional system. Results indicate that coupled with Mn, Ni promoted CH4 production, Cu increased CO conversion, K enhanced olefin selectivity and olefin-to-paraffin ratio. In double promotion of Cu and K, Cu balanced the activity and stability loss due to K, while K enhanced olefin selectivity. n-pentane aided impregnation slightly enhanced catalytic performance. Differences observed in catalytic performance were regarded as related to the structural changes caused by promoter and impregnation type based on characterization data obtained by H2-TPR, XRD, SEM, EDS mapping and N2 adsorption.

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There is a large worldwide demand for light olefins (C2=-C4=), which are needed for the production of high value-added chemicals and plastics. Light olefins can be produced by petroleum processing, direct/indirect conversion of synthesis gas (CO + H2) and hydrogenation of CO2. Among these methods, catalytic hydrogenation of CO2 is the most recently studied because it could contribute to alleviating CO2 emissions into the atmosphere. However, due to thermodynamic reasons, the design of catalysts for the selective production of light olefins from CO2 presents different challenges. In this regard, the recent progress in the synthesis of nanomaterials with well-controlled morphologies and active phase dispersion has opened new perspectives for the production of light olefins. In this review, recent advances in catalyst design are presented, with emphasis on catalysts operating through the modified Fischer-Tropsch pathway. The advantages and disadvantages of olefin production from CO2 via CO or methanol-mediated reaction routes were analyzed, as well as the prospects for the design of a single catalyst for direct olefin production. Conclusions were drawn on the prospect of a new catalyst design for the production of light olefins from CO2.

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Zeolite molecular sieves are widely used in gas separation and shape-selective catalysis, but these applications often require discriminating differences as little as 0.1 Å. Molecular sieving with such size selectivity demands zeolites with highly tunable pore diameters and adsorption properties, which are technically challenging to prepare. Nevertheless, it is shown that a wide range of organic functional groups can be covalently functionalized onto the interior pore walls of the zeolites, MOR, LTL, FAU, and MFI, to systematically "tune" their effective pore diameters with respect to the size of organic groups. For organic functionalization, small and aggressive organic electrophiles are used (e.g., organo-halide and -diazonium) as grafting agents, which are accessible to the intracrystalline void space, forming a C-Ozeolite bond in a reaction with a bridging oxygen as proved by multiple analysis data. It is demonstrated that the post-functionalization can be used to tailor the molecular sieving action of a parent zeolite to give size-selective adsorbents for light olefin/paraffin separations. 4-Methoxybenzene-functionalized MOR separates ethylene from ethane with an ideal-adsorbed-solution-theory selectivity of ≈5873, whereas toluene-grafted MOR completely separates propylene/propane mixtures. Therefore, tailoring the molecular-sieving properties of zeolites by organic functionalization broadens their applications to challenging separations.

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The kinetics of oxidative cracking of n-hexane to light olefins using the lattice oxygen of VOx /SrO-γAl2 O3 catalysts has been investigated. Kinetic experiments were conducted in a CREC Riser Simulator (CERC: Chemical Reactor Engineering Center), which mimics fluidized bed reactors. The catalyst's performance is partly attributed to the moderate interaction between active VOx species and the SrO-γAl2 O3 support. This moderate interaction serves to control the release of lattice oxygen to curtail deep oxidation. The incorporation of basic SrO component in the support also helped to moderate the catalyst's acidity to checkmate excessive cracking. Langmuir-Hinshelwood model was applied to formulate the rate equations. The intrinsic kinetic parameters were obtained by fitting the experimental data to the kinetic model using a nonlinear regression algorithm at a 95% confidence interval, implemented in MATLAB. n-Hexane transforms to olefins at a specific reaction rate of 1.33 mol/gcat.s and activation energy of 119.2 kJ/mol. These values when compared with other duplets (i. e., ki° and EA ) for paraffins to olefins, show that indeed olefins are stable products of the oxidative conversion of n-hexane over VOx /SrO-γAl2 O3 under a fluidized bed condition. Values of activation energy for all COx formation routes indicate that intermediate paraffins are likely to be cracked to form CH4 than to be converted directly to COx . On the other hand, olefins may transform partly, and directly to COx (E9 =9.65 kJ/mol) than to form CH4 (E8 =89.1 kJ/mol) in the presence of excess lattice oxygen. Overall, olefins appear to be stable to deep oxidation due to the role of SrO in controlling the amount of lattice oxygen of the catalyst at the reaction temperature.

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Valorization of biomass to olefin or aromatics harbours tremendous practical value due to growing concerns about sustainable production of chemicals. Herein, the olefin or aromatics yields of ex-situ catalytic pyrolysis of pine can be regulated by impregnating Sn on hollow-structured ZSM-5 (M-ZSM-5) and microporous ZSM-5 catalysts in fixed-bed reactor, respectively. Results showed that Sn/ZSM-5 catalyst simultaneously increased medium acidic sites and maintained strong acidic sites, which obtained the maximum carbon yield of aromatics (33.77%) due to enhanced cracking and deoxygenation reactions. In addition, Sn boosted alkylation between olefin and aromatics, generating more alkylbenzene. In contrast, Sn/M-ZSM-5 catalyst produced the highest olefins carbon yield (12.39%) because the reduction of strong acidic sites and microporous volume inhibited the olefin aromatization. Moreover, olefins were easier to desorb from Sn/M-ZSM-5 due to the enhanced mass transfer ability, which weakened the alkylation reactions. The synergistic effect harbours great significance to manipulate the distribution of products.

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In the present study, SAPO-34 particles were synthesized using hydrothermal (HT) and dry gel (DG) conversion methods in the presence of diethyl amine (DEA) as an organic structure directing agent (SDA). Carbon nanotubes (CNT) were used as a hard template in the synthesis procedure to introduce transport pores into the structures of the synthesized samples. The synthesized samples were characterized with different methods to reveal the effects of synthesis method and using hard template on their structure and catalytic performance in methanol to olefin reaction (MTO). DG conversion method results in smaller particle size in comparison with hydrothermal method, resulting in enhancing catalytic performance. On the other side, using CNT in the synthesis procedure with DG method results in more reduction in particle size and formation of hierarchical structure, which drastically improves catalytic performance.

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AIM AND OBJECTIVE: The effect of two different modification methods for introducing Ni into the ZSM-5 framework was investigated under high-temperature synthesis conditions. The nickel was successfully introduced into the MFI structures at different crystallization conditions to enhance the physicochemical properties and catalytic performance. MATERIALS AND METHODS: A series of impregnated Ni/ZSM-5 and isomorphous substituted NiZSM- 5 nanostructure catalysts were prepared hydrothermally at different high temperatures and within short times. X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy dispersive X-ray (EDX), Brunner, Emmett and Teller-Barrett, Joyner and Halenda (BETBJH), Fourier transform infrared (FTIR) and Temperature-programmed desorption of ammonia (TPD-NH3) were applied to investigate the physicochemical properties. RESULTS: Although all the catalysts showed pure silica MFI-type nanosheets and coffin-like morphology, using the isomorphous substitution for Ni incorporation into the ZSM-5 framework led to the formation of materials with lower crystallinity, higher pore volume and stronger acidity compared to using impregnation method. Moreover, it was found that raising the hydrothermal temperature increased the crystallinity and enhanced the more uniform incorporation of Ni atoms in the crystalline structure of catalysts. TPD-NH3 analysis demonstrated that high crystallization temperature and short crystallization time of NiZSM-5(350-0.5) resulted in fewer weak acid sites and medium acid strength. The MTO catalytic performance was tested in a fixed bed reactor at 460ºC and GHSV=10500 cm3/gcat.h. A slightly different reaction pathway was proposed for the production of light olefins over impregnated Ni/ZSM-5 catalysts based on the role of NiO species. The enhanced methanol conversion for isomorphous substituted NiZSM-5 catalysts could be related to the most accessible active sites located inside the pores. CONCLUSION: The impregnated Ni/ZSM-5 catalyst prepared at low hydrothermal temperature showed the best catalytic performance, while the isomorphous substituted NiZSM-5 prepared at high temperature was found to be the active molecular sieve regarding the stability performance.

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Previously, 3D printing of porous materials and metal oxides was limited to low loading metal loadings, as increasing the nitrate salt concentrations, which are used to generate the oxide component, gave rise to poor rheological properties beyond 10 wt %. In this study, we addressed this problem by directly printing insoluble oxides alongside H-ZSM-5 zeolite, which allowed for increased oxide loadings. Various metal oxides such as V2O5, ZrO2, Cr2O3, and Ga2O3 were doped onto H-ZSM-5 through the additive manufacturing method. Characterization and correlation between the X-ray diffraction, NH3-temperature-programmed desorption, O2-temperature programmed oxidation, temperature-programmed reduction, scanning electron microscopy-energy dispersive spectroscopy, and in situ CO2 DRIFTS experiments revealed that directly 3D printing metal oxides/H-ZSM-5 inks leads to significant modification in the surface properties and oxide bulk dispersion, thereby enhancing the composites' reducibility and giving rise to widely differing product distributions in n-hexane cracking reaction. The obtained metal oxide/zeolite structured materials were used as bifunctional structured catalysts for the selective formation of light olefins from hexane at 550-600 °C and GHSV = 9000 mL/gcatalst·h in a packed-bed reactor. Among the various compositions of metal oxides/H-ZSM-5 examined (i.e., 15 wt % Ga2O3, 15 wt % ZrO2, 15 wt % V2O5, 15 wt % Cr2O3, or 5 wt % Cr/10 wt % ZrO2/10 wt % V2O5/10 wt % Ga2O3 balanced with H-ZSM-5), the 15 wt % Cr/ZSM-5 monolith displayed the best n-hexane cracking performance, as it achieved 80-85% conversion of hexane with a 40% selectivity toward propylene, 30% selectivity toward ethylene, and 10% selectivity toward butene at 550 °C. The sample also showed zero benzene/toluene/xylene selectivity and no deactivation after 6 h. This study represents a proof-of-concept for tailoring customizable heterogeneous structured catalysts by directly 3D printing high loading of metal oxides/porous zeolite and is a breakthrough in material science.