CH4 Conversion Research Articles

Influence of the La/Ce ratio on La-Ce oxides promoted by Sr in the methane oxidative coupling reaction

The high methane availability and its significant role as a greenhouse gas have led the scientific community to pursue methods for its use. This paper proposes the usage of the oxidative coupling of methane (OCM) as a promising path to transform methane directly into value-added hydrocarbons, mostly ethylene, which serves as a crucial compound in the petrochemical sector. An efficient OCM catalyst should contain substantial basicity and oxygen vacancies for providing surface electrophilic oxygen species, such as superoxides and peroxides, instrumental for boosting selectivity towards C2 products. Mixed lanthanum-cerium oxide (La-Ce) catalysts have emerged as strong candidates in OCM due to their high thermal stability, oxygen mobility, and high alkalinity. In this study, they were prepared through a surfactant-assisted hydrothermal method with different La/Ce ratios for fine-tuning their basic properties and promoting oxygen mobility on the surface of the catalysts. Samples followed a volcano-shaped relationship between C2 yield and La content, with optimal performance at a La/Ce molar ratio of 2.1, attributed to the interplay between the high amount of basic sites and oxygen vacancies, increasing the presence of superoxide species over lattice oxygen. Moreover, the Sr-promoted catalyst showed high density of strong basic sites while preserving the reactive oxygen species, achieving 20 % CH4 conversion, with 57 % C2 compounds selectivity at 750 °C and GHSV of 18.000 mL.gcat−1.h−1.

Cu-Fe bimetallic MOFs with long lifetime separated-state charge for enhancing selectivity for CO2 photoreduction to CH4

Improving the CO2 to CH4 conversion efficiency of Cu metal-organic frameworks (Cu-MOFs) catalysts is important for promoting carbon capture and utilization. In this work, a series of novel Cu-Fe bimetallic MOFs photocatalysts (Cu-BTB-Fe with 0.5 wt%, 1.0 wt%, 2.0 wt%, and 4.0 wt% of Fe; H3BTB = 1,3,5-tris(4-carboxyphenyl) benzene) were synthesized by a bimetallic site (Cu and Fe) design strategy in order to improve the electron-hole separation efficiency and CO2 adsorption activation. Findings indicated that the as-synthesized Cu-BTB-2 wt% Fe catalyst exhibited excellent catalytic performance for the conversion of CO2 to CH4 and CO under simulated sunlight irradiation, providing a yield of 32.20 μmol∙g−1∙h−1 and a selectivity of 69.24 % for CO2 to CH4 conversion as well as a yield of 14.29 μmol∙g−1∙h−1 for CO2 to CO conversion without liquid phase products. This is because the Cu-Fe bimetallic sites can continuously supply photoinduced electrons with long separated-state decay lifetime to efficiently activate CO2. Specifically, the Cu-BTB-Fe catalysts provided a high proportion of effective photoinduced electrons with long decay lifetime for the CO* hydrogenation process through a unique electron transfer mechanism, while the strong affinity between CO2 and [Cu2(COO)4]-Fe active units enabled high CO2 adsorption activation and rapid CO2 reduction. The present approach, hopefully, would help to establish feasible pathway for the development of novel highly selective Cu-based MOFs photocatalysts for CO2 photocatalytic reduction yielding CH4.

Ni-Sr/TiZr for H2 from methane via POM: Sr loading & optimization.

Achieving remarkable H2 yield with significantly high H2/CO over Ni-based catalysts through partial oxidation of methane (POM) is a realistic approach to depleting the concentration of CH4 and using H2 and CO as synthetic feedstock. This study examined Ni catalysts on titania-zirconia for methane conversion via POM at 600 °C and atmospheric pressure. The addition of strontium to the catalyst was explored to improve its performance. Catalysts were characterized by X-ray diffraction, Raman-infrared-UV-vis spectroscopy, and Temperature-programmed reduction-desorption techniques (TPR, TPD). 2.5 wt% Sr addition induced the formation of the highest concentration of extreme basic sites. Interestingly, over the unpromoted catalyst, active sites are majorly generated by hardly reducible NiO species whereas upon 2.5 wt% promoted Sr promotional addition, most of active sites are derived by easily reducible NiO species. 45% CH4 conversion and 47% H2 yield with H2/CO = 3.5 were achieved over 2.5 wt% Sr promoted 5Ni/30TiO2 + ZrO2 catalyst. These results provide insight into the role of basic sites in enhancing activity through switching indirect pathways over direct pathways for POM. Further process optimization was carried out in the range of 10 000-22 000 SV, 0.35-0.75 O2/CH4, and 600-800 °C reaction temperature over 5Ni2.5Sr/30TiO2 + ZrO2 by using central composite design under response surface methodology. The optimum activity as high as ∼88% CH4 conversion, 86-87% yield of H2, and 2.92H2/CO were predicted and experimentally validated at 800 °C reaction temperature, 0.35O2/CH4 ratio, and 10 000 space velocity.

Tandem Catalysis for Simultaneous Removal of NOx and C3H8 with Inhibition of N2O.

Tandem catalysis is widely adopted for multipollutant control in mobile sources but has rarely been reported in stationary source emission elimination. This work proposed a tandem arrangement way with up-streamed V2O5/TiO2 + down-streamed Cr2O3/TiO2 catalysts, which could achieve the efficient synergistic control of NOx and C3H8 in industrial flue gas. Moreover, this arrangement successfully alleviated the unwanted N2O formation during the NH3 -SCR process. Compared to the conventional impregnation method of the Cr2O3-V2O5/TiO2 catalyst, the tandem catalysts of V2O5/TiO2 + Cr2O3/TiO2 could enhance the NOx and C3H8 conversion by 4.2% and 39.5%, respectively, at 350 °C. It might be attributed to the fact that Cr species was the active site for C3H8 oxidation, and the tandem arrangement of catalysts was beneficial to even dispersion of active components on supports. Furthermore, due to the preferential NOx removal over the up-streamed V2O5/TiO2 catalyst, the tandem catalysts obviously alleviated the N2O formation caused by Cr species during the NH3-SCR process. Herein, it significantly decreased N2O formation by 240.5% at 350 °C compared to the Cr2O3-V2O5/TiO2 catalyst, achieving multipollutant emission control from industrial flue gas with the performance of "one stone three birds".

Defect Engineering of WO3 by Rapid Flame Reduction for Efficient Photoelectrochemical Conversion of Methane into Liquid Oxygenates

Photoelectrochemical (PEC) conversion is a promising way to utilize methane (CH4) as a chemical building block without harsh conditions. However, PEC CH4 conversion to value-added chemicals remains challenging due to the thermodynamically favorable over-oxidation of CH4. Here, we report WO3 nanotubes (NTs) photoelectrocatalysts for PEC CH4 conversion with high liquid product selectivity through defect engineering. By tuning the flame reduction treatment, the oxygen vacancies of WO3 NTs were carefully controlled. The optimally reduced WO3 NTs suppressed over-oxidation of CH4 showing high total C1 liquid selectivity of 69.4% and production rate of 0.174 μmol⋅cm-2⋅h-1. Scanning electrochemical microscopy revealed that oxygen vacancies can restrain the production of hydroxyl radicals, which in excess could further oxidize C1 intermediates to CO2. Additionally, band diagram analysis and computational studies elucidated that oxygen vacancies thermodynamically suppress over-oxidation. This work introduces a strategy to understand and control the selectivity of photoelectrocatalysts for direct CH4 conversion to liquids.

Electrocatalytic Conversion of CH4 to High Value-Added Liquid Fuel over Binary Metal Oxide Tandem Catalysts

As the main component (> 85%) of combustible ice and shale gas, methane (CH4), plays a significant role in the greenhouse effect.(1) Although CH4 was widely used to synthesize high value-added Cx oxygenates via indirect industrial reforming with high-energy consumption. The accurate control of oxidation degree in CH4 conversion remains a great challenge.(2) Therefore, it is difficult to achieve high conversion rate and high selectivity at the same time. The convenience and reliability of the control of reaction potential, as one of the advantages of electrocatalysis technology, can effectively address the above problems.(1, 3) Electrochemical technologies of CH4-to-Cx oxygenates are regarded as one of the most attractive pathways to produce bulk industrial liquid fuels.(4) Especially in the premise of clean energy as an energy source, the electrochemical conversion of methane demonstrates very advantageous market potential. In this work, we prepared a ZrO2 modified FeOx binary metal oxides tandem catalyst to accelerate partial oxidation of CH4 under ambient condition. With CO3 2- as an oxidant, ZrO2@FeOx tandem catalyst shows remarkable CH4 conversion performance with large current density gap (13.65 mA cm-2) and long-term electrochemical stability (negligible attenuation (8 %) after 48 hours) in three-electrodes cell. In addition, in a flow reactor, ZrO2@FeOx-based electrode also exhibits a highly stable operating lifespan over 72 hours at a large current density 50 mA cm-2 and achieve a feasible CH4-liqid fuel conversion with high total faradaic efficiency.References F. Liu, Y. Yan, G. Chen and D. Wang, Green Chemistry, 26, 655 (2024).S. Yuan, Y. Li, J. Peng, Y. M. Questell-Santiago, K. Akkiraju, L. Giordano, D. J. Zheng, S. Bagi, Y. Román-Leshkov and Y. Shao-Horn, Advanced Energy Materials, 10, 2002154 (2020).M. R. A. Kishore, S. Lee and J. S. Yoo, Adv Sci (Weinh), 10, e2301912 (2023).L. Fu, R. Zhang, J. Yang, J. Shi, H. Y. Jiang and J. Tang, Advanced Energy Materials, 13 (2023).

Oxidative and Reductive Manipulation of C1 Resources by Bio-Inspired Molecular Catalysts to Produce Value-Added Chemicals.

ConspectusTo tackle the energy and environmental concerns the world faces, much attention is given to catalytic reactions converting methane (CH4) and carbon dioxide (CO2) as abundant C1 resources into value-added chemicals with high efficiency and selectivity. In the oxidative conversion of CH4 to methanol, it is necessary to solve the requirement of strong oxidants due to the large bond-dissociation energy (BDE) of the C-H bonds in methane and achieve suppression of overoxidation due to the smaller BDE of the C-H bond in methanol as the product. On the other hand, to efficiently perform CO2 reduction, proton-coupled electron transfer (PCET) processes are required since the reduction potential of CO2 becomes positive by using proton-coupled processes; however, under the acidic conditions required for PCET, hydrogen evolution by the reduction of protons becomes competitive with CO2 reduction. Thus, it is indispensable to develop efficient catalysts for selective CO2 reduction. Recently, we have developed efficient catalytic reactions toward the alleviation of the concerns mentioned above. Concerning CH4 oxidation, inspired by metalloenzymes that oxidize hydrophobic organic substrates, a hydrophobic second coordination sphere (SCS) was introduced to an FeII complex bearing a pentadentate N-heterocyclic carbene ligand, and the FeII complex was used as a catalyst for CH4 oxidation in aqueous media. Consequently, CH4 was efficiently and selectively oxidized to methanol with 83% selectivity and a turnover number of 500. In contrast, when methanol was used as a substrate for catalytic oxidation by the FeII complex, oxidation products were obtained in a negligible yield, which was comparable to that of the control experiment without the catalyst. Therefore, the hydrophobic SCS of the FeII complex can capture only hydrophobic substrates such as CH4 and release hydrophilic products such as methanol to the aqueous medium for suppressing overoxidation ("catch-and-release" mechanism). On the other hand, for photocatalytic CO2 reduction, we have developed NiII complexes with N2S2-chelating ligands as catalysts, which have been inspired by carbon monoxide dehydrogenase, and have also introduced a binding site of Lewis-acidic metal ions to the SCS of the Ni complex. When Mg2+ was applied as a moderate Lewis acid, a Mg2+-bound Ni catalyst allowed us to achieve remarkable enhancement of the photocatalytic CO2 reduction to afford CO as the product with over 99% selectivity and a quantum yield of 11.4%. Divalent metal ions besides Mg2+ also showed similar positive impacts on photocatalytic CO2 reduction, whereas monovalent metal ions exhibited almost no effects and trivalent metal ions exclusively promoted hydrogen evolution. In this Account, we highlight our recent progress in the catalytic manipulations of CH4 and CO2 as C1 resources.

Engineering In-Co3O4/H-SSZ-39(OA) Catalyst for CH4-SCR of NOx: Mild Oxalic Acid (OA) Leaching and Co3O4 Modification.

Zeolite-based catalysts efficiently catalyze the selective catalytic reduction of NOx with methane (CH4-SCR) for the environmentally friendly removal of nitrogen oxides, but suffer severe deactivation in high-temperature SO2- and H2O-containing flue gas. In this work, SSZ-39 zeolite (AEI topology) with high hydrothermal stability is reported for preparing CH4-SCR catalysts. Mild acid leaching with oxalic acid (OA) not only modulates the Si/Al ratio of commercial SSZ-39 to a suitable value, but also removes some extra-framework Al atoms, introducing a small number of mesopores into the zeolite that alleviate diffusion limitation. Additional Co3O4 modification during indium exchange further enhances the catalytic activity of the resulting In-Co3O4/H-SSZ-39(OA). The optimized sample exhibits remarkable performance in CH4-SCR under a gas hourly space velocity (GHSV) of 24,000 h-1 and in the presence of 5 vol% H2O. Even under harsh SO2- and H2O-containing high-temperature conditions, it shows satisfactory stability. Catalysts containing Co3O4 components demonstrate much higher CH4 conversion. The strong mutual interaction between Co3O4 and Brønsted acid sites, confirmed by the temperature-programmed desorption of NO (NO-TPD), enables more stable NxOy species to be retained in In-Co3O4/H-SSZ-39(OA) to supply further reactions at high temperatures.

Pressure-Induced Enhancement in Chemical Looping Reforming of CH4: A Thermodynamic Analysis with Fe-Based Oxygen Carriers.

Chemical looping reforming of methane (CLRM) with Fe-based oxygen carriers is widely acknowledged as an environmentally friendly and cost-effective approach for syngas production, however, sintering-caused deactivate of oxygen carriers at elevated temperatures of above 900 °C is a longstanding issue restricting the development of CLRM. Here, in order to reduce the reaction temperature without compromising the chemical-looping CH4 conversion efficiency, we proposed a novel operation scheme of CLRM by manipulating the reaction pressure to shift the equilibrium of CH4 partial oxidation towards the forward direction based on the Le Chatelier's principle. The results from thermodynamic simulations showed that, at a fixed reaction temperature, the reduction in pressure led to the increase in CH4 conversion, H2 and CO selectivity, as well as carbon deposition rate of all investigated oxygen carriers. The pressure-negative CLRM with Fe3O4, Fe2O3 and MgFe2O4 could reduce the reaction temperature to below 700 °C on the premise of a satisfactory CLRM performance. In a comprehensive consideration of the CLRM performance, energy consumption, and CH4 requirement, NiFe2O4 was the Fe-based OCs best available for pressure-negative CLRM, especially for an excellent syngas yield of 23.08 mmol/gOC. This study offered a new strategy to address sintering-caused deactivation of materials in chemical looping from the reaction thermodynamics point of view.

Few-layered-graphene - Si3N4 composite powders prepared by decomposition of methane onto a Si3N4 powder bed: Control of the average number of layers in the graphene stack

The chemical vapor deposition of carbon is performed onto a commercial silicon nitride powder bed. This produces few-layered-graphene (FLG) films or islands on the Si3N4 particles. The samples are characterized by several techniques including Raman spectroscopy, scanning and transmission electron microscopy. The experimental parameters of the methane (CH4) decomposition (temperature, CH4 concentration, dwell time) are correlated to the average number of graphene layers (N). Complete coverage of the Si3N4 particles is achieved for FLG with N controlled in the range 5–12, corresponding to 4–12 wt%. of carbon. Below that, for stacks with N = 3–4, the coverage of the surface by FLG islands is not total. The value found for the activation energy of CH4 conversion into carbon shows that island-growth is favored over layer-growth. A macroscopical method based on a carbon proportion evaluation gives an approximation of both the coverage ratio and the average number of layers in the stack.

Enhanced activity and water resistance of SiO2-coated Co/In-SSZ-13 catalysts in the selective catalytic reduction of NOx with CH4

CH4 selective catalytic reduction of NOx (CH4-SCR) is a promising technology to synergistic control of CH4 and NOx emission from LNG-powered vehicles and ships, while its insufficient catalytic activity and H2O resistance are key barriers for application. In this work, SiO2 coated Co3O4/In-SSZ-13 catalysts (Co/In-Z@Si) were prepared to simultaneously improve the CH4-SCR activity and H2O tolerance. The proper Co3O4 introduction enhanced the catalytic performance of the In-SSZ-13, while excessive amount of Co3O4 addition led to more CH4 being oxidized and insufficient CH4 participating in the CH4-SCR reaction. There was a “seesaw effect” between NO oxidation and CH4 oxidation performance of the catalysts. The H2O resistance of the Co/In-Z catalysts significantly enhanced via ultrathin SiO2 coating. The NOx and CH4 conversion maintained 81 % and 90 % in the presence of H2O at 500 °C for the Co/In-Z@Si catalyst, respectively. The in situ DRIFTS confirmed that the SiO2 coating could adsorb H2O molecules, prevent H2O from contacting the active sites, and limit the competitive adsorption between H2O and CH4 on the catalyst. This work provides a good candidate with superior catalytic performance and H2O resistance for removal of NOx and CH4 from LNG-powered vehicles and ships simultaneously.

W Single‐Atoms Anchored on Rutile TiO2 for Direct Methane Photocatalytic Conversion under Mild Conditions

Photo-driven direct CH4 conversion to value added liquid oxygenates attracts great attention for its enormous energy and environment benefits. However, because of the intrinsic inertness of CH4, realizing highly efficient direct CH4 conversion and prevent peroxidation remains a great challenge. Herein, a novel photocatalyst of rutile TiO2 supported W single-atoms was prepared for CH4 direct conversion to C1 products with 100% selectivity. The electron deficient property of the atomically-dispersed W active sites together with the photo-excited electron transferring from Ti to W can facilitate H2O2 adsorption and decomposition, and promote CH4 activation and conversion to varied products with a yield as high as 7 mmol gcat‐1 h‐1. This yield equaled to 238.5 mol molW‐1 h‐1, 82 times higher than that of the reported Cr single-atoms. In-situ ESR, FTIR and DFT simulation were combined to elucidate the CH4 conversion mechanism.

Oxidation of lean methane by dielectric barrier discharge plasma and Mn–Ce catalyst

The synergistic dielectric barrier discharge plasma and Mn-Ce catalysts are employed to facilitate the low temperature and highly efficient oxidation of lean methane. The effect of the catalyst alone, plasma alone, and their synergistic effect on CH4 conversion are experimentally analyzed. It shows that the CH4 conversion rate under plasma catalysis is more than three times that of catalyst alone and plasma alone, with a maximum of 66.7% at 375 °C and 21 W, revealing a significant synergistic effect of plasma catalysis. The influence of Mn/Ce mass ratios (11Mn/Ce and 45Mn/Ce) and operational conditions (CH4/O2 molar ratio, preheating temperature, and discharge power) on CH4 conversion by plasma catalysis are also investigated. The CH4 conversion rate increases with the decrease of the CH4/O2 molar ratio and the increase in preheating temperature and discharge power. Meanwhile, the Mn/Ce mass ratio affects the CH4 oxidation and the synergistic effect of plasma catalysis. The oxidation activity of the 11Mn/Ce catalyst is mostly affected by the power at the preheating temperature below 325 °C. However, the 45Mn/Ce catalyst is affected by both preheating temperature and power. In addition, as the discharge power increases, the CH4 conversion rate exhibits a linear increase for 11Mn/Ce but exponential for 45Mn/Ce.

Flame made low Pt loading catalysts supported on different metal oxides for catalytic combustion of CO and CH4

Catalytic combustion is an effective approach to remove air pollutants from various emission sources. For this purpose, supported noble metal catalysts are preferred in commercial applications due to their outstanding catalytic activity for eliminating CO, hydrocarbon compounds and NOx. In this paper, we employ the flame spray pyrolysis method to prepare a series of Pt-based catalysts with four different supports (TiO2, ZrO2, MgO and ZnO) and variable low Pt loadings for catalytic combustion of CO and CH4. The performance of 0.5 Pt/TiO2 is the best in all samples, in which the T90 temperatures are 107 and 500 °C for 90% conversion of CO and CH4, respectively. To examine its thermal stability, a time-on-stream test at 700 °C for 420 min is carried out, resulting in a decrease of about 5% in the final conversion of CH4. The X-ray diffraction results show that TiO2 support is a mixed phase with a major amount of anatase and a small amount of rutile other than a pure phase of ZrO2, MgO and ZnO. Furthermore, X-ray photoelectron spectroscopy analysis and high-angle annular dark-field scanning transmission electron microscopy observation show that when the Pt loading is low, the Pt species exist as highly dispersed single atoms on the surface of the TiO2 support. As the Pt loading gradually increases, the state of the Pt species transitions from single atoms to Pt clusters, resulting in a decrease in dispersion. Ultimately, the Pt can successfully accumulate on the surface of the TiO2 nanoparticles, providing abundant active sites for efficient catalytic combustion reactions.

Enhanced catalytic performance for gas phase epoxidation of propylene with H2 and O2 by multiple pretreated Au/TS-1 catalysts

Direct epoxidation of propylene (C3H6) with hydrogen (H2) and oxygen (O2) over Au/TS-1 catalyst was promising way for the synthesis of propylene oxide (PO). However, high selectivity of PO (>95 %) and conversion of C3H6 (>5 %) cannot be achieved at the same time. The industrialization process was severely restricted. In this paper, Au/TS-1 catalysts were synthesized by deposition precipitation method with alkali metal promoter. And alkaline gases and silane coupling post-treatment were performed to promote the catalytic activity. The prepared samples exhibited a much better C3H6 conversion (6.5 %) and PO selectivity (95.1 %) compared with general catalyst using normal synthetic technology. Cs2CO3 was beneficial to increasing Au nanoparticles uptake efficiency. Both NH3 and triethoxyvinylsilane post-treatment were good for smaller and more uniform loading of Au nanoparticles. The decreasing in surface hydroxyl density effectively alleviated the occurrence of PO ring opening isomerization. The increased hydrophobicity of TS-1 surface was conducive to the rapid desorption of generated PO and significantly increased PO selectivity. Multiple pretreatment was also favorable for extending the lifetime of Au/TS-1 catalyst.

Deciphering the role of Moringa oleifera seeds and probiotic bacteria on mitigation of biogas production from ruminants

Maintaining cleaner and more sustainable ecosystems by mitigating greenhouse gas (GHG) emissions from livestock through dietary manipulation is in demand. This study was aimed to assess the effect of Moringa oleifera seeds and probiotics (Pediococcus acidilactici BX-B122 and Bacillus coagulans BX-B118) as feed supplements on GHG production and fermentation profile from steers and sheep. The treatments included diets containing 0, 6, 12, and 18% of M. oleifera seeds meal and a mixture of probiotic bacteria (0.2 ml/g of diet). Total biogas production, CH4, CO, and H2S emission from animals (up to 48 h), rumen fermentation profile, and CH4 conversion efficiency were recorded using standard protocols. Results showed interaction among M. oleifera seeds and probiotics on asymptotic biogas production and total biogas production up to 48 h (P < 0.05). The rate of CH4 emission in steers was reduced from 0.1694 to 0.0447 ml/h using 6 and 18% of M. oleifera seeds (P < 0.05). Asymptotic CO and the rate of CO production were increased (P < 0.05) by supplementing different doses of M. oleifera seeds and probiotics. Adding 12% of M. oleifera seeds and probiotics reduced H2S production from 0.0675 to 0.0112 ml H2S/g DM (at 48 h of fermentation) in steers. In sheep, the additives mitigated H2S production from 0.0364 to 0.0029 ml H2S/g DM (at 48 h of fermentation), however there were not interaction (P = 0.7744). In addition, M. oleifera seeds and probiotics reduced the pH level and dry matter degradability (DMD) in steers and sheep (P < 0.0001) showing a positive impact on CH4:ME and CH4:OM (in steers) and CH4:SCFA (in sheep), while the interaction was not significant (P > 0.05) for CH4:SCFA (in steers) and CH4:ME and CH4:OM (in sheep). In conclusion, the interaction of M. oleifera seeds and probiotics in the feeding diet reduced GHG emissions and affected the fermentation profile of steers and sheep.

Unbounding the Future: Designing NiAl-Based Catalysts for Dry Reforming of Methane.

Dry reforming of methane (DRM), the catalytic conversion of CH4 and CO2 into syngas (H2+CO), is an important process closely correlated to the environment and chemical industry. NiAl-based catalysts have been reported to exhibit excellent activity, low cost, and environmental friendliness. At the same time, the rapid deactivation caused by carbon deposition, Ni sintering, and phase transformation exerts great challenges for its large-scale applications. This review summarizes the recent advances in NiAl-based catalysts for DRM, particularly focusing on the strategies to construct efficient and stable NiAl-based catalysts. Firstly, the thermodynamics and elementary steps of DRM, including the activation of reactants and coke formation and elimination, are summarized. The roles of Al2O3 and its mixed oxides as the support, and the influences of the promoters employed in NiAl-based catalysts over the DRM performance, are then illustrated. Finally, the design of anti-coking and anti-sintering NiAl-based catalysts for DRM is suggested as feasible and promising by tailoring the structure and states of Ni and the modification of Al-based supports including small Ni size, high Ni dispersion, proper basicity, strong metal-support interaction (SMSI), active oxygen species as well as high phase stability.

Bimetallic Single Atom/Nanoparticle Ensemble for Efficient Photochemical Cascade Synthesis of Ethylene from Methane

AbstractLight‐driven photoredox catalysis presents a promising approach for the activation and conversion of methane (CH4) into high value‐added chemicals under ambient conditions. However, the high C−H bond dissociation energy of CH4 and the absence of well‐defined C−H activation sites on catalysts significantly limit the highly efficient conversion of CH4 toward multicarbon (C2+) hydrocarbons, particularly ethylene (C2H4). Herein, we demonstrate a bimetallic design of Ag nanoparticles (NPs) and Pd single atoms (SAs) on ZnO for the cascade conversion of CH4 into C2H4 with the highest production rate compared with previous works. Mechanistic studies reveal that the synergistic effect of Ag NPs and Pd SAs, upon effecting key bond‐breaking and ‐forming events, lowers the overall energy barrier of the activation process of both CH4 and the resulting C2H6, constituting a truly synergistic catalytic system to facilitate the C2H4 generation. This work offers a novel perspective on the advancement of photocatalytic directional CH4 conversion toward high value‐added C2+ hydrocarbons through the subtle design of bimetallic cascade catalyst strategy.

Bimetallic Single Atom/Nanoparticle Ensemble for Efficient Photochemical Cascade Synthesis of Ethylene from Methane.

Light-driven photoredox catalysis presents a promising approach for the activation and conversion of methane (CH4) into high value-added chemicals under ambient conditions. However, the high C-H bond dissociation energy of CH4 and the absence of well-defined C-H activation sites on catalysts significantly limit the highly efficient conversion of CH4 toward multicarbon (C2+) hydrocarbons, particularly ethylene (C2H4). Herein, we demonstrate a bimetallic design of Ag nanoparticles (NPs) and Pd single atoms (SAs) on ZnO for the cascade conversion of CH4 into C2H4 with the highest production rate compared with previous works. Mechanistic studies reveal that the synergistic effect of Ag NPs and Pd SAs, upon effecting key bond-breaking and -forming events, lowers the overall energy barrier of the activation process of both CH4 and the resulting C2H6, constituting a truly synergistic catalytic system to facilitate the C2H4 generation. This work offers a novel perspective on the advancement of photocatalytic directional CH4 conversion toward high value-added C2+ hydrocarbons through the subtle design of bimetallic cascade catalyst strategy.

Optimization of Cu/MnO2 catalyst for enhanced methane bi-reforming: a response surface methodology approach for sustainable syngas production

Hydrogen or syngas, valued for its clean and high-energy properties, stands as a promising solution to future energy shortages by converting CO2 and CH4 waste into renewable syngas through a reaction known as methane bi-reforming. Hence, the purpose of this current research is to examine the effectiveness of Cu/MnO2 catalyst in methane bi-reforming (MBR) using response surface methodology (RSM). The synthesis of the 15%Cu/MnO2 catalyst was accomplished using the ultrasonic impregnation method, followed by a comprehensive analysis and characterization of the catalyst using CO2-TPD, BET, H2-TPR, TPO, and XRD evaluation. The effect of reaction parameters was investigated using RSM analysis, including temperature, CO2/CH4 ratio, and gas hourly space velocity (GHSV) (700–900 °C, 0.2–1.0, and 16–36 L g cat−1 h−1, respectively). According to the analysis of variance and three-dimensional response surface plots, it was determined that CH4 conversion and H2 yield were largely influenced by temperature, whereas CO2 conversion and CO yield could be manipulated through CO2/CH4 feed ratio. Meanwhile, the GHSV appeared to have a significant influence on the H2/CO ratio and CH4 conversion. From the experimental data, it was found that the 15%Cu/MnO2 catalyst performed best under specified optimal conditions of 800 °C, a CO2/CH4 ratio of 0.6, and a GHSV of 26 L g cat−1 h−1. These optimal conditions resulted in the maximum conversion of CH4 (54.67%), CO2 conversion (47.52%), H2 yield (43.81%), CO yield (36.29%), and H2/CO ratio (1.384). Despite the inevitability of carbon formation resulting from the breakdown of CH4 and CO at high temperatures, the examination of the spent catalysts under optimal conditions yielded a smaller quantity of carbon of approximately 28.27% in comparison to the suboptimal conditions with 55.37%.