Al2O3 Catalyst Research Articles

Favorable formation of needle-shaped NiAl2O4 phase over macroporous Ni/CexZr1-xO2–Al2O3 catalysts in one-pot preparation and coke-resistant catalytic performance in dry reforming of methane

In this study, we report the formation of needle-shaped NiAl2O4 via favorable interactions between Ni and Al species over macroporous Ni/CexZr1-xO2–Al2O3 catalysts for dry reforming of methane (DRM) and its remarkable improvement in the catalytic performance. The macroporous catalysts prepared by a one-pot (OP) method promote a favorable interaction between Ni and Al species that results in the formation of unique needle-shaped NiAl2O4 due to easy access to each other compared with that by incipient wetness impregnation. The NiAl2O4 phase in the calcined catalysts transforms into highly dispersed Ni and defective Al2O3 via the Ni exsolution in the reduction step. The presence of oxygen vacancies near Ni0 species facilitates the CO2 activation and enhances the catalyst stability over DRM. The optimized distribution of active sites with abundant defects over macroporous Ni/CexZr1-xO2-Al2O3 catalysts (OP) result in high conversions of CH4 and CO2 and a low coking rate in DRM.

A Highly Efficient Catalytic Co-Combustion of Aromatic and Oxygenated Volatile Organic Compounds (VOCs) via H2-Driven Onsite Heating

Catalytic combustion, a highly efficient technique for reducing volatile organic compounds (VOCs), is the focus of this study. We investigate the improved catalytic efficiency of the physical mixing of nanosized Pt and atomically dispersed Co, supported on Al2O3 catalysts (Pt-Co)/Al2O3 (PM) for the catalytic combustion of VOCs. The catalyst efficiency is evaluated for the hydrogen-assisted catalytic oxidation of various VOCs, including aromatic and oxygenated VOCs such as benzene, toluene, methanol, and formic acid. Our study aims to understand the impact of hydrogen incorporation on the combustion process of various VOCs. The findings of this work underscore the potential of hydrogen-assisted catalytic ignition, which can achieve ignition at ambient temperature, a significant departure from conventional electric heating that typically requires additional energy to raise the temperature. Various characterization techniques, such as BET, STEM, and XRD, are employed to assess the structure–activity relationship of the catalyst. The optimal hydrogen concentration for complete VOC conversion is 3%. Notably, even at a lower hydrogen concentration of 2%, benzene and methanol reach an ideal ignition temperature of over 500 °C when introduced into the physically mixed catalyst. This study highlights the significant potential of hydrogen-assisted catalytic combustion, inspiring further research and offering a promising method to reduce VOCs effectively.

Effect of Ga-Promoted on Ni/Zr + Al2O3 Catalysts for Enhanced CO2 Reforming and Process Optimization

AbstractIn this study, zirconia-modified alumina support (S) was used to investigate Ga-promoted Ni catalysts for dry reforming of methane (DRM). The catalysts (Ni + (0–3) wt% Ga/S) were prepared using the wet impregnation method and calcined at 700 °C for 3 h. The inclusion of Ga enhanced the surface area, basicity, and metal-support interaction of the Ni-Ga/S catalysts. Smaller Ni particles containing Ga were seen in the TEM. The most active and stable catalyst was Ni + 2.0 Ga/S, having a conversion of 35% CO2 and 28% CH4 at 600 °C and displaying less (17%) carbon deposition. Furthermore, the DRM process was optimized by a mathematical model. The model determined the optimal conditions as follows: temperature (800 °C), gas flow rate (GHSV—30,000 ml h−1gcat−1), and methane to carbon dioxide ratio (1:1). The model predicts CH4 and CO2 conversions of 76.76% and 82.0%, respectively, and an H2/CO ratio of 1.02, compared to experimental results showing CH4 conversion at 74.56%, CO2 conversion at 83.25%, and an H2/CO ratio of 1.01. The model demonstrates excellent agreement with the experimental observations, exhibiting less than 3% error. Graphical Abstract

Catalytic pyrolysis of cashew de-oiled shell and spent lemongrass

Residual/ spent biomasses are rising each day due to the increased processing of crops to extract essential oils. An efficient method is required for its management and value-addition. Therefore, this study aims to explore the catalytic pyrolysis of two residual biomasses, i.e., cashew de-oiled shell and spent lemongrass biomass. Different metal oxide(s) catalysts prepared using Al2O3 support, i.e., Fe2O3/Al2O3, Co3O4/Al2O3, Mn2O3/Al2O3, and NiO/Al2O3, are considered for this study. From the product distribution, it was analysed that the incorporation of catalyst led to a decrease in the bio-oil yield as compared to non-catalytic pyrolysis, which showed that Al2O3-supported catalysts promote the cracking reactions of pyrolysis vapours and produce lighter molecules. It was found that the incorporation of catalysts significantly affected the content of the functionalities present in the pyrolysis bio-oil. Fe2O3/Al2O3 was observed to greatly increase the area % of phenolics up to 52.35 and 75.57 area % in spent lemongrass and cashew de-oiled shell bio-oil, respectively. Metal oxide catalysts were also observed to reduce the oxygenates and produce high-quality bio-oil. Overall, this study demonstrates the effective utilization of cashew de-oiled shell and lemongrass biomass for cleaner energy/chemicals production through catalytic pyrolysis, highlighting the potential of metal oxide supported on Al2O3 catalysts in biomass valorization.

Construction of La/Al2O3 nanorod-like catalyst with rich basic sites: Enabling efficient conversion of COS-superior selectivity and theoretical insights

The introduction of surface basic sites to COS hydrolysis catalysts can improve H2O activation and COS adsorption, leading to enhanced catalytic performance. However, maximizing the concentration of basic sites remains a challenge due to the limited exposed surface area of these catalysts. Herein, a La/Al2O3 catalyst with abundant alkaline sites to catalyze the hydrolysis of COS was prepared by a simple ammonia-assisted hydrothermal method. This synthesized La/Al2O3 catalyst exhibits a thin rod-like structure formed by the random accumulation of nanoparticles. Lanthanum, one of the most abundant rare earth metals, is an ideal doping aid to further promote the COS-catalyzed hydrolysis performance of Al2O3. Characterization studies show that the proper lanthanum loading effectively enhances the formation of basic sites, leading to improved lattice oxygen reactivity and –OH adsorption capacity. As a result, the prepared La-loaded Al2O3 nanorod sample with abundant basic sites exhibits nearly 100 % COS conversion and total H2S yield at 160 °C. In addition, the reaction pathways and deactivation mechanisms for selective catalytic hydrolysis of COS on the La-doped Al2O3 catalyst were revealed by using in situ DRIFTS to evaluate COS adsorption and hydrolysis. Density functional theory calculations showed that La loading enhances the electron transfer between the La and Al atoms, improves the formation of basic sites, and enhances the adsorption of –OH. This study provides new insights into the design of efficient alumina-based catalysts for the catalytic hydrolysis of COS.

Selective reduction of CO2 to CO over alumina-supported catalysts of group 5 transition metal carbides

We show the applicability of a preparation method, previously reported for obtaining tailored bulk VCx catalysts, for alumina-supported G5TMCs. The characteristics of the G5TMCs/Al2O3 catalysts and their behaviour in the selective reduction of CO2 to CO through the RWGS reaction is reported. VCx/Al2O3 catalysts were active, stable and highly selective; meanwhile NbC/Al2O3 and TaC/Al2O3 were not active. VCx/Al2O3 catalysts exhibited selectivity to CO over 99.5 % at temperature above 773 K. The characteristics of alumina-supported vanadium carbide particles depended on the vanadium precursor and on the atmosphere used during the catalyst preparation. XPS characterization of VCx/Al2O3 catalysts revealed the presence of carbide species on surface before and after RWGS reaction. The catalytic behaviour of VCx/Al2O3 is analysed in the light of their characteristics and compared with bulk VCx counterparts. The most performant catalyst, VC(Pr)/Al2O3, was stable over 4 days at 723 K, with ∼100 % selectivity to CO and CO2 conversion of ∼11 %.

Highly Stable Ni-B/Honeycomb-Structural Al2O3 Catalysts for Dry Reforming of Methane.

Two-component catalysts have garnered significant attention in the field of catalysis due to their ability to inhibit Ni sintering. In the present work, honeycomb-structuralstructured Al2O3-supported Ni and B were prepared to enhance coke tolerance during dry reforming of methane (DRM). Transmission electron microscopy (TEM) results revealed that the average particle sizes on Ni/Al2O3 and Ni-0.16B/Al2O3 were 7.6 nm and 4.2 nm, respectively, indicating that B can effectively inhibit Ni sintering. After a 100-hour reaction, the conversion of CH4 and CO2 on Ni/Al2O3 decreased by approximately 5 %, whereas on Ni-0.16B/Al2O3, there was no significant decrease in CH4 and CO2 conversion, with values of approximately 81.6 % and 87.2 %, respectively. In situ DRIFT spectra demonstrated that Ni-0.16B/Al2O3 enhanced the activation of CO2, thus improving the catalyst's stability. A Langmuir-Hinshelwood-Hougen-Watson (LHHW) model was developed for intrinsic kinetics, and the resulting kinetic expressions were well-fitted fit to the experimental data, with R2 values exceeding 0.9. ActivationThe activation energies were also calculated. The outstanding stability of Ni-0.16B/Al2O3 can be attributed to its stable honeycomb structure and B's ability to significantly inhibit Ni sintering, reduce catalyst particle size, and enhance coke tolerance.

Hydro-co-processing Jatropha oil and crude oil blend with Ni-Mo-supported Al2O3 catalyst to produce hybrid fuels: the effect of catalyst particle size

Hydro-co-processing Jatropha oil and crude oil blend with Ni-Mo-supported Al2O3 catalyst to produce hybrid fuels: the effect of catalyst particle size

Modulating the Reaction Pathway of Ni2P/Al2O3 by Introducing Different Noble Metals for Hydrodesulfurization of Diesel.

Regulating the reaction pathway of a hydrodesulfurization (HDS) catalyst to achieve ultradeep desulfurization of diesel is a low-energy-consumption yet effective strategy but remains a tricky challenge. Herein, we present a Ni2P/Al2O3 catalyst with mesoporous properties synthesized by a facile hydrothermal-temperature-programmed reduction and normal impregnation (TPRI) method, and then different precious metals with similar loadings were introduced to prepare M-Ni2P/Al2O3 (M = Pt, Pd) catalysts through incipient wetness impregnation. Their structures were analyzed by a series of characterization methods, and their catalytic performances were examined for 4,6-dimethyldibenzothiophene (4,6-DMDBT) HDS. The correlation characterization results revealed that the kind of precious metals significantly affected the surface acidity and then the metal-support interaction (MSI) between Ni2P and Al2O3. Among them, the Pt-Ni2P/Al2O3 catalyst exhibits superior HDS activity with 88.5% 4,6-DMDBT conversion to Pd-Ni2P/Al2O3 (76.3%) and pristine Ni2P/Al2O3 (58.6%) catalysts under reaction conditions of 3.4 MPa, 340 °C, and LHSV = 4.8 h-1. This should be due to the introduction of Pt, which significantly facilitates the dissociation rate of H2 and the subsequent generation of more active hydrogen species than Pd, thereby promoting the formation of Brønsted acid sites, remarkably facilitating the isomerization (ISO) pathway, and markedly enhancing the 4,6-DMDBT HDS conversion of Pt-Ni2P/Al2O3. This work provides an efficient protocol to tame the reaction pathway and thereafter the catalytic performance of the HDS catalyst in the future.

Hydrolysis of carbonyl sulfide using non-ionic surfactant-modified mesoporous γ-Al2O3 catalysts with high efficiency

Carbonyl sulfur (COS) was difficult to be removed by conventional desulfurization technologies because of its stable chemical properties. Mesoporous γ-Al2O3 (MA) showed excellent potential for hydrolysis of COS, but the catalyst life was greatly shortened with the progress of the reaction. Therefore, improving the catalyst life is the key to MA which can apply to hydrolysis of COS. In this study, P123 modified mesoporous γ-Al2O3 (P-MA) catalyst was prepared by sol–gel method, and it was regulated by template agent and acidity regulator. These preparation conditions of P-MA were optimized to improve the hydrolysis efficiency of COS. The effects of temperature, space velocity, relative humidity and oxygen concentration for the hydrolysis efficiency of COS were studied. The results show that the optimized P-MA catalyst is suitable for COS low-temperature hydrolysis reaction, and it can maintain 99 % for 10 h under the tough reaction conditions. The only crystal of P-MA was γ-Al2O3 with large specific surface area and uniform distribution pore, which are beneficial to the COS hydrolysis. In addition, the hydrolysis efficiency of COS can also remain 97 % for 10 h in the O2 and CO2 atmosphere, indicating that the P-MA catalyst has a specific anti-poisoning ability. The kinetics and reaction mechanism of COS catalytic hydrolysis were studied, which showed that the adsorption of H2S was the key to hindering the continuous reaction. The P-MA can effectively inhibit the adsorption of H2S, which greatly improved COS hydrolysis life of P-MA. This study provided a theoretical basis for the application of Al2O3 catalyst in the COS hydrolysis.

Selective production of phenol from the end-of-life wind turbine blade through catalytic pyrolysis

This study employed catalytic pyrolysis to enhance the selectivity and yield of phenol in the pyrolysis oil derived from the end-of-life wind turbine blade (WTB). It was confirmed that the NiO(10)/Al2O3 catalyst exhibited the best activity, reaching a phenol selectivity of 28.57 % at 500 °C with a heating rate of 10 °C/min. Furthermore, a competitive phenomenon between the catalytic formation of phenol and that of gaseous products was observed. Characterization results indicated that at lower loading content of NiO on the Al2O3 carrier, NiAl2O4 crystals tended to form preferentially, which reduced catalyst activity by covering surface strong acid sites. With increasing the loading content of NiO, saturation of NiAl2O4 formation occurred, and free NiO crystals became dominant. This resulted in the creation of abundant Lewis acid sites, enhancing the catalytic formation of phenol. Whilst, excessive accumulation of free NiO crystals increased strong acid sites and significantly generated lattice oxygen, promoting the cracking of pyrolysis oil to gaseous products, which was detrimental to phenol enrichment but facilitated the production of H2-rich syngas. The conclusions offered valuable insights for upgrading pyrolysis products derived from epoxy resin polymers during the recovery of end-of-life WTB.

Fe2O3/γ-Al2O3 and NiO/γ-Al2O3 catalysts for the selective catalytic oxidation of ammonia

Ammonia, a significant atmospheric pollutant, requires effective emission control due to its inherent toxicity and the generation of secondary pollutants like particulate matter. This control can be achieved through various methods, including catalytic processes. Therefore, our study focuses on evaluating the potential of catalysts based on iron oxide and nickel oxide supported on γ–Al2O3 for the selective catalytic oxidation of NH3 to N2 (NH3-SCO). The γ–Al2O3 was obtained by thermal decomposition of aluminum hydroxide, and 5 or 10 wt% of Fe or Ni was added through wetness incipient impregnation. XRD diffractograms confirmed the formation of the γ–Al2O3 phase. XRD, H2-TPR, and UV–vis DRS data showed the presence of Fe2O3, NiO, and NiAl2O4 in the catalysts. Introducing metal oxides onto the support led to a drop in the specific area, pore size, pore volume, and NH3 desorption, which was higher for the catalysts containing Fe. The catalysts were active in NH3-SCO, and the insertion of Fe or Ni was essential because it promoted a significant increase in the NH3 conversion (∼75 % Fe and ∼55 % Ni), compared to pure support (∼8 %), mainly from 400 °C. However, doubling the metal content has not resulted in a considerable increase in NH3 conversion. The N2 selectivity was higher for the catalysts containing Ni (∼85 %) from 400 °C compared to catalysts containing Fe (∼76 %). Such behavior was due to the larger surface area of the Ni-containing catalysts. Despite that, the 5Fe/γ–Al2O3 catalyst emerged as the most effective option for NH3-SCO applications, combining higher NH3 conversion and good N2 selectivity.

LaCoO3 is a promising catalyst for the dry reforming of benzene used as a surrogate of biomass tar.

Tar build-up is one of the bottlenecks of biomass gasification processes. Dry reforming of tar is an alternative solution if the oxygen chemical potential on the catalyst surface is at a sufficient level. For this purpose, an oxygen-donor perovskite, LaCoO3, was used as a catalyst for the dry reforming of tar. To circumvent the complexity of the tar and its constituents, the benzene molecule was chosen as a model compound. Dry reforming of benzene vapor on the LaCoO3 catalyst was investigated at temperatures of 600, 700, and 800 °C; at CO2/C6H6 ratios of 3, 6, and 12; and at space velocities of 14,000 and 28,000 h-1. The conventional Ni(15 wt.%)/Al2O3 catalyst was also used as a reference material to determine the relative activity of the LaCoO3 catalyst. Different characterization techniques such as X-ray diffraction, N2 adsorption-desorption, temperature-programmed reduction, and oxidation were used to determine the physicochemical characteristics of the catalysts. The findings demonstrated that the LaCoO3 catalyst has higher CO2 conversion, higher H2 and CO yields, and better stability than the Ni(15 wt.%)/γ-Al2O3 catalyst. The improvement in activity was attributed to the strong capacity of LaCoO3 for oxygen exchange. The transfer of lattice oxygen from the surface of the LaCoO3 catalyst facilitates the oxidation of carbon and other surface species and leads to higher conversion and yields.

Construction of Ni−Re Supported on Hydrotalcite‐Derived MgAl Catalysts for Promoting the Ring Hydrogenation of Furfural into Tetrahydrofurfuryl Alcohol in Water

AbstractBiomass‐derived feedstocks play a vital role in sustainable economies for renewable energy, waste management, energy security, and commercial prospects. This study focused on promoting the ring hydrogenation of furfural (FAL) into tetrahydrofurfuryl alcohol (THFA) in an aqueous solution using a potential Ni−Re‐supported hydrotalcite‐derived MgAl catalyst at different Ni : Re molar ratios. Structural analyses, such as an in situ time‐resolved X‐ray absorption near edge structure, under H2 reduction elucidated the simultaneous transformation of Re6+ and Re7+ to Re0 with the remaining highly stable Ni2+. The construction of Ni−Re on hydrotalcite‐derived MgAl catalyst resulted in the alleviated H2 reduction behavior, facilitated H2 adsorption and desorption processes, and suitable catalyst acidity detected by H2 temperature‐programmed reduction, and H2 and NH3 temperature‐programmed desorption experiments, respectively. Under optimized conditions, a maximum THFA yield of 78 % with a complete FAL conversion was attained using Ni1Re0.16/MgO−Al2O3 catalyst at a reaction temperature of 140 °C, H2 pressure of 20 bar, catalyst loading of 20 %, and reaction time of 2 h in a H2O system. Isotopic deuterium (D2O) labeling revealed that D substitution was notably pronounced through isotopic exchange between the D atom from D2O and H atom in FAL during its hydrogenation to THFA.

Coke formation and mineral accumulation on HZSM-5/Al2O3 catalysts during in-situ catalytic fast pyrolysis of microalgae over multiple regeneration cycles

Catalyst deactivation caused by coke formation and mineral accumulation occurs simultaneously and intensively during the catalytic pyrolysis of biomass. A comprehensive understanding of their distinction and interactions during the deactivation and regeneration process of shaped catalysts are essential for catalyst advancement and longevity in industrial application. In this study, we report the reversible and non-reversible catalyst deactivation caused by coke formation, mineral accumulation and the interactions thereof by a multi-technique characterization of a HZSM-5/Al2O3 catalyst (crushed extrudates; particle size 1–3 mm) in fast pyrolysis. A total of 5 cycles of catalyst reaction/regeneration were performed in a bench scale reactor (60 g/h feedstock feeding rate; pyrolysis temperature of 500°C) using both raw microalgae (Scenedesmus almeriensis, or SA) and citric acid treated microalgae (CA-SA). The measured properties of the fresh and used catalysts (SA-R5, 5th recycled and reacted catalyst mixed with SA) disclosed the anticorrelation of the metal contents (increased by a factor of 2.5 times) with surface area (-4.4 %) and Brønsted acid (-70.4 %). The presence of minerals in the feedstock might catalytically alter the pyrolysis chemistry, interfere with the shape selectivity and acidity of the catalysts, thus reduced the formation of coke. Additionally, metal species from the microalgae ash that ended up on the catalyst could promote coke combustion during the regeneration process. This work revealed the demineralization of the microalgae prior to fast pyrolysis minimized the rate of irreversible catalyst deactivation. Whereas, the trade-off between promoted coke formation after the ash removal of microalgae and accelerated minerals accumulation without microalgae demineralization should be evaluated.

Enhancement of non-thermal plasma-catalytic CO2 reforming of CH4 using Ni/Mg–Al2O3 catalysts in a parallel plate dielectric barrier discharge reactor

CO2 and CH4 are converted to syngas by dry reforming of methane (DRM) reaction. This research investigated the effects of the Mg promoter on Al2O3-supported Ni catalysts and Mg calcination temperature on the DRM performance in a parallel plate dielectric barrier discharge reactor. The Mg promoter played a crucial role in the DRM performance, as increasing the Mg calcination temperature from 700 °C to 800 °C significantly improved the DRM performance and catalyst properties, including increased specific surface area, decreased total acidity, reduced crystallite and particle sizes, and more uniform dispersion of the Ni nanoparticles. Under these conditions, the H2 and CO selectivity were 77.0 % and 70.7 %, the CH4 and CO2 conversion were 25.1 % and 20.6 %, and the energy efficiency was 8.4 %. In addition, the catalyst was associated with a lower coking rate (0.5 mg C/gcat h), a relatively low carbon deposit of 1.5 %, and a carbon loss of 2.8 %, possibly because the weak acidity hindered the Boudouard reaction and CH4 decomposition. However, increasing the Mg calcination temperature to 900 °C increased the total acidity and Ni particle size, decreasing H2 and CO selectivities and increasing carbon deposits on the catalyst surface.

The promotion of rare earth on Pt-SiO2-Al2O3 catalyst for NO oxidation in diesel exhaust

The effective oxidation of NO is the key to the catalytic treatment of diesel vehicle exhaust. Improving the NO oxidation ability is mainly to optimize the chemical state of the active site (Pt), followed by increasing the number of active centers. Considering that the atoms with electronegativity weaker than Pt can provide electrons to change the chemical state of Pt, rare earth elements with weak electronegativity are selected as additives to obtain Pt/M-SiO2-Al2O3 (M = Sc, Y, La, Ce, Pr, Nd, Sm, Eu) catalysts by co-impregnation method. Among them, the Pt/La-SiO2-Al2O3 catalyst has the best NO oxidation performance, compared with the Pt-SiO2-Al2O3, the NO conversion rate increased by 28 %. Due to the special outer electron arrangement of La, its electronegativity is the smallest in rare earth, which makes its outer electrons easy to transfer to Pt atoms, and has the strongest electron interaction. Thus, the highest content of Pt0 was detected in CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS) and X-ray photoelectron spectroscopy (XPS). In addition, CO chemisorption and transmission electron microscopy (TEM) confirmed that the introduction of La in the catalyst can significantly improve the dispersion of precious metals. Notably, this simple approach of affecting electron interaction by introducing weakly electronegative elements provides a reference for the design of noble metal catalysts with different valence states to solve complex problems.

Catalytic co-pyrolysis behaviour and kinetics study of waste lignocellulosic non-edible seeds and Covid-19 plastic over Al2O3 catalyst

The current research centred on estimating kinetic parameters and examining the composition of pyrolysis vapours from neem seeds and COVID-19 waste nitrile gloves (NG) using Pyro-GC–MS. Owing to the intricacy of the co-pyrolysis process, kinetic parameters were studied using KAS, OFW, FM, and VZ models. Biomass and plastic were mixed in different proportions (1:1, 3:1, and 5:1), whereas feed to catalyst was mixed at 3:1, 5:1 and 8:1, respectively. The estimation of the kinetic parameters of co-pyrolysis of NMS and NG confirmed that the 3:1 ratio and the feeds-to-catalyst ratio at 5:1 were found to be most effective in producing maximum hot vapours. Moreover, the analysis of pyrolysis vapours confirmed that a ratio of 3:1 for (NMS to NG) and a ratio of 5:1 for feed to catalyst (NMS + NG(3:1) + Al2O3 (5:1) resulted in the highest production of hydrocarbons while decreasing the presence of acids and oxygenated compounds.

Direct coupling of CH4 and CO2 into acetic acid over CuPdO2/Al2O3 in the presence of H2O2

Direct conversion of methane and carbon dioxide into acetic acid is a dream way to address the two greenhouse gases, but is challenged by their chemical inertness. Cu and Pd are promising candidates both in CH4 and CO2 activation as well as the subsequent C-C coupling reactions at low temperature. Herein, we report that acetic acid can be produced by the direct coupling of CH4 and CO2 in the presence of H2O2 over Cu-Pd/Al2O3 catalysts at 50 °C. Results show that the acetic acid yield reaches 48.1 μmol·gcat−1·h−1 on the optimized reaction condition over Cu3.8-Pd1.6/Al2O3 catalyst, which is higher than that of either mono-Cu or mono-Pd catalyst. Extensive characterization indicates the higher activity of Cu3.8-Pd1.6/Al2O3 catalyst is attributed to the strong synergistic effect between Cu and Pd, which results in the formation of CuPdO2 phase, and thus promoting the electron transfer from Cu to Pd. DRIFTS experiments reveal that acetic acid is produced by the coupling of CH3* and COOH* over CuPdO2 active sites via Langmuir-Hinshelwood mechanism, where CH3* is originated from CH4 dehydrogenation step, and COOH* may formed by the activation of CO2 by H2O2. This study provides a new approach for the co-conversion of CH4 and CO2 into acetic acid at low temperature.

Surface Carbon Formation and its Impact on Methane Dry Reforming Kinetics on Rhodium‐based Catalysts by Operando Raman Spectroscopy

A mechanism for carbon deposition and its impact on the reaction kinetics of Methane Dry Reforming (MDR) using Rhodium‐based catalysts is presented. By integrating Raman spectroscopy with kinetic analysis in an operando‐annular chemical reactor under strict chemical conditions, we discovered that carbon deposition on a Rh/α‐Al2O3 catalyst follows a nucleation‐growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 concentration. The findings elucidate the spatiotemporal development of carbon aggregates on the catalyst surface and their effects on catalytic performance. Furthermore, the proposed mechanism for carbon formation shows that the influence of CO2 on MDR kinetics is an indirect result of carbon accumulation over time frames exceeding the turnover frequency, thus reconciling conflicting reports in the literature regarding CO2's kinetic role in MDR.