Temperature-programmed Surface Reaction Research Articles

Ru/MgO catalyst with dual Ru structure sites for efficient CO production from CO2 hydrogenation

The development and comprehension of supported metal catalysts for CO2 hydrogenation is of paramount importance in mitigating the net CO2 emissions. Supported Ru catalysts have been widely recognized in facilitating CO2 methanation, on which recent findings suggest that the CO2 hydrogenation process can be manipulated to favor the reverse water–gas shift (RWGS) pathway by precisely adjusting the size of Ru particles. However, the size-dependent impact of Ru remains a topic of lively debate. In this work, Ru/MgO catalysts with Ru in the form of single atoms (Ru1) and few-atom cluster (RuFAC) structures were prepared for CO2 hydrogenation. The 1.0Ru/MgO catalyst (with 1 wt.% of Ru), featuring a mixture of Ru1 and RuFAC with a size of 0.6–1.0 nm, showed the highest CO yield (38% at 500 °C) with balanced CO2 conversion and CO selectivity. Transient CO2 hydrogenation and temperature-programmed surface reaction (TPSR) studies suggested that the adsorbed CO2 species participated in CO2 hydrogenation. On Ru1 sites, CO2 hydrogenation followed the RWGS pathway, resulting in the production of CO. In contrast, on RuFAC sites, the enhanced H2 dissociation ability, along with the presence of adsorbed bidentate and monodentate carbonate species at the Ru−MgO interfaces, facilitated the formation of CH4 through the CO2 methanation pathway. This study highlights the critical roles of Ru structure and local environment in defining the CO2 hydrogenation pathways and provides new design principles for highly active Ru-based catalysts.

Boosting N2O Catalytic Decomposition by the Synergistic Effect of Multiple Elements in Cobalt-Based High-Entropy Oxides.

Nitrous oxide (N2O) has a detrimental impact on the greenhouse effect, and its efficient catalytic decomposition at low temperatures remains challenging. Herein, the cobalt-based high-entropy oxide with a spinel-type structure (Co-HEO) is successfully fabricated via a facile coprecipitation method for N2O catalytic decomposition. The obtained Co-HEO catalyst displays more remarkable catalytic performance and higher thermal stability compared with single and binary Co-based oxides, as the temperature of 90% N2O decomposition (T90) is 356 °C. A series of characterization results reveal that the synergistic effect of multiple elements enhances the reducibility and augments oxygen vacancy in the high-entropy system, thus boosting the activity of the Co-HEO catalyst. Moreover, density functional theory (DFT) calculations and the temperature-programmed surface reaction (TPSR) with isotope labeling demonstrate that N2O decomposition on the Co-HEO catalyst follows the Langmuir-Hinshelwood (L-H) mechanism with the promotion of abundant oxygen vacancies. This work provides a fundamental understanding of the synergistic catalytic effect in N2O decomposition and paves the way for the novel environmental catalytic applications of HEO.

Visualization of the Active Sites of Zinc-Chromium Oxides and the CO/H2 Activation Mechanism in Direct Syngas Conversion.

Despite wide studies demonstrating the versatility of the metal oxide-zeolite (OXZEO) catalyst concept to tackle the selectivity challenge in syngas chemistry, the active sites of metal oxides and the mechanism of CO/H2 activation remain to be elucidated. Herein, we demonstrate experimentally the role of Cr in zinc-chromium oxides and unveil visually, for the first time, the active sites for CO activation employing scanning transmission electron microscopy-electron energy loss spectroscopy using the volumetric density of surface carbon species as a descriptor. The ZnCr2O4 spinel surface with atomic ZnOx overlayer is the most active site for C-O bond dissociation, particularly at the narrow ZnCr2O4(110) facets constrained between the (311) and (111) facets, followed by the Cr-doped wurtzite ZnO surface. In comparison, the surfaces of ZnCr2O4 with aggregated ZnOx overlayers, pure ZnO, and the stoichiometric ZnCr2O4 exhibit a significantly lower activity. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometric study on different temperature programmed surface reactions with isotopes of C18O, 13CO, and D2 validates direct CO dissociation over ZnCrn oxides in CO, forming CH2 and further to hydrocarbons if H2 is present and CH2CO intermediates in syngas. The activity of CO dissociation and hydrogenation over ZnCrn oxides correlates well with the syngas-to-light-olefins activity of ZnCrn-SAPO-18 composite catalysts as a function of the Cr/Zn ratio.

Insight into the enhanced catalytic performance of phosphate-modified ZrO2/SBA-15 for the conversion of biobased 2,5-dimethylfuran and ethylene into p-xylene

Catalytic conversion of biomass-derived platform chemicals into bulk chemicals p-xylene (PX) is appealing yet challenging due to low catalytic efficiency and severe reaction conditions. In this work, we fabricated a series of phosphate-modified ZrO2/SBA-15 (xP-Zr/SBA-15) via adjusting the addition of phosphoric acid, and used them for the catalytic conversion biomass-derived 2,5-dimethylfuran (DMF) and ethylene to PX. Because of the enhanced adsorption capability for the reactant molecules (DMF and ethylene) and the good synergistic effect between Brønsted acid sites (P-OH) and Lewis acid sites (Zr4+), 30P-Zr/SBA-15 revealed an excellent catalytic performance in the selective conversion of DMF into PX. The DMF conversion was 98.5%, PX yield was 92.0% at 250 °C for 12 h, and the corresponding PX productivity was upto 50.5 mmolPX·gcat−1·h−1. The results are far superior to those obtained on most previously reported catalysts in the literature under similar reaction conditions. The kinetic study revealed that 30P-Zr/SBA-15 has a lower apparent activation energy for the tandem reaction including the Diels-Alder reaction (57.0 kJ·mo−1) and dehydration reaction (37.7 kJ·mo−1). Moreover, the 30P-Zr/SBA-15 catalyst exhibited the excellent recyclability and could be recycled at least six times without a significant loss of activity. On the basis of the temperature-programmed surface reaction of DMF and ethylene, a reasonable reaction mechanism was proposed.

Rb-Ni/Al2O3 as dual functional material for continuous CO2 capture and selective hydrogenation to CO

Ni-based dual-functional materials (DFMs) have been widely investigated for CO2 capture and reduction with H2 (CCR). However, controlling the selectivity of CO2 hydrogenation to CH4 or CO is a fundamental challenge. Most Ni-based DFMs favor the selectivity of CH4 over CO, although CO is more desirable than CH4 from a chemical-synthesis perspective. In this study, Rb-promoted Ni nanoparticles on Al2O3, Rb-Ni/Al2O3, are developed as an effective DFM for selective CO production through CCR with a CO2 conversion of 68% and a CO selectivity of 97% under isothermal conditions at 450 °C in the mixture of O2 during CO2 capture process. The developed Rb-Ni/Al2O3 is applicable to continuous CCR using double reactor system. The roles of Rb and Ni in CCR over Rb-Ni/Al2O3 for CO formation are also discussed based on temperature-programmed surface reactions and in situ spectroscopic studies.

Activation of dimethyl carbonate on CeO2 surface: A combined experimental and theoretical study

Dimethyl carbonate (DMC) has recently emerged as a green reagent that finds versatile applications in methoxycarbonylation, carbonylation, and methylation reactions due to its multiple functionalities. In order to optimize the activity/selectivity of DMC-mediated heterogeneous catalytic reaction, it is imperative to enhance the fundamental understanding of the activation of DMC on the catalyst surface. In this study, the chemistry of DMC on the CeO2(111) surface was investigated using in-situ infrared spectroscopy, temperature-programmed surface reaction, and density functional theory calculations. It is shown that DMC readily converts into adsorbed methoxycarbonyl and methoxy on CeO2(111) at near room temperature. Upon heating, methoxycarbonyl decomposes into methoxy and carbonyl; the formed carbonyl could react with the surface oxygen atom (OS) of CeO2(111) to form desorbed carbon dioxide (COOS), leaving a surface oxygen vacancy. The surface methoxy groups undergo intermolecular hydrogen transfer to form CH3OH and HCHO, which upon heating either desorb or dehydrogenate with OS to form adsorbed methoxy and formate (with OSH), respectively. Adsorbed formate could react with OS to form desorbed COOS at higher temperatures. These findings provide fundamental insights into the catalytic chemistry of DMC on CeO2(111) surface, which may prove informative for the CeO2-catalyzed DMC-mediated reactions.

Catalytic Activity of Methane Oxidation on Nickel-doped Lanthanum Strontium Titanate Perovskite from Three Synthesis Methods

BackgroundThree perovskites of nickel-doped lanthanum strontium titanate (LSTN) were made and compared for their activity toward methane oxidation. MethodThe perovskite was synthesized separately via solid-state reaction, citrate complexation, and microwave-assisted methods. Significant FindingsThe perovskite from solid state reaction gave the highest activity of syngas production in repetitive redox cycles without any deterioration, demonstrating a great potential for use in chemical looping technology. Nevertheless, the material required activation in methane, as evidenced in studies of temperature-programmed surface reaction. On the contrary, the perovskite from the complexation method behaved completely different while the microwave-synthesized one gives the poorest activity. The variation of the activity was correlated with the distinct structure from different synthesis routes, which influences where a metal phase resides and how the metal anchors onto host oxides. The information obtained here would be of great benefit in making good material with desirable properties for catalysis and potential applications.

Mechanistic Insights into the Induction Period of Methanol-to-Olefin Conversion over ZSM-5 Catalysts: A Combined Temperature-Programmed Surface Reaction and Microkinetic Modeling Study

Mechanistic Insights into the Induction Period of Methanol-to-Olefin Conversion over ZSM-5 Catalysts: A Combined Temperature-Programmed Surface Reaction and Microkinetic Modeling Study

Advanced in situ IR spectroscopy study of anisole hydrodeoxygenation over Ni/SiO2 catalysts

Hydrodeoxygenation (HDO) of anisole was investigated over Ni/SiO2 catalysts prepared by incipient wetness impregnation (IWI) and deposition–precipitation (DP). The in situ FTIR, temperature-programmed surface reaction (TPSR-MS), as well as high pressure flow reactions were carried out to relate catalyst properties and reaction mechanism. The small-size Ni0-Ni+ species (2.0 nm) in Ni/SiO2-DP catalyst exhibits a strong hydrogenolysis activity for anisole, favouring the formation of phenol and benzene. The demethylation of anisole to phenol is a rapid step compared to the deoxygenation of phenol to benzene as indicated by in situ FTIR studies. The intensity of C–C stretching vibration in the two rings was enhanced with increasing temperature, suggesting the formation of condensed-ring products was promoted by high reaction temperature. The Ni/SiO2-IWI catalyst, which exhibits a larger Ni0 particle size (14.1 nm) and higher amount of desorbed H2 per surface Ni compared to Ni/SiO2-DP, shows a high hydrogenation but low hydrogenolysis activity, towards the formation of methoxycyclohexane under 40 bar H2 pressure flow reaction.

Ni-CeO2 nanocomposite with enhanced metal-support interaction for effective ammonia decomposition to hydrogen

Ammonia is a promising hydrogen storage material due to its ease of storage and decomposition to COx-free hydrogen. Herein, we report colloidal solution combustion synthesis (CSCS) to construct Ni-CeO2 nanocomposite catalysts for efficient ammonia decomposition to generate hydrogen. Unlike conventional supported Ni/CeO2 catalyst, the prepared Ni-CeO2 nanocomposite catalyst exhibited nickel embedded in CeO2 matrix with enhanced metal-support interaction. The physicochemical properties and metal-support interaction of the catalysts can be tuned by adjusting the amount of silica sol template. The resulted Ni-CeO2 nanocomposite catalysts exhibited outstanding catalytic performance in terms of activity and stability. The hydrogen production rate reached 32.9 mmol gcat−1 min−1 at 500 °C, which is superior to other state-of-the-art Ni-based catalysts and even comparable or better than some reported Ru-based catalysts. The systematic characterizations demonstrated that the unique Ni-CeO2 nanocomposite structure with enhanced metal-support interaction, not only provided a rich Ni-CeO2 interface to stabilize small-sized Ni nanoparticles, but also had a high concentration of oxygen vacancy to strengthen electronic metal-support interaction, making nickel surface electron-rich. The integrated studies of kinetics, temperature-programmed surface reaction, and DFT calculations corroborated that this enhanced metal-support interaction including geometric and electronic effects, favored the enrichment of NH3 on the catalyst surface and facilitated rate-determining N≡N bond formation step, thereby boosting the reaction rate. This study highlights the importance of designing new structural catalysts with enhanced metal-support interaction for boosting hydrogen production from ammonia decomposition.

The Role of Fe in Ni-Fe/TiO2 Catalysts for the Dry Reforming of Methane

A series of nickel- and iron-modified titanium dioxide (Ni-Fe/TiO2) are studied for the dry reforming of methane (DRM) at 550 °C. Temperature-programmed surface reactions using CH4 and CO2 as probe molecules, as well as activity results, confirmed that both CO2 and CH4 conversion decreased with the addition of Fe. The XPS results obtained from reduced and used catalysts suggested changes in the surface nickel and iron species. Characterizations, particularly thermogravimetric analysis (TGA) and Raman spectroscopy over used catalysts, revealed that the addition of Fe can greatly inhibit the coke formation. In situ DRIFTS further identified that the addition of Fe favored the formation of carbonate species, which can facilitate the removal of coke deposited on the surface.

Crystal Plane Effect of Co3O4 on Styrene Catalytic Oxidation: Insights into the Role of Co3+ and Oxygen Mobility at Diverse Temperatures.

In the oxidation reaction of volatile organic compounds catalyzed by metal oxides, distinguishing the role of active metal sites and oxygen mobility at specific preferentially exposed crystal planes and diverse temperatures is challenging. Herein, Co3O4 catalysts with four different preferentially exposed crystal planes [(220), (222), (311), and (422)] and oxygen vacancy formation energies were synthesized and evaluated in styrene complete oxidation. It is demonstrated that the Co3O4 sheet (Co3O4-I) presents the highest C8H8 catalytic oxidation activity (R250°C = 8.26 μmol g-1 s-1 and WHSV = 120,000 mL h-1 g-1). Density functional theory studies reveal that it is difficult for the (311) and (222) crystal planes to form oxygen vacancies, but the (222) crystal plane is the most favorable for C8H8 adsorption regardless of the presence of oxygen vacancies. The combined analysis of temperature-programmed desorption and temperature-programmed surface reaction of C8H8 proves that Co3O4-I possesses the best C8H8 oxidation ability. It is proposed that specific surface area is vital at low temperature (below 250 °C) because it is related to the amount of surface-adsorbed oxygen species and low-temperature reducibility, while the ratio of surface Co3+/Co2+ plays a decisive role at higher temperature because of facile lattice oxygen mobility. In situ diffuse reflectance infrared Fourier spectroscopy and the 18O2 isotope experiment demonstrate that C8H8 oxidation over Co3O4-I, Co3O4-S, Co3O4-C, and Co3O4-F is mainly dominated by the Mars-van Krevelen mechanism. Furthermore, Co3O4-I shows superior thermal stability (57 h) and water resistance (1, 3, and 5 vol % H2O), which has the potential to be conducted in the actual industrial application.

Coke-resistant NdFe0.7Ni0.3O3 perovskite catalyst with superior stability for dry reforming of ethane

Effects of A-site cation substitution and B-site active metal doping-segregation on physicochemical properties of Ni-doped perovskite-structured LnFe0.7Ni0.3O3 (Ln = La, Nd, Sm, Eu) catalysts and their catalytic performance for dry reforming of ethane (DRE) were studied. The DRE activity follows the trend: NdFe0.7Ni0.3O3 > SmFe0.7Ni0.3O3 > EuFe0.7Ni0.3O3 > LaFe0.7Ni0.3O3. The doping-segregation process of Ni was demonstrated by in-situ X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements, which significantly improves the dispersion of Ni and enhance the interaction between metal and support. The results of temperature-programmed surface reactions (TPSR) and pulse reactions indicate that oxygen vacancies generated by the exsolution of Ni play an important role in the elimination of coke and shift the product from surface carbon to gaseous CO. According to the in-situ Raman experiments, the superior catalytic stability (no coke deposition or activity loss over 100 h) of NdFe0.7Ni0.3O3 is ascribed to its strong resistance towards carbon deposition.

The complementary relationship between Ru/Al2O3 and Ni/Al2O3 catalyst for dry reforming of methane

We report a physical mixture of 1 wt% Ru/Al2O3 with 10 wt% Ni/Al2O3 obtained from the NiAl2O4 phase as a highly active, durable, and cost-effective catalyst for the dry reforming of methane (DRM). Since the presence of Ru facilitates the reduction of Ni oxides, resulting in not only enhanced CH4 conversion but also increased carbon deposits, the optimal formation of metallic Ni sites is a key factor for the mixed Ru-Ni catalyst. Here, we used a NiAl2O4/Al2O3 catalyst and reduced it with CH4 under reaction conditions for the limited formation of metallic Ni sites, depending on the reaction temperatures. As a result, this mixed catalyst showed higher performance for DRM than a Ru single catalyst with mild carbon deposits at both low (650 ℃) and high (800 ℃) temperatures taking advantage of improved cost-effectiveness, on top of that, the existence of a Ni catalyst compensated for the loss of activity of a Ru catalyst due to sintering. We also suggest different mechanisms for DRM over the Ru catalyst and Ni catalyst respectively from the results of temperature-programmed surface reaction and CH4/CO2 cycling experiments.

Low-temperature NH3 abatement via selective oxidation over a supported copper catalyst with high Cu+ abundance

Selective catalytic NH3-to-N2 oxidation (NH3-SCO) is highly promising for abating NH3 emissions slipped from stationary flue gas after-treatment devices. Its practical application, however, is limited by the non-availability of low-cost catalysts with high activity and N2 selectivity. Here, using defect-rich nitrogen-doped carbon nanotubes (NCNT-AW) as the support, we developed a highly active and durable copper-based NH3-SCO catalyst with a high abundance of cuprous (Cu+) sites. The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T50 (i.e. the temperature to reach 50% NH3 conversion) of 174°C in the NH3-SCO reaction, which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs (OCNTs) or NCNT with less surface defects, but also those most active Cu catalysts in open literature. Reaction kinetics measurements and temperature-programmed surface reactions using NH3 as a probe molecule revealed that the NH3-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction (i-SCR) route involving nitric oxide (NO) as a key intermediate. According to mechanistic investigations by X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray absorption spectroscopy, the superior NH3-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants. Specifically, surface defects promoted the anchoring of CuO nanoparticles on N-containing sites and, thereby, enabled efficient electron transfer from N to CuO, increasing significantly the fraction of SCR-active Cu+ sites in the catalyst. This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu+-rich Cu catalysts for efficient abatement of slip NH3 emissions via selective oxidation.

Synthesis of Heteroatom Pd-ZrOx Species on Zeolite for Complete Methane Oxidation

Realizing the potential benefits of nanoscale metal catalysts requires highly dispersed active sites and control of their local environment. Herein, we develop a catalyst synthesis route for manipulating the local environment of highly dispersed metal-active sites via the targeted deposition of Pd near highly dispersed ZrOx on ZSM-5 zeolite using electrostatic interactions. The formed heteroatom Pd-ZrOx in zeolite catalysts is characterized by scanning transmission electron microscopy (STEM), in situ infrared spectroscopy, temperature-programmed desorption (TPD) of O2, and temperature-programmed surface reaction (TPSR) of CH4. The combination of diverse characterization results demonstrates the heteroatom Pd-ZrOx species rendering a higher dispersion and lower oxygen coordination of Pd species, appropriately tuning the strength of Pd–O bonds, and providing abundant active oxygen species to accelerate the dissociation of CH4. Therefore, the catalytic performance of Pd species is effectively enhanced with the lowest temperature of 90% CH4 conversion decreasing from 390 °C (without ZrOx) to 340 °C. Our work provides a strategy of engineering to anchor highly dispersed noble metal species and regulate the local environment to tune catalytic properties.

Enhancing Coke Resistance of Mg1–xNixAl2O4 Catalysts for Dry Reforming of Methane via a Doping‐Segregation Strategy

AbstractDry reforming of methane (DRM) is an important reaction to utilize two greenhouse gases (CO2 and CH4) simultaneously and produce syngas (CO and H2) for the manufacture of downstream high‐value chemicals. One of the major obstacles to preventing the commercialization of Ni‐based catalysts in DRM is the serious coking problem. This work develops a doping‐segregation method to manipulate the active metal structure and metal‐support interaction of Mg1–xNixAl2O4 catalysts to enhance their coke resistance for DRM. The Mg1–xNixAl2O4 catalysts prepared via the sol‐gel method exhibit outstanding coke resistance: the coke deposition rate of supported catalyst Ni/MgAl2O4 is 326 times higher than that of the Mg0.7Ni0.3Al2O4 catalyst at 600 °C. The Ni structure and metal‐support interaction of Mg1–xNixAl2O4 catalysts have been systematically studied using various characterization. Combined with the temperature‐programmed surface reaction (TPSR) experiments, the enhanced coke resistance of Mg1–xNixAl2O4 catalysts is attributed to smaller Ni particles, higher Ni dispersion, and stronger metal‐support interaction, which significantly inhibit the direct dissociation of CH4 and promote the oxidation of formed coke. The findings of this work provide insights into the correlation between the enhanced coke resistance and the Ni structure of Mg1–xNixAl2O4 catalysts synthesized via the doping‐segregation strategy using spinel as the precursor, leading to a stable catalyst design for many dry reforming reactions.

Unraveling the Lattice O Assisted Internal Selective Catalytic Reduction Mechanism on High N2 Selectivity of CuOx/PtCu Catalysts in NH3-SCO

Supported Pt catalysts suffer from low reaction selectivity (<65% at 100% conversion) in the selective catalytic oxidation of ammonia (NH3-SCO) because of their intrinsic over-oxidation tendencies. Herein, a strategy based on facilitating byproduct NOx reduction to N2 is demonstrated at CuOx/PtCu catalysts, aiming to tackle the low selectivity challenge. This PtCu alloy sample with a CuOx-rich surface displays an N2 selectivity of 95%, while its turnover frequencies are the highest among reported supported Pt-based catalysts. The enhanced reaction activities and N2 selectivities are primarily attributed to the Pt-Cuδ+ dual-site synergies at the CuOx/PtCu interface, in which dual sites exhibit distinct NH3 adsorption, activation, and dehydrogenation behaviors. The Olat assisted internal selective catalytic reduction mechanism at CuOx/PtCu with N2O22– as the central intermediates is proposed. Density functional theory calculation and temperature-programmed surface reaction measurements show that the N–O bond in N2O22– tends to break simultaneously with the assistance of Ov in CuOx followed by the easy transition from N2O22– to N2, which serve as the origin of the high selectivity.

Nickel Oxide Nanoparticles on KIT-6: An Efficient Catalyst in Methane Combustion

KIT-6 silica with well-ordered three–dimensional (3D) mesopores has been synthesized as a support for nickel-based catalysts. Transmission Electron Microscopy (TEM) and low-angle X-ray Diffraction (XRD) analysis are used to ensure that the ordered 3D mesostructure is stable after NiO incorporation. In this study, the catalytic activities of the NiO/KIT-6 samples are investigated. Additionally, the results show that a 10 wt% NiO/KIT-6 catalyst exhibits high catalytic performance in methane combustion, with T10, T50 and T90 being only 386 °C, 456 °C and 507 °C, respectively. Hydrogen Temperature Programmed Reduction (H2-TPR) studies have shown that the interaction between NiO and KIT-6 in the 10 wt% NiO/KIT-6 catalyst is weak. Methane Temperature programmed Surface Reaction (CH4-TPSR) results show that the surface oxygen of the NiO/KIT-6 catalyst allows it to exhibit a high catalytic performance. NiO/KIT-6 catalysts exhibit superior activities to SBA-15, MCF and SiO2 support catalysts because KIT-6 has a higher surface area and ordered 3D mesopore connectivity, which is favorable for better NiO dispersion and peculiar diffusion for reactant and products. Furthermore, the used catalyst maintained an ordered mesostructure and reduction property.

Gold and Ceria Modified NiAl Hydrotalcite Materials as Catalyst Precursors for Dry Reforming of Methane

Structured hydrotalcite NiAl-HT material with Ni/Al atomic ratio of 2.5 was prepared by co-precipitation of Ni and Al nitrate precursors and then modified by the addition of 1 wt% Ce and/or 3 wt% Au species. The obtained materials, after calcination at 600 °C, were characterized by XRD, XPS and TPR. Their catalytic performance was tested through dry reforming of methane (DRM) and by the temperature-programmed surface reaction of methane (TPSR-CH4). Thermal gravimetry analysis (TGA) of the spent catalysts was performed to determine the amount of carbon accumulated during the reaction. The effects of the addition of cerium as a support promoter and gold as nickel promoter and the sequential addition of cerium and gold on the structural properties and on the catalytic efficiency were investigated. Under the severe condition of high space velocity (600,000 mL g−1 h−1), all the catalysts were quite active, with values of CH4 conversion between 67% and 74% at 700 °C. In particular, the combination of cerium and gold enhanced the CH4 conversion up to 74%. Both additives, individually and simultaneously, enhanced the nickel dispersion with respect to the unpromoted NiAl and favored the reducibility of the nickel. During DRM all the catalysts formed graphitic carbon, contributing to their deactivation. The lower carbon gasification temperature of the promoted catalysts confirmed a positive effect played by Ce and Au in assisting the formation of an easier-to-remove carbon. The positive effect was testified by the better stability of the Ce/NiAl with respect to the other catalysts. In the gold-containing samples, this effect was neutralized by Au diffusing towards the catalyst surface during DRM, masking the nickel active sites. TPSR-CH4 test highlighted different CH4 activation capability of the catalysts. Furthermore, the comparison of the deposited carbon features (amount and removal temperature) of the DRM and TPSR spent catalysts indicated a superior activation of CO2 by the Au/Ce/NiAl, to be related to the close interaction of gold and ceria enhancing the oxygen mobility in the catalyst lattice.