Activity In Dry Reforming Of Methane Research Articles

Dry Reforming of Methane on Low‐Loading Rh Catalysts

Dry reforming of methane (DRM) is a promising catalytic process for converting greenhouse gases (CH4 and CO2) into syngas (CO and H2). This study investigates DRM under moderate conditions (550 °C) using supported ultra‐low loading (0.05 wt%) metal (M) catalysts (M = Rh, Ru, Pt, Pd, Ir, Au, and Ni). The reaction was carried out for 6 h with a flow rate of 30 mL/min for both CH4 and CO2, using 0.10 g of catalyst. Among these catalysts, 0.05 wt% Rh/Al2O3 exhibited the highest DRM activity. The effect of catalyst supports revealed that Al2O3 is the most effective support for 0.05 wt% Rh. The DRM activity of Rh species supported on Al2O3 and SiO2 was compared, and the Rh species on Al2O3 outperformed those on SiO2, indicating Al2O3 enhances the DRM activity of Rh. When comparing the DRM activity of Rh nanoparticles and Rh single atoms, it was suggested that Rh nanoparticles might exhibit superior performance for DRM. Coke deposited on 0.05 wt% Rh/Al2O3 is removed by CO2, maintaining stable catalytic activity. These findings provide valuable insights into the design of catalysts that minimize the use of noble metals in DRM reactions.

Highly porous Ni/MgO-ZrO2 catalysts for dry reforming of methane and the effects of MgO addition on the mechanisms

Dry reforming of methane (DRM) is a promising pathway to convert greenhouse gas into syngas. However, the commonly used Ni based catalysts suffer deactivation due to severe sintering and coking. In this paper, a series of porous Ni/MgO-ZrO2 catalysts (5Ni/xM(1-x)Z, x = 0, 20, 40, 60, 80 wt%, respectively) with high specific surface area were synthesized by a facile combustion method followed by incipient impregnation. It is found that the appropriate amount of MgO (40 %) addition in ZrO2 favors high porosity and high specific area. More MgO enhances the basicity of the catalyst as well as the metal-support interaction (MSI) by the formation of NiO-MgO solid solution, thus improving DRM activity and coking resistance. However, excessive MgO addition leads to over-strong MSI and lower porosity, resulting in lower DRM activity. The catalyst with 40 % MgO addition (5Ni/40M60Z) exhibits the best activity (conversions of CH4 ∼ 76 %, CO2 ∼ 83 %) and stability (>50 h) at high GHSV = 96000 ml/gcat·h and 750 °C. in situ DRIFTS reveals the mechanism that MgO addition improves DRM activity and stability. Compared with ZrO2 where CO2 adsorbs as monodentate carbonate, CO2 tends to adsorb on 40 %MgO-60 %ZrO2 as bidentate carbonate and then easily transfer to more stable intermediate bidentate formate, thus improving DRM activity and coking resistance. This study provides new insights on the role of Mg addition in Ni/MgO-ZrO2 DRM catalysts.

LDH@MgSiO3 multi-core@shell catalyst for dry reforming of methane

In this paper, LDH@SiO2 catalyst was prepared via coating a layer of silica over LDH (Layered Double Hydroxide) nanoplates. Then it was calcined and further treated by hydrothermal method with magnesium acetate to convert silica layer into MgSiO3. After H2- reduction, a layer of branch-like MgSiO3 was observed as the shell and nickel nanoparticles with average diameter around 10 nm were encapsulated within the shell, which was called as LDH@MgSiO3 multi-core@shell catalyst. This catalyst was then tested in dry reforming of methane (DRM) at 675 °C and the CH4 conversion was kept stable around 25% for 30 h time on stream at GHSV of 360 L/gcat/h. Besides, the H2/CO ratio in the product gas was 0.85, much higher than that of LDH@SiO2 catalyst, indicating its superb selectivity. Characterization revealed that the formation of MgSiO3 was beneficial to reduce the nickel particle size, modify the porosity and improve the surface alkalinity, which enhanced the DRM activity and selectivity. More importantly, it enhanced the hydrothermal stability, thus preventing the reconstruction of the shell.

Comparison between the structural characteristics and process activity of bulk and mesoporous Ni-Co-Ce/Al2O3 catalysts in the dry reforming of methane

Dry reforming of methane (DRM) is a potential way to exploit greenhouse gases and generate hydrogen. Catalyst deactivation is the biggest DRM commercialization obstacle. Lately, Ni-Co bimetallic catalysts have demonstrated improved carbon resistance over Ni-based catalysts. The aim of this research is not just to investigate the impact of Ni-Co catalysts on the DRM activity, but also to evaluate the Ni-Co alloy creation effect on the catalyst characteristics and activity. Mesoporous alumina (MA) was used as a catalyst support for Ni-Co particles in this process and its structure and activity were compared to those of bulk alumina (BA) supported catalysts. In addition, cerium was included into all of the catalysts developed as a suitable promoter for reducing the amount of deposited coke. The results obtained from the XRD and nitrogen adsorption/desorption analysis indicated the formation of a mesoporous structure and nanocrystalline morphology in the Ni-Co/MA samples, as compared to the Ni-Co/BA ones. The results showed that the bimetallic 2Ni-1Co-1Ce/MA sample had the best catalytic activity, with a CH4 conversion of 98.30 %, CO2 conversion of 96.35 %, and H2 yield of 96.30 % at 700 °C.

Construction of metal-anchored and defect-rich N-doped lignite-char supported cobalt catalysts for pressurized dry reforming of methane

Dry reforming of methane (DRM) offers a promising path for greenhouse gas conversion, but industry usually relies on pressurization conditions, and the drawback of rapid carbon deposition leading to deactivation of conventional catalysts under pressurization has hindered its industrial development. In this study, a cost-effective N-doped Co-based DRM catalyst was developed by utilizing melamine to induce heteroatom doping defects on modified lignite to overcome the problem of deactivation due to rapid carbon deposition under pressurized conditions. The catalyst, Co/CN-40 (Impregnated with 40 wt% melamine), has the smallest metal particle size (3.13 nm), the largest specific surface area (376 m2/g), high defectivity (ID/IG ratio = 0.84), enhanced metal-support interactions and a relatively high pyridine N content (48%). The evaluation of DRM activity and stability at 780 °C and 0.5 MPa demonstrates that Co/CN-40 offers the highest catalytic efficiency. The highest conversion was quickly achieved by the catalyst during activity assessments, and maintain an efficient conversion with suppressed metal agglomeration over a 100-h stability test. These improvements are attributed to the increase in the number of defects which enhances electron transfer, improves metal anchoring and boosts the adsorption and activation of reactant molecules.

Synergistic Ni-Ce-SSZ-13 catalysts for enhanced dry reforming of methane

The dry reforming of methane (DRM) serves as a pivotal reaction for hydrogen generation and the simultaneous conversion of methane and carbon dioxide, two major greenhouse gases, into syngas that can further be converted into high-value fuels and chemicals. However, catalyst deactivation imposes a major challenge that prohibits the market penetration of DRM. Here we reported a series of bifunctional Ni-Ce catalysts supported on SSZ-13 (Ni-Ce-SSZ-13) and discovered that a small amount of Ce could significantly enhance the activity, selectivity, and stability for DRM. Optimal ratio of Ni to Ce has been identified to yield peak catalytic performance. The optimal performance is correlated with the maximum Ce3+/Ce4+ ratio as revealed by XPS analysis, which implies an increased presence of oxygen vacancies in the catalysts. It played a crucial role in facilitating the oxidation of activated CH4 species at Ni sites, thereby enhancing DRM activity and diminishing the detrimental coke formation. It is also disclosed that integrating proper amount of Ce fosters its interactions with Ni, effectively preventing the agglomeration of Ni sites. This work presents great implications for the rational design and catalytic synergy of bi-/multi-functional zeolite catalysts for other technological applications.

Regenerable Ni-Au/La2O3 catalysts for dry reforming of methane

Dry reforming of methane (DRM) has been proposed as an effective way of converting CO2 and CH4, two major greenhouse gases, into synthesis gas (H2 + CO), a ubiquitous feedstock for various chemical industries. Ni-based bimetallic catalysts have been widely explored as an attractive route to improve DRM activity, selectivity, and stability. In this study, we synthesized LaNiO3 (LNO) and 1% Au-doped LaNiO3 (Au/LaNiO3 – A/LNO) using the modified sol-gel method. The material properties were studied using various characterization techniques, including XRD, BET, H2-TPR, TPO, STEM-HAADF with EDX mapping, Raman spectroscopy, and XPS. Ni nanoparticles with sizes ranging from 10 to 70 nm were successfully exsolved from the perovskite material after reduction at 800 °C. DRM activity of the reduced catalysts was probed from 400 to 800 °C. The Au-doped LNO exhibits significant enhancement in DRM activity at a lower temperature range (600–700 °C) compared to LNO. The A/LNO was also shown to retard coke formation and improve the selectivity for DRM. A computational study using density functional theory (DFT) reveals that the Ni3Au sites have a lower methane activation barrier due to the formation of NiAu alloy and the synergetic effect between Ni and Au.

Dry Reforming of Methane on Ni/LaZrO2 Catalyst under External Electric Fields: A Combined First-Principles and Microkinetic Modeling Study.

Dry reforming of methane (DRM) reaction has great potential in reducing the greenhouse effect and solving energy problems. Herein, the DRM reaction mechanism and activity on Ni16/LaZrO2 catalyst under electric fields were comprehensively investigated by combining density functional theory calculations with microkinetic modeling. The results showed that La doping increases the interaction between Ni and ZrO2 by Ni cluster transfer of more electrons. The adsorption strength of species followed the order Ni16/ZrO2 > Ni16/LaZrO2, which is consistent with the results for the d-band center but opposite to the metal-support interaction. The best DRM reaction path on Ni16/LaZrO2 was the CH2-O pathway, which is different from the CH-O pathway on Ni(111) and Ni16/ZrO2. Both positive and negative electric fields of strong and weak metal-support interactions reduced the energy barrier of DRM reaction. Importantly, our results showed that the more dispersed and smaller Ni12/LaZrO2 model by considering the dispersing effect induced by La doping, which displayed very different results from that of Ni16/LaZrO2: reduced the energy barrier for methane decomposition, thereby promoting DRM reaction activity. Microkinetic results showed that the carbon deposition behavior of DRM becomes weaker on Ni16/LaZrO2 due to the suppression of methane decomposition in the presence of La doping compared to Ni16/ZrO2, but the opposite result is obtained on Ni12/LaZrO2. The order of DRM reactivity was Ni16/LaZrO2 < Ni16/ZrO2 < Ni12/LaZrO2, which is consistent with the experiment observations. The conversion of methane and CO2 was higher in positive electric fields than in negative electric fields at low temperatures, but the results were opposite at high temperature. Negative electric fields can improve the carbon deposition resistance of Ni-based catalysts compared to positive electric fields. The degree of rate control analysis showed that CHx* oxidation also plays an important role in the DRM reaction. We envision that this study could provide a deeper understanding for guiding the widespread application of electric field catalysis.

Improved Selectivity and Stability in Methane Dry Reforming by Atomic Layer Deposition on Ni-CeO2-ZrO2/Al2O3 Catalysts.

Ni can be used as a catalyst for dry reforming of methane (DRM), replacing more expensive and less abundant noble metal catalysts (Pt, Pd, and Rh) with little sacrifice in activity. Ni catalysts deactivate quickly under realistic DRM conditions. Rare earth oxides such as CeO2, or as CeO2-ZrO2-Al2O3 (CZA), are supports that improve both the activity and stability of Ni DRM systems due to their redox activity. However, redox-active supports can also enhance the undesired reverse water gas shift (RWGS) reaction, reducing the hydrogen selectivity. In this work, Ni on CZA was coated with an ultrathin Al2O3 overlayer using atomic layer deposition (ALD) to study the effects of the overlayer on catalyst activity, stability, and H2/CO ratio. A low-conversion screening method revealed improved DRM activity and lower coking rate upon the addition of the Al2O3 ALD overcoat, and improvements were subsequently confirmed in a high-conversion reactor at long times onstream. The overcoated samples gave an H2/CO ratio of ∼1 at high conversion, much greater than uncoated catalysts, and no evidence of deactivation. Characterization of used (but still active) catalysts using several techniques suggests that active Ni is in formal oxidation state >0, Ni-Ce-Al is most likely present as a mixed oxide at the surface, and a nominal thickness of 0.5 nm for the Al2O3 overcoat is optimal.

Dry Reforming of Methane over Pyrochlore-Type La2Ce2O7-Supported Ni Catalyst: Effect of Particle Size of Support.

The properties of supports (such as oxygen vacancies, oxygen species properties, etc.) significantly impact the anti-carbon ability due to their promotional effect on the activation of CO2 in dry reforming of methane (DRM). Herein, pyrochlore-type La2Ce2O7 compounds prepared using co-precipitation (CP), glycine nitrate combustion (GNC) and sol-gel (S-G) methods, which have highly thermal stability and unique oxygen mobility, are applied as supports to prepare Ni-based catalysts for DRM. The effect of the calcining temperature (500, 600 and 700 °C) on La2Ce2O7(CP) has also been investigated. Based on multi-technique characterizations, it is found that the synthesis method and calcination temperature can influence the particle size of the La2Ce2O7 support. Changes in particle size strongly modulate the pore volume, specific surface area and numbers of surface oxygen vacancies of the La2Ce2O7 support. As a result, the distribution of supported Ni components is affected due to the different metal-support interaction, thereby altering the activity of the catalysts for cracking CH4. Moreover, the supports' abilities to adsorb and activate CO2 are also adjusted accordingly, accelerating the removal of the carbon deposited on the catalysts. Finally, La2Ce2O7(CP 600) with an appropriate particle size exhibits the best catalytic activity and stability in DRM.

Enhanced Methane Dry Reforming with Ni/SiO2 Catalysts Featuring Hierarchical External Nanostructures

Global energy demand escalates the interest in effective and durable catalytic systems for the dry reforming of methane (DRM), a process that converts CO2/CH4 into H2/CO syngas. Porous silica-supported nickel (Ni) catalysts are recognized as a promising candidate due to robust DRM activity associated with the confinement of Ni particles in the mesopores that reduces the catalyst deactivation by carbon byproduct deposits and sintering of active Ni sites. However, the small-sized pore configurations in the mesoporous catalysts hinders the fast mass transfer of reactants and products. A unique combination of the hierarchical nanostructure with macro–mesoporous features of the support is adopted to enhance the catalytic performance via the dual effect of the efficient mass transfer and minimized sintering issue. This study delves into the influence of SiO2 geometry and pore structure on the catalytic performance of Ni-based catalysts. Three types of porous silica supports were synthesized through various methods: (a) hydrothermal-assisted sol–gel for dendritic mesoporous silica (DMS), (b) spray-pyrolysis-assisted sol–gel for spray evaporation-induced self-assembly (EISA) silica, and (c) oven-assisted sol–gel for oven EISA silica. Among the prepared catalysts the hierarchical external nanostructured Ni/DMS showed the superior CH4 and CO2 conversion rates (76.6% and 82.1%), even at high space velocities (GHSV = 360 L∙g−1·h−1). The distinctive macro–mesoporous geometry effectively prevents the sintering of Ni particles and promotes the smooth diffusion of the reactants and products, thus improving catalytic stability over extended reaction periods (24 h). This research highlights the significant impact of macro–mesoporosity revealed in DMS support catalysts on the physicochemical properties of Ni/DMS and their crucial role in enhancing DRM reaction efficiency.

Local coordination environment triggers key Ni-O-Si copolymerization on silicalite-2 for dry reforming of methane

The development of dry reforming of methane (DRM) catalysts with good Ni loading, while retaining high metal dispersion is a critical issue, given the harsh industrial-relevant conditions. Here, we demonstrate the impact of the local coordination environment on the DRM activity of Ni-silicalite-2 (Ni-S2) catalysts. The grafted Ni(II) intermediates with high Ni-O-Si copolymerization (coordination number ratio Si: Ni=2.28) are discovered to redisperse Ni sites, even at 10 wt% Ni loading. Then, the partial S2 recrystallizes into new SiO2-nanowires to anchor Ni nanoparticles, via an ethylenediamine-assisted dissolution-recrystallization (enDR). Compared to the typical Ni-S2 catalyst with Ni phyllosilicate (CN ratio Si: Ni＜1), the Ni-S2-enDR shows high dispersion and stability at 800 °C and 450 L gcat−1 h−1, exhibiting negligible coke deposition and no growth of 4.25 nm Ni nanoparticles. The atomic level insights in nickel and silicon coordination reported in this work provide an instructive way of designing stable DRM catalysts.

Deciphering the role of nano-CeO2 morphology on the dry reforming of methane over Ni/CeO2 using transient and isotopic techniques

The effect of ceria morphology, nanorods-NR and nanopolyhedra-NP on important kinetic parameters of the dry reforming of methane (DRM) over Ni/nano-ceria (dNi ∼20 nm) was investigated by transient and isotopic experiments. Transient isothermal reduction by hydrogen evidenced lower activation energy and higher reduction rates of lattice oxygen in the case of CeO2-NR compared to those of CeO2-NP. Transient 16O/18O isotopic exchange provided a lower Eapp of bulk oxygen diffusion (by ∼90 kJ mol−1) for CeO2-NR compared to CeO2-NP. 18O/16O isotopic exchange followed by DRM revealed higher carbon oxidation rates by lattice oxygen to C18O(g) in the case of CeO2-NR compared to those of CeO2-NP, in harmony with the lower amount of carbon accumulated in the former catalyst. The lower Eapp of DRM and carbon oxidation by lattice oxygen confirm the higher DRM activity on Ni/CeO2-NR compared to Ni/CeO2-NP. HAADF-STEM and Raman studies were linked to the observed transient kinetic results.

Hydrothermally synthesized tremella-like monometallic Ni/SiO2 for effective and stable dry reforming of methane (DRM) to syngas

Despite its activity, monometallic Ni-catalyst is highly susceptible to coke deposition and sintering in catalyzing dry reforming of methane (DRM). To counter these, a novel tremella-like monometallic Ni/SiO2 catalyst was hydrothermally synthesized herein, realizing excellent activity, outstanding coke inhibition and robust structural stability for a durable DRM reaction. Functionality-speaking, the tapered ends of Ni-petals, sized at 8–15 nm, permit high DRM activity with suppressed coke formation while its thicker base spatially prevents Ni-sintering during high temperature reaction. Meanwhile, the open structure of catalyst resulting from such tremella-like structure also enhances the diffusion of reactants/products gas to/from catalytic surface, thus augmenting its activity for DRM. With merely 5 wt% Ni incorporated, CO2 and CH4 conversions of ∼90% could be attained with only ∼15% activity drop after 75 h of DRM. Full-restoration of activity could facilely be attained using 90 min in-situ oxidative regeneration. Mechanistic study coupling sorptive investigation, ex-situ XRD, and SEM reveals the pronounced adsorption tendency of CH4 over those of CO2, H2 and CO, confirming the adherence of DRM to Eley-Rideal reaction model in current study. Significantly, this study provides a new morphological-controlled strategy to conveniently impart excellent coke-inhibiting and sintering-resisting capability to monometallic Ni-catalyst.

High activity in the dry reforming of methane using a thermally switchable double perovskite and in situ generated molecular level nanocomposite.

This work emphasizes the dry reforming of methane (DRM) reaction on citrate sol-gel-synthesized double perovskite oxides. Phase pure La2NiMnO6 shows very impressive DRM activity with H2/CO = 0.9, hence revealing a high prospect of next-generation catalysts. Although the starting double perovskite phase gets degraded into mostly binary oxide phases after a few hours of DRM activity, the activity continues up to 100 h. The regeneration of the original double perovskite out of decomposed phases by annealing at near synthesis temperature, followed by the spectacular retention of activity, is rather interesting and hitherto unreported. This result unravels unique reversible thermal switching between the original double perovskite phase and decomposed phases during DRM without compromising the activity and raises challenge to understand the role of decomposed phases evolved during DRM. We have addressed this unique feature of the catalyst via structure-property relationship using the in situ generated molecular level nanocomposite.

Coating Effects of Sm0.2Ce0.78M0.02O2- δ (M=Ni, Co, Pd, NiCo) Layer on Ni/YSZ Anode for Internal Dry Reforming in Solid Oxide Fuel Cells

Internal dry reforming of methane (DRM) in solid oxide fuel cells (SOFCs) has environmental advantages because CH4 and CO2 are considered as two major greenhouse gases causing global warming. Carbon coking, however, can be major drawback in the DRM via pyrolysis of methane and Boudouard reaction. In this study, Sm0.2Ce0.78M0.02O3- δ (SCM, M=Ni, Co, Pd, NiCo) was investigated to minimize carbon coking and to improve the catalytic activity for internal DRM in SOFCs. Samarium doped ceria (Ce0.8Sm0.2O2- δ) has been widely used in SOFCs due to the excellent ionic conductivity and the mixed ionic and electronic conductivity (MIEC). To improve the catalytic activity of Ce0.8Sm0.2O2- δ, Ni, Co, Pd, and NiCo alloy were substituted into the Ce. The SCM phase was stable in internal DRM condition. The morphology and compositions are analyzed with XRD, SEM, TEM, XPS, etc. Sm0.2Ce0.78Ni0.01Co0.01O2- δ(SCNC) showed excellent DRM results with over 90% in CH4 and CO2 conversion and close to 1 in H2/CO selectivity at 800oC. The carbon deposition of SCNC catalysts was minimized. In addition, power density of SCNC-coated Ni/YSZ anode was improved with 2.3 times higher in CH4/CO2 fuel conditions comparing to that of Ni/YSZ anode.

La2O3-CeO2-Supported Bimetallic Cu-Ni DRM Catalysts.

The present work is focused on nickel catalysts supported on La2O3-CeO2 binary oxides without and with the addition of Cu to the active component for the dry reforming of methane (DRM). The catalysts are characterized using XRD, XRF, TPD-CO2, TPR-H2, and low-temperature N2 adsorption-desorption methods. This work shows the effect of different La:Ce ratios (1:1 and 9:1) and the Cu addition on the structural, acid base, and catalytic properties of Ni-containing systems. The binary LaCeOx oxide at a ratio of La:Ce = 1:1 is characterized by the formation of a solid solution with a fluorite structure, which is preserved upon the introduction of mono- or bimetallic particles. At La:Ce = 9:1, La2O3 segregation from the solid solution structure is observed, and the La excess determines the nature of the precursor of the active component, i.e., lanthanum nickelate. The catalysts based on LaCeOx (1:1) are prone to carbonization during 6 h spent on-stream with the formation of carbon nanotubes. The Cu addition facilitates the reduction of the Cu-Ni catalyst carbonization and increases the number of structural defects in the carbon deposition products. The lanthanum-enriched LaCeOx (9:1) support prevents the accumulation of carbon deposition products on the surface of CuNi/La2O3-CeO2 9:1, providing high DRM activity and an H2/CO ratio of 0.9.

Understanding Coke Deposition Vis-à-Vis DRM Activity over Magnesia-Alumina Supported Ni-Fe, Ni-Co, Ni-Ce, and Ni-Sr Catalysts.

The catalytic conversion of CH4 and CO2 into H2-rich syngas is known as the dry reforming of methane (DRM). The dissociation of CH4 over active sites, coupled with the oxidation or polymerization of CH4-x (x = 1-4), plays a crucial role in determining in determining the DRM product yield and coke deposition. Herein, a series of bimetallic-supported catalysts are prepared by the dispersion of Ni-M (M = Ce, Co, Fe, and Sr) over 60 wt% MgO-40 wt% Al2O3 (60Mg40Al) support. Catalysts are tested for DRM and characterized with XRD, surface area and porosity, temperature-programmed reduction/desorption, UV-VIS-Raman spectroscopy, and thermogravimetry. 2.5Ni2.5Sr/60Mg40Al and 2.5Ni2.5Fe/60Mg40Al, and 2.5Ni2.5Ce/60Mg40Al and 2.5Ni2.5Co/60Mg40Al have similar CO2 interaction profiles. The 2.5Ni2.5Sr/60Mg40Al catalyst nurtures inert-type coke, whereas 2.5Ni2.5Fe/60Mg40Al accelerates the deposition of huge coke, which results in catalytic inferiority. The higher activity over 2.5Ni2.5Ce/60Mg40Al is due to the instant lattice oxygen-endowing capacity for oxidizing coke. Retaining a high DRM activity (54% H2-yield) up to 24 h even against a huge coke deposition (weight loss 46%) over 2.5Ni2.5Co/60Mg40Al is due to the timely diffusion of coke far from the active sites or the mounting of active sites over the carbon nanotube.

Synergistic effect of macroporosity and crystallinity on catalyst deactivation behavior over macroporous Ni/CexZr1-xO2–Al2O3 for dry reforming of methane

Dry reforming of methane (DRM) is an outstanding process for transforming methane and carbon dioxide into synthesis gases (H2 and CO). In this study, a special geometrical modification on Ni/CexZr1-xO2–Al2O3 catalyst was applied by introducing a macroporous structure into the support to accelerate the metal support interaction that optimized the distribution of the active sites over the catalyst. Furthermore, we investigated a synergistic effect of the macroporosity and CexZr1-xO2 (CZ) crystallinity over the Ni/CexZr1-xO2–Al2O3 catalyst on its catalytic performance in DRM. Macroporous Ni/CexZr1-xO2–Al2O3 catalysts were prepared via washing (Ni-MaCZA-W) and hydrothermal (Ni-MaCZA-H) methods. Non-macroporous Ni-CZA-H with crystalline CZ was prepared for comparison. The crystalline CZ over macroporous Ni-MaCZA-H had a strong interaction with Ni due to easy accessibility of Ni species to CZ in the macroporous support, resulting in highly dispersed Ni nanoparticles and abundant oxygen vacancies. The unique properties of Ni-MaCZA-H increased catalytic activity and stability in DRM, suppressing coke formation via efficient coke gasification. The Ni species and amorphous CZ over Ni-MaCZA-W resulted in a bimodal Ni size distribution and fast catalyst deactivation. However, even though the crystalline CZ over Ni-CZA-H generated a unimodal distribution of Ni nanoparticles, the non-macroporous Ni-CZA-H resulted in gradual deactivation in the catalytic activity and the production of a different type of coke.

A novel strategy for the fabrication of highly active and stable hydrochar-based catalysts for efficient dry reforming of methane

Strong metal-support interaction (SMSI) has pivotal importance for stabilizing metal sites and tuning catalytic performance in high-temperature gas phase chemistry. Conventional SMSI construction strategy, however, suffers from limited exposure of active sites caused by gas or thermally-induced metal redistribution and heavily deteriorates the catalytic performance. Herein we showed that the rationally constructed metal–carbon interface by pressure-induced SMSI greatly impacted the activity of core–shell nickel nanoparticles supported on hydrochar (Ni/NiO/HC) in dry reforming of methane (DRM). The electronic and geometric structures of Ni/NiO/HC were effectively tailored by simply adjusting the compression pressure. In particular, the NiO shell thickness was highly sensitive to compression pressure, which could be precisely manipulated from 2 to 5 atomic layers by imposing the pressures from ambient to 3.6 Gpa. With the optimized thickness of NiO shell of 3–5 atomic layers, the highest activity of Ni/NiO/HC catalysts were up to 57.2 times than their uncompressed analogues in DRM, and far outperformed benchmarks in the literature, especially at low reforming temperatures (500–600 °C). The active sites responsible for this promising performance were associated with the fraction of low-coordinated corner and perimeter Ni atoms from 20.1 to 61.6%, which dramatically enhanced the DRM activity of Ni/NiO/HC catalysts over 2 orders of magnitude. This study introduced a new paradigm for SMSI construction via a pressure-induced construction strategy and highlighted the importance of a rationally designed core–shell metal particles/hydrochar interface.