Strategies to enhance dry reforming of methane: Synthesis of ceria-zirconia/nickel–cobalt catalysts by freeze-drying and NO calcination

To improve the activity of nickel–cobalt (NiCo) catalyst supported on ceria-zirconia (CeZr) in the dry reforming of methane (DRM) with carbon dioxide, and to lower the coking rate in this process, 1.5 wt.% and 2.5 wt.% NiCo catalysts were prepared using two approaches, i.e. freeze-drying (FD) and NO calcination for comparison against oven-drying (OD) and air calcination (air), respectively. Their impact was studied for 20 h of DRM at 750 ^°C and 1.2 bar, with undiluted CH₄–CO₂ feed simulating the real conditions. NO-calcined samples show, on average, more pronounced improvement through increased conversion of CH₄ (90%), followed by FD samples (85%) from the air and OD-prepared samples (both 82%). Coking content varied between 0.67 and 0.82 wt.%. The observed slow catalyst deactivation might be caused by sintering of the catalysts. Higher quantity of CO than H₂ for syngas production was obtained, owing to concurrent reverse water-gas shift side reaction, and high redox properties of the defective CeZr lattice that enabled surface carbon gasification by continuous replenishment of oxygen from the support to produce CO, of which the latter phenomenon also explains the low carbon deposition. H₂/CO ratio between 0.42 and 0.85 was achieved, with FD and NO samples fared better (0.83–0.85) over the ones prepared by conventional methods (0.73–0.82) for 2.5%NiCo loaded catalysts.     

Partial oxidation of methane over high coke-resistant bimetallic Pt-Ni/CeO2 catalyst: Profound influence of Pt addition on stability

We have developed a bimetallic Pt-Ni/CeO₂ catalyst by straightforward citric acid complex combustion method for low-temperature partial oxidation of methane. Furthermore, we also compared the catalytic performance of bimetallic Pt-Ni/CeO₂ with monometallic Ni/CeO₂ catalysts. The bimetallic 0.5%Pt-2.5%Ni/CeO₂ (PNC2.5) catalyst exhibited >99% conversion of methane with a H₂/CO ratio of 2, whereas monometallic 2.5%Ni/CeO₂ (NC2.5) catalyst showed ～92% methane conversion with a H₂/CO ratio of 1.9 at 700 °C. In addition, the PNC2.5 catalyst does not show any deactivation and structural changes during 500 h time-on-stream (TOS), also confirmed by TEM, Raman, and TGA analysis. Conversely, a substantial activity loss (～61%) was noticed in the NC2.5 catalyst owing to the coking and sintering of Ni species. The excellent performance of the PNC2.5 catalyst can be attributed to the modified electronic-structural properties. The activation of CH₄ molecules was studied by DFT calculation over Pt-Ni/CeO₂(111) and Ni/CeO₂(111) model systems, which explain the promotional effect of Pt in the methane C-H bond activation with ～8 kcal/mol reduction in the activation barrier.     

Hydrogen production through autothermal reforming of CH4: Efficiency and action mode of noble (M = Pt,Pd) and non-noble (M = Re,Mo, Sn) metal additives in the composition of Ni-M/Ce0.5Zr0.5O2/Al2O3 catalysts

Hydrogen production through autothermal reforming of methane (ATR of CH₄) over promoted Ni catalysts was studied. The control of the ability to self-activation and activity of Ni-M/Ce_0.5Zr_0.5O₂/Al₂O₃ catalysts was achieved by tuning their reducibility through the application of different types (M = Pt, Pd, Re, Mo or Sn) and content (molar ratio M/Ni = 0.003, 0.01 or 0.03) of additive. The comparison of the efficiency and action mode of noble (M = Pt, Pd) and non-noble (M = Re, Mo, Sn) metal additives in the composition of Ni-M/Ce_0.5Zr_0.5O₂/Al₂O₃ catalysts was performed using X-ray fluorescence analysis, N₂ adsorption, X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction with hydrogen, and thermal analysis. The composition-characteristics-activity correlations were determined. It was shown that the introduction of a promoter does not affect the textural and structural properties of catalysts but influences their reducibility and performance in ATR of CH₄. At the similar dispersion of NiO active component (11 ± 2 nm), the Ni²⁺ reduction is intensified in the following order of additives: Mo < Sn < Re ≤ Pd < Pt. It was found that for the activation of Ni and Ni–Sn catalysts before ATR of CH₄ tests, the pre-reduction is required. On the contrary, the introduction of Pt, Pd and Re additives leads to the self-activation of catalysts under the reaction conditions and an increase of the H₂ yield due to the enhanced reducibility of Ni²⁺. The efficient and stable catalyst for hydrogen production has been developed: in ATR of CH₄ at 850 °C over an optimum 10Ni-0.9Re/Ce_0.5Zr_0.5O₂/Al₂O₃ catalyst the H₂ yield of 70% is attained. The designed catalyst has enhanced stability against oxidation and sintering of Ni active component as well as high resistance to coking.     

Hydrogen production from aqueous phase reforming of glycerol over attapulgite-supported nickel catalysts: Effect of acid/base treatment and Fe additive

In this paper, a series of nickel-based catalysts supported on modified attapulgite (ATP) by acid (citric acid and EDTA) and base (NaOH) were prepared and applied to the aqueous phase reforming of glycerol (APRG). The modified ATP (MA) and as-prepared catalysts were detected using N₂ adsorption-desorption, ICP-OES, XRD, FT-IR, SEM-EDS, HRTEM, XPS, H₂-TPR, NH₃-TPD. The results manifested that the acid/base treatment of ATP significantly increased the surface area and pore volume, enhanced the metal-support interaction (MSI) and decreased the Ni particle size, resulting in the better glycerol conversion and H₂ selectivity, especially for Ni/MA-E catalyst, where the ATP was pretreated using EDTA. In addition, the bimetallic NiFe/MA-E catalyst exhibited the highest conversion of glycerol to gas product (54.4%) and H₂ selectivity (84.6%) at very low temperature (280 °C). These results were attributed to the strongest the interplay of active metal with support by the formation of Ni–Fe alloy, resulting in the highest active metal dispersion, smallest metal particle size, lowest the reducibility of active metal and most surface Ni⁰ content. According to the characterizations of spent catalysts, it demonstrated that monometallic Ni catalysts presented obvious sintering of Ni metal particle and larger accumulation of carbon deposition, which led to the deactivation of the catalyst. While NiFe/MA-E catalyst showed less particle agglomeration and coke formation attributed to the lower content of surface acid site. Apart from that, another cause of catalyst deactivation might be the destruction of ATP skeleton during APRG.     

Double oxalates of Rh(III) with Ni(II) and Co(II) – Effective precursors of nanoalloys for hydrocarbons steam reforming

Heteronuclear coordination compounds of d-metals are suitable single-source precursors for bimetallic nanoalloys, which often show extraordinary catalytic properties due to synergetic effect. In particular, Ni- and Rh-based catalysts are highly effective in low temperature steam reforming processes. Double oxalates of Rh with Ni and Co of the formula {[Rh(H₂O)₂(C₂O₄)μ-(C₂O₄)]₂M(H₂O)₂}·6H₂O (M = Ni, Co) were synthesized and structurally characterized. According to thermogravimetric analysis, the complexes decompose completely in He and H₂ atmospheres to form corresponding nanoalloys at ∼300 °C. The calcination in O₂ atmosphere leads to formation of spinel type mixed oxide. The supported Co–Rh/Al₂O₃ and Ni–Rh/Al₂O₃ catalysts were prepared by impregnation of double oxalate complexes in porous support with subsequent calcination and tested in propane low temperature steam reforming in CH₄ excess. The Co-containing catalyst showed comparable activity regarding to pure Rh/Al₂O₃ sample, while bimetallic Ni–Rh/Al₂O₃ catalyst revealed to be appreciably more active, than monometallic catalysts with higher active component loadings. Rh–Ni catalyst allowed for complete propane conversion at T ≈ 350 °C, whereas for Rh catalyst the temperature was T ≈ 410 °C, and Rh–Co did not reach complete C₃H₈ conversion at all.     

NiCo layered double hydroxide/hydroxide nanosheet heterostructures for highly efficient electro-oxidation of urea

Urea oxidation is an important reaction for direct urea fuel cells as well as hydrogen production and/or water remediation via electrolysis using urea-rich wastewater. The key to efficient urea oxidation is to explore a well-designed high-performing catalyst. Herein, NiCo layered double hydroxide/hydroxide (NiCo LDH/NiCo(OH)₂) microspheres composed of ultrasmall nanosheets have been grown on Ni foam by a solution method at room temperature. The NiCo LDH/NiCo(OH)₂ heterostructures have been confirmed by TEM and XRD analysis. The high activity with a small onset potential of 0.29 V vs. Hg/HgO is mainly attributed to the rich NiCo LDH-NiCo(OH)₂ interfaces and the bimetallic nature of the catalysts. The NiCo LDH/NiCo(OH)₂ heterostructures can be promising catalysts for urea oxidation and offer new insights into the design of high-performance nickel-based catalysts.     

Hydrogen production from catalytic steam reforming of bio-oil aqueous fraction over Ni/CeO2–ZrO2 catalysts

A series of composite catalysts Ni/CeO₂–ZrO₂ were prepared via impregnation method with Ni as the active metal. A laboratory-scale fixed-bed reactor was employed to investigate the catalyst performance during hydrogen production by steam reforming bio-oil aqueous fraction. Effects of water-to-bio-oil ratio (W/B), reaction temperature, and the loaded weight of Ni and Ce on the hydrogen production performance of Ni/CeO₂–ZrO₂ catalysts were examined. The obtained results were compared with commercial nickel-based catalysts (Z417). The best performance of Ni/CeO₂–ZrO₂ catalyst was observed when the Ni and Ce loaded weight were 12% and 7.5% respectively. At W/B = 4.9, T = 800 °C, H₂ yield reaches the highest of 69.7% and H₂ content of 61.8% were obtained. Under the same condition, H₂ yield and H₂ content were higher than commercial nickel-based catalysts (Z417).     

Study of Ni/CeO2–ZnO catalysts in the production of H2 from acetone steam reforming

This paper reports the study of new Ni/ZnO-based catalysts for hydrogen production from substoichiometric acetone steam reforming (ASR). The effect of CeO₂ introduction is analyzed regarding the catalytic behavior and carbon deposits formation. ASR was studied at 600 °C using a steam/carbon ratio S/C = 1. Ni/xCeZnO (x = 10, 20, 30 CeO₂ wt %) catalysts showed a better performance than the bare Ni/ZnO. Ni/xCeZnO generated a lower amount and less ordered carbon deposits than Ni/ZnO. The higher the CeO₂ content in Ni/xCeZnO, the lower the amount of carbon deposits in the post-reaction catalyst. The highest H₂ production under ASR at the experimental conditions used was achieved for the Ni/xCeZnO catalysts. In-situ DRIFTS-MS experiments under ESR conditions showed different reaction pathways over Ni/20CeZnO and Ni/ZnO catalysts.     

H2 production from oxidative steam reforming of 1-propanol and propylene glycol over yttria-stabilized supported bimetallic Ni–M (M = Pt,Ru, Ir) catalysts

This paper reports hydrogen production from oxidative steam reforming of 1-propanol and propylene glycol over Ni–M/Y₂O₃–ZrO₂ (10% wt/wt Y₂O₃; M = Ir, Pt, Ru) bimetallic catalysts promoted with K. The results are compared with those obtained over the corresponding monometallic catalyst. The catalytic performance of the calcined catalysts was analyzed in the temperature range 723–773 K, adjusting the total composition of the reactants to O/C = 4 and S/C = 3.2–3.1 (molar ratios). The bimetallic catalysts showed higher hydrogen selectivity and lower selectivity of byproducts than the monometallic catalyst, especially at 723 K. Ni–Ir performed best in the oxidative steam reforming of both 1-propanol and propylene glycol. The presence of the noble metal favours the reduction of the NiO and the partial reduction of the support. The NiO crystalline phase present in the calcined catalysts was transformed to Ni° during oxidative steam reforming. The adsorption and subsequent reactivity of both 1-propanol and propylene glycol over Ni–Ir and Ni catalysts were followed by FTIR; C–C bond cleavage was found to occur at a lower temperature in propylene glycol than in 1-propanol.     

Cu,Mg and Co effect on nickel-ceria supported catalysts for ethanol steam reforming reaction

Ethanol steam reforming is a promising reaction which produces hydrogen from bio and synthetic ethanol. In this study, the nano-structured Ni-based bimetallic supported catalysts containing Cu, Co and Mg were synthesized through impregnation method and characterized by XRD, BET, SEM, TPR and TPD analysis. The prepared catalysts were tested in steam reforming of ethanol in the S/C = 6, GHSV of 20,000 mL/(g_cat h) at the temperature range of 450–600 °C. Among the xNi/CeO₂ (x = 10, 13, 15 wt%) catalyst, the sample containing 13 wt% Ni with surface area of 64 m²/g showed the best performance with 89% ethanol conversion and 71% H₂ selectivity as well as low CO selectivity of 8% at 600 °C and The addition of Cu, Mg, and Co to catalyst structure were evaluated and it was found that the nature of second metal has a strong influence on the catalyst selectivity for H₂ production. Considering to results of TPR analysis, the 13Ni–4Cu/CeO₂ catalyst showed proper reduction which caused in better activity. On the other side based on TPD analysis, the more basic property of 13Ni–4Mg/CeO₂ bimetallic catalyst provided a better condition to methane steam reforming, leading to lower CH₄ selectivity and consequently more H₂ production. The 13Ni–4Cu/CeO₂ exhibited the highest activity and lowest selectivity towards ethanol conversion and CO production about 99% and 4%, while the 13Ni–4Mg/CeO₂ catalyst possessed the highest H₂ selectivity and lowest CH₄ selectivity about 74% and 1% respectively at 600 °C. The Ni–Cu and Ni–Mg bimetallic catalysts shows good stability with time on stream.     

Promotion of palladium catalysis by silver for ethanol electro-oxidation in alkaline electrolyte

Bimetallic Pd_mAg alloy nanostructures (m being the atomic Pd/Ag ratio, m = 0.1–1.5), prepared through a simple co-reduction process, are employed as the catalysts toward ethanol electro-oxidation reaction (EOR). XPS results show that the electronic structure of Pd can be modified due to the presence of Ag, which is crucial for the enhancement of the catalytic performance of the Pd_mAg/C catalysts. It is found that the catalytic activity of Pd was strongly dependent on the composition of the Pd_mAg/C catalysts, with the best performance found with the Pd_0.5Ag/C. The mass-specific activity (MSA) and intrinsic activity (IA) data of Pd_0.5Ag/C is 3.6 and 2.4 times higher than that of the monometallic Pd/C catalyst, respectively, which might be ascribed to the electronic and synergistic effect. These findings would be promising in understanding the mechanism of EOR on Pd-based catalysts and designing the bimetallic catalysts for direct ethanol fuel cells and other applications.     

Growth of ultrathin nanosheets of nickel iron layered double hydroxide for the oxygen evolution reaction

Because of low cost and abundance, nickel-iron double layered hydroxide (NiFe LDH) is seen as a viable substitute for noble-metal-based electrodes for the oxygen evolution reaction (OER). Herein, we report the growth of NiFe LDH in the form of fine nanosheets in a single step using benzyl alcohol-mediated chemistry. The electrochemical studies clearly suggest that benzyl alcohol is capable of inducing effective chemical interaction between Ni and Fe in the NiFe LDH. The overpotential to produce benchmark 10 mA cm^?2 (η₁₀) for the NiFe LDH electrode is only ～270 mV_RHE, which is much smaller than those of benchmark IrO₂ (η₁₀ = 318 mV_RHE), nickel hydroxide (η₁₀ = 370 mV_RHE) and iron hydroxide (η₁₀ = 410 mV_RHE) for the OER. The difference of the overpotential requirement increases further with increasing current density, indicating faster kinetics of the OER at the catalytic interface of the NiFe LDH. Estimation of Tafel values verifies this notion – the Tafel slopes of NiFe LDH, Ni(OH)₂, and FeOOH are calculated to be 48.6, 55.8, and 59.3 mV dec^?1, respectively. At η = 270 mV, the turnover frequency (TOF) of the NiFe LDH is 0.48 s^?1, which is ～8 and ～11 folds higher than those of Ni(OH)₂ (0.059 s^?1) and FeOOH (0.042 s^?1). In addition to Tafel and TOF, the NiFe LDH electrode has favorable electrochemically active surface area and electrochemical impedance. The electrochemical stability of the NiFe LDH electrode is assessed by conducting potentiostatic measurements at η = 270 mV_RHE (～10 mA cm^?2) and at η = 355 mV_RHE (～30 mA cm^?2) for 24 h of continuous oxygen production.     

Hydrogen production from waste-derived synthesis gas over Ni(x)Fe(3-x)-CeO2 catalyst: optimization of Ni/Fe ratio

In this study, the effect of the Ni/Fe molar ratio on the Ni_(x)Fe_(3-x)-CeO₂ catalyst was investigated for the high-temperature water-gas shift reaction, which produces hydrogen from waste-derived synthesis gas. The catalysts were synthesized via a co-precipitation method, using different Ni/Fe molar ratios (0.5:2.5, 1.0:2.0, 1.5:1.5, 2.0:1.0, and 2.5:0.5). The physicochemical properties of these catalysts were analyzed by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction using hydrogen (H₂-TPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and H₂-O₂ pulse analyses to determine their reaction performance. The Ni_1.0Fe_2.0-CeO₂ catalyst exhibited the highest activity (X_co = 88%, T = 500 °C) without any side reactions at a high gas hourly space velocity of 41,823 mL·g⁻¹ h⁻¹, compared to the other catalysts tested, owing to its high oxygen vacancies and oxygen storage capacity (OSC). In addition, when the Ni/Fe molar ratio was higher than 1, a side reaction (methanation) occurred. Therefore, it was concluded that the Ni_1.0Fe_2.0-CeO₂ catalyst is optimal for hydrogen production via the high-temperature water-gas shift reaction from waste-derived synthesis gas.     

Synthesis of fatty acid methyl esters via the methanolysis of palm oil over Ca3.5xZr0.5yAlxO3 mixed oxide catalyst

Novel mixed metal oxide catalyst Ca_3.5xZr_0.5yAl_xO₃ was synthesized through the coprecipitation of metal hydroxides. The textural, morphological, and surface properties of the synthesized catalysts were characterized via Brunauer–Emmett–Teller method, X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and energy-dispersive X-ray spectroscopy. The catalytic performance of the as-synthesized catalyst series was evaluated during the transesterification of cooking palm oil with methanol to produce fatty acid methyl esters (FAME). The influence of different parameters, including the calcination temperature (300–700 °C), methanol to oil molar ratio (6:1–25:1), catalyst amount (0.5–6.5 wt%), reaction time (0.5–12 h) and temperature (70–180 °C), on the process was thoroughly investigated. The metal oxide composite catalyst with a Ca:Zr ratio of 7:1 showed good catalytic activity toward methyl esters. Over 87% of FAME content was obtained when the methanol to oil molar ratio was 12:1, reaction temperature 150 °C, reaction time 5 h and 2.5 wt% of catalyst loading. The catalyst could also be reused for over four cycles.     

Ni supported on MgO modified attapulgite as catalysts for hydrogen production from glycerol steam reforming

A series of Mg-modified Ni/Attapulgite (ATP) catalysts have been prepared by impregnation method for glycerol steam reforming to produce hydrogen. The physicochemical properties of catalysts were characterized using various techniques including N₂ physical adsorption analysis, XRD, H₂-TPR, SEM, TEM and NH₃-TPD. The results of N₂ physical adsorption indicated MgO modified Ni-based catalysts had unique mesostructure, resulting in the high metal dispersion and interaction between active metal and support as proven by XRD, TEM and H₂-TPR. Results of glycerin reforming experiments showed that Ni/10MgO/ATP catalyst had the highest activity than that of the other catalysts. Ni/10MgO/ATP catalyst had the smallest Ni average crystal size (10.1 nm) and the highest surface area (110.31 m²/g). These excellent properties made it show the enhanced glycerol conversion (94.71%) and a higher H₂ yield (88.45%) and the longest stability (30 h) during glycerol steam reforming (GSR) at 600 °C, W/G = 3, and WHSV = 1 h^?1. The used catalysts after 60 h of glycerin reforming experiments were also investigated by XRD, SEM, TEM, Roman and TG-DTG. The results indicated that the addition of Mg significantly inhibited the sintering of nickel grains and the formation of amorphous carbon. Therefore, Ni/10MgO/ATP catalyst increased the activity of the catalyst and extended the life of the catalyst.     

Investigation of effects of sulfur on dry reforming of biogas over nickel–iron based catalysts

The aim of this study is to maintain and increase the activity of the catalyst in the presence of H₂S with the addition of iron to the Ni catalyst. Alumina-supported monometallic iron and bimetallic nickel-iron catalysts with different weight percentages (8% Fe, 3% Ni – 3% Fe and 8% Ni – 8% Fe) were synthesized using the wet impregnation method in this study. Alumina was prepared by the sol-gel method. The activities of these synthesized catalysts in the methane dry reforming reaction were investigated at different H₂S concentrations (0 ppm, 2 ppm, and 50 ppm) with a total flow rate of 60 mL/min containing an equimolar ratio of CH₄, CO₂, and Ar at 750 °C and atmospheric pressure. To investigate the effect of sulfur compounds on the catalytic activity, the catalysts were also exposed to different gas compositions such as the mixture of H₂S + He, H₂S + CO₂ + He, and H₂S + CO₂ + CH₄ + He. In this case, FT-IR with a gas cell was used to determine the components in the gas stream at the reactor outlet. To explain catalytic performance, characterization studies were carried out using XRD, N₂ adsorption/desorption, DRIFT, SEM, TGA, and XPS analysis. All-synthesized materials showed Type-IV isotherm with a hysteresis loop corresponding to an ordered mesoporous structure. The DRIFT analysis showed a decrease in the Lewis acid sites after the addition of iron into the Ni-catalysts. In the activity test carried out in the presence of 50 ppm H₂S, it was observed that the iron-containing 8Ni–8Fe@SGA catalyst increased the sulfur resistance slightly, compared to the monometallic 8Ni@SGA catalyst. TGA analysis showed that Fe addition reduced coke deposition, as the Ni–Fe catalyst had a lower nickel crystal size than the Ni-based catalyst. FTIR analysis with a gas cell showed that sulfur in H₂S transformed to other sulfur compounds such as COS and/or SO₂ during dry reforming of biogas over alumina-supported Ni–Fe catalysts.     

Wet-impregnated bimetallic Pd-Ni catalysts with enhanced activity for dehydrogenation of perhydro-N-propylcarbazole

Palladium/platinum-based catalysts are widely used in the dehydrogenation process of Liquid Organic Hydrogen Carriers (LOHCs). The cost of noble metal has become a main drawback for LOHCs large-scale application. Partial replacement of Pd/Pt by other transition metals can be an effective solution. In this paper, we synthesize the bimetallic Pd–Ni catalyst by incipient wet impregnation and the catalytic dehydrogenation performance of perhydro-N-propylcarbazole (12H-NPCZ) as a LOHC candidate. Ni and Pd were impregnated on mesoporous alumina to obtain both monometallic and bimetallic catalysts, i.e. Pd/Al₂O₃, Ni/Al₂O₃ and Pd–Ni/Al₂O₃ (Pd:Ni = 1:1) with total metal loading of 5 wt%, respectively. The above catalysts were characterized by N₂-adsorption/desorption, H₂-temperature programmed reduction, X-Ray diffraction, X-Ray photoelectron spectroscopy, Inductively coupled plasma - optical emission spectrometer, CO pulse adsorption and Transmission electron microscopy. The catalytic dehydrogenation results indicated that the bimetallic Pd–Ni/Al₂O₃ showed best catalytic activity, followed by Pd/Al₂O₃, commercial Pd/Al₂O₃ and Ni/Al₂O₃. Notably, the catalytic activity of bimetallic was well maintained after 5 cycles at 200 °C with no degradation, indicating this bimetallic catalyst has potential prospect for large-scale application.     

Hydrogen production by low-temperature reforming of organic compounds in bio-oil over a CNT-promoting Ni catalyst

Present study reports on high catalytic activity of CNTs-supported Ni catalyst (x% Ni-CNTs) synthesized by the homogeneous deposition–precipitation method, which was successfully applied for low-temperature reforming of organic compounds in bio-oil. The optimal Ni-loading content was about 15 wt%. The H₂ yield over the 15 wt% Ni-CNTs catalyst reached about 92.5% at 550 °C. The influences of the reforming temperature (T), the molar ratio of steam to carbon fed (S/C) and the current (I) passing through the catalyst, on the reforming process of the bio-oil over the Ni-CNTs' catalysts were investigated using the stream as the carrier gas in the reforming reactor. The features of the Ni-CNTs' catalysts with different loading contents of Ni were investigated via XRD, XPS, TEM, ICP/AES, H₂-TPD and the N₂ adsorption–desorption isotherms. From these analyses, it was found that the uniform and narrow distribution with smaller Ni particle size as well as higher Ni dispersion was realized for the CNTs-supported Ni catalyst, leading to excellent low-temperature reforming of oxygenated organic compounds in bio-oil.     

Effects of metal loading and support modification on the low-temperature steam reforming of ethanol (LTSRE) over the Ni–Sn/CeO2 catalysts

This article presents the effect of metal loading and support modification with MgO on low-temperature steam reforming of ethanol (LTSRE) over Ni–Sn/CeO₂ catalysts prepare by a single-pot solution combustion synthesis (SCS) method. Atmospheric pressure activity study of these catalysts (0.5 g) is performed at different temperatures (200–400 °C), H₂O:EtOH = 12: 1 mol ratio, and feed flow rate 0.1 ml/min. After 10 h TOS at 400 °C, NiSn(5)/CM12 catalyst with 5 wt.% total metal loading, optimal Sn (Ni:Sn = 14:1), and Ce:Mg = 1:2 mol ratio shows EtOH conversion 100% and H₂ selectivity 70% with low coke deposition. Physicochemical characterizations (XRD, Raman, FESEM, TEM, and N₂ adsorption-desorption) reveal that addition of MgO in CeO₂ and an optimal amount of Sn decrease both Ni and support particle sizes while oxygen storage capacity (OSC) of the support increases (by XPS). Alkaline characteristics of MgO reduces support's acidity and improves active metal-support interaction, as evaluated by NH₃-TPD and H₂-TPR.     

Optimization for hydrogen production from methanol partial oxidation over Ni–Cu/Al2O3 catalyst under sprays

In this work, a novel Ni–Cu/Al₂O₃ catalyst is used to trigger the partial oxidation of methanol (POM) for hydrogen production. This reaction system also employed ultrasonic sprays to aid in dispersing methanol fuel. The prepared catalyst is analyzed by scanning electron microscope (SEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray diffraction (XRD) to explore the catalyst's surface structure, elemental composition, and physical structure, respectively. The Box-Behnken design (BBD) of response surface methodology (RSM) is utilized for experimental design to achieve process optimization. The operating parameters comprise the O₂/C molar ratio (0.5–0.7), preheating temperature (150–250 °C), and weight percent (wt%) of Ni (10–30%) in the catalyst. The results show that methanol conversion is 100% in all the operating conditions, while the reaction temperature for H₂ production ranges from 160 to 750 °C, stemming from heat released by POM. The significance and suitability of operating conditions are also analyzed by analysis of variance (ANOVA). It indicates that the highest H₂ yield is 2 mol (mol CH₃OH)^?1, occurring at O₂/C = 0.5, preheating temperature = 150 °C, and Ni wt% = 10. Compared with the commercial h-BN-Pt/Al₂O₃ catalyst, the prepared Ni–Cu/Al₂O₃ catalysts have higher activity for H₂ production. The O₂/C ratio is the most influential factor in the H₂ yield. Moreover, the interaction of the O₂/C ratio and Ni content is sound, reflecting that changing Ni content in the catalyst will affect the trend of H₂ yield under each O₂/C.