Ni/Al2O3 catalysts for CO2 methanation: Effect of silica and nickel loading

Samples containing from 1 to 33 wt.% of NiO on silica and alumina doped with silica (1 and 20 wt.% silica in the support) have been prepared and characterized by BET, XRD, FT-IR, UV–vis–NIR, FE-SEM, EDXS, and TPR techniques. Catalysts have been pre-reduced in situ before catalytic experiments and data have been compared with Ni/Al₂O₃ reference sample. Characterization results showed that SiO₂ support has a low Ni dispersion ability mainly producing segregated NiO particles and a small amount of dispersed Ni²⁺ in exchange sites. Instead, for the Si-doped alumina a “surface spinel monolayer phase” is formed by increasing Ni loading and, only when the support surface is completely covered by this layer, NiO is formed. Moreover, H₂-TPR results indicated that NiO particles are more easily reduced compared to Ni species. Low loading Ni/SiO₂ catalysts show high selectivity and moderate activity for RWGS (reverse Water Gas Shift) reaction, likely mainly due to nickel species dispersed in silica exchange sites, as evidenced by visible spectroscopy. High loading Ni/SiO₂ catalysts show both methanation and RWGS but evident short-term deactivation for methanation, attributed to large, segregated Ni metal particles, covered by a carbon veil. Ni on alumina -rich carriers, where nickel disperses forming a surface spinel phase, show high activity and selectivity for methanation, and short-term catalyst stability as well. This activity is attributed to small nickel clusters or metal particles interacting with alumina, formed upon reaction. The addition of SiO₂ in Al₂O₃ support decreases the activity of Ni catalysts in CO₂ methanation, because it reduces the ability of the support to disperse nickel in form of the surface spinel phase, thus reducing the amount of Ni clusters in the reduced catalysts.     

Effect of surface properties controlled by Ce addition on CO2 methanation over Ni/Ce/Al2O3 catalyst

Ce-promoted Ni/Al₂O₃ catalysts with Ce contents of 0, 5, 10, 15, and 20 wt% were investigated for CO₂ methanation. Ni/15Ce/Al₂O₃ showed good selectivity and catalytic performance in CO₂ methanation and remained stable at 350 °C for 80 h with minor fluctuations. Interactions between Ni and the Ce/Al₂O₃ support was characterized using X-ray diffraction, temperature-programmed reduction of H₂, temperature-programmed desorption of CO₂, X-ray photoelectron spectroscopy, Raman spectroscopy, and thermogravimetric analysis. Addition of Ce did not increase the catalytic surface area, which can significantly enhance the heterogeneous catalytic activity. However, XPS analysis showed that the Ce on the Ni/Al₂O₃ catalyst changed the surface electron states of Ni, Ce, and O. Additionally, CO₂ adsorption/desorption was confirmed to be related to the amount of Ce present on Ni/Al₂O₃ by TGA and CO₂-TPD. The Ce addition thus played an important role in determining the CO₂ adsorption, desorption, and conversion.     

Assessing the potential of xNi-yMg-Al2O3 catalysts prepared by EISA-one-pot synthesis towards CO2 methanation: An overall study

Mesoporous xNi-yMg-Al₂O₃ catalysts prepared by combined evaporation induced self-assembly (EISA) and one-pot techniques were tested in CO₂ methanation reaction. All calcined/reduced materials were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), N₂ physisorption, thermogravimetric analysis (TGA), CO₂ adsorption, H₂ temperature programmed reduction (H₂-TPR) and transmission electron microscopy (TEM). The effects of Mg and Ni loadings on the catalysts properties and performances were systematically studied. Higher Mg contents enhanced methanation performances due to more favourable metallic interactions between the Ni, Mg and Al species. In addition, higher Ni contents led to better selectivity to CH₄ by enhancing methane formation that involves H₂ dissociation on Ni⁰ sites. The mesoporous 5Ni–Al₂O₃ catalyst obtained by the EISA-one-pot technique was significantly more active than silica-based catalysts with same 5 wt% Ni content supported on USY zeolite and SBA-15. Moreover, the performances of the most promising 15Ni–7Mg–Al₂O₃ mesoporous material were similar to those of a commercial 25Ni/γ-Al₂O₃ catalyst in spite of its reduced nickel content.     

Vanadium promoted Ni(Mg,Al)O hydrotalcite-derived catalysts for CO2 methanation

A series of V-promoted hydrotalcite-derived nickel catalysts (1.0, 2.0, and 4.0 wt%) were tested in CO₂ methanation. Ni–I–V2.0 with 2.0 wt% vanadium loading showed the highest catalytic activity, achieving 74.7% of CO₂ conversion and 100% of CH₄ selectivity at 300 °C. XRD and XANES analyses showed that the smallest Ni⁰ particles in Ni–I–V2.0 were consistent with the improved textural features observed for this catalyst. Moreover, CO₂-TPD revealed the highest sum of weak and medium basic sites in Ni–I–V2.0 that can positively influence catalytic behavior. For the studied catalysts, a clear correlation was demonstrated between the catalytic activity and specific surface area, as well as the basic properties.     

Syngas production from glycerol-dry(CO2) reforming over La-promoted Ni/Al2O3 catalyst

A 3 wt% La-promoted Ni/Al₂O₃ catalyst was prepared via wet co-impregnation technique and physicochemically-characterized. Lanthanum was responsible for better metal dispersion; hence higher BET specific surface area (96.0 m² g⁻¹) as compared to the unpromoted Ni/Al₂O₃ catalyst (85.0 m² g⁻¹). In addition, the La-promoted catalyst possessed finer crystallite size (9.1 nm) whilst the unpromoted catalyst measured 12.8 nm. Subsequently, glycerol dry reforming was performed at atmospheric pressure and temperatures ranging from 923 to 1123 K employing CO₂-to-glycerol ratio from zero to five. Significantly, the reaction results have yielded syngas as main gaseous products with H₂:CO ratios always below than 2.0 with concomitant maximum 96% glycerol conversion obtained at the CO₂-to-glycerol ratio of 1.67. In addition, the glycerol consumption rate can be adequately captured using power law modelling with the order of reactions equal 0.72 and 0.14 with respect to glycerol and CO₂ whilst the activation energy was 35.0 kJ mol⁻¹. A 72 h longevity run moreover revealed that the catalyst gave a stable catalytic performance.     

Nano composite composed of MoOx-La2O3Ni on SiO2 for storing hydrogen into CH4 via CO2 methanation

The crucial problems for the catalysts of CO₂ methanation are the low activity at low temperature and deactivation caused by metal sintering. In order to overcome the problems or to improve the shortages, a new scheme has been put forward by loading LaNi_1-xMo_xO₃ with perovskite-type structure on SiO₂. After reduction, Ni nanoparticles, MoO_x and La₂O₃ would be all stay together and highly dispersed on SiO₂ (Ni/MoO_x-La₂O₃/SiO₂). The techniques of BET, XRD, H₂-TPR, HRTEM, ICP, H₂ chemisorption and XPS were used to characterize the prepared samples. Through effectively combining MoO_x which is active for the reaction of reverse water gas shift and Ni which can catalyze CO methanation, the resultant Ni/MoO_x-La₂O₃/SiO₂ catalyst exhibited pretty good performance for CO₂ methanation, especially showing very good resistance to metal sintering. NiLa₂O₃/SiO₂ catalyst without adding Mo was investigated for comparison. Since many metallic ions can enter into the lattice of a perovskite-type oxide, therefore, many combined catalysts for sequential reactions may be designed via this scheme.     

Impact of Ce-Loading on Ni-catalyst supported over La2O3+ZrO2 in methane reforming with CO2

This paper investigated the effect of doping Ni supported catalysts with different ceria loading. The catalysts (5%Ni+x%Ce/La₂O₃+ZrO₂, where x = 0, 1, 2, 2.5, 3, 5) were synthesized via the wet impregnation technique and tested for methane reforming with carbon dioxide at atmospheric pressure, 700 °C and 42, 000 ml/g_cat.h gas hourly space velocity. The fresh catalysts were subjected to different characterization techniques such as X-ray diffraction, Surface area and pore analysis, H₂-temperature programmed reduction, CO₂-temperature programmed desorption and thermogravimetric analysis (TGA). A fine correlation between characterization results and catalytic activity is found. The results of the reactions indicated that 5%Ni/La₂O₃+ZrO₂ has the lowest conversion which increased with the percentage loading of CeO₂ up to 2.5 wt % and then began to decline. This suggests that 2.5 wt % loading is the optimum for CH₄ and CO₂ conversion. This particular catalyst composition has NiO species that could be reduced easily, as well as dense and wide distribution of all type of basic sites with respect to other catalyst system. The used catalysts were again subjected to TGA and RAMAN analysis where the least carbon deposition and the least deactivation factor was observed for 5%Ni+5%Ce/La₂O₃+ZrO₂ catalysts.     

Synergistic regulation of hydrogen adsorption/desorption via dual interfaces of Cu/Ni/Ni(OH)2 toward efficient hydrogen evolution reaction

Nickel-based catalysts have attracted tremendous attention as alternatives to precious metal-based catalysts for electrocatalytic hydrogen evolution reaction (HER) in virtue of their conspicuous advantages such as abundant reserves and high electrochemical activity. Nevertheless, a great challenge for Ni-based electrocatalyst is that nickel sites possess too strong adsorption for key intermediates H1, which severely suppresses the hydrogen-production activities. Herein, we report a hierarchical architecture Cu/Ni/Ni(OH)₂ consisting of dual interfaces as a high-efficient electrocatalyst for HER. The Cu nanowire backbone could provide geometric spaces for loading plenty of Ni sites and the formed Ni/Cu interface could effectively weakened the adsorption intensity of H1 intermediates on the catalyst surface. Moreover, the H1 adsorption could be further controlled to appropriate states by in-situ formed Ni(OH)₂/Ni interface, which simultaneously promotes water adsorption and activation, thus both Heyrovsky and Volmer steps in HER could be obviously accelerated. Experimental and theoretical results confirm that this interface structure can promote water dissociation and optimize H1 adsorption. Consequently, the Cu/Ni/Ni(OH)₂ electrocatalyst exhibits a low overpotential of 20 mV at 10 mA cm^?2 and an ultralow Tafel slope of 30 mV dec^?1 in 1.0 M KOH, surpassing those of reported transition-metal-based electrocatalysts and even the prevailing commercial Pt/C.     

A review on ethanol steam reforming for hydrogen production over Ni/Al2O3 and Ni/CeO2 based catalyst powders

Hydrogen is contemplated as an alternative clean fuel for the future. Ethanol steam reforming (ESR) is a carbon-neutral, sustainable, green hydrogen production method. Low cost Ni/Al₂O₃ and Ni/CeO₂ powder catalysts demonstrate high ESR activity. However, acidic nature of Al₂O₃ and instability of CeO₂ lead to deactivation of the catalysts easily. This article examines the research articles published on the modification of Ni by various noble and non-noble metals and on alteration of the supports by different metal oxides in detail and their effect on ESR all through 2000–2021. The ESR reaction mechanisms on Ni/Al₂O₃ and Ni/CeO₂ powder catalysts and basic thermodynamics for different possible reactions and H₂ yield are explored. Manipulation of catalyst morphology (surface area and particle size) via preparation method, selection of active metal promoter and support modifier are found to be significantly important for H₂ production and minimizing carbon deposition on catalysts.     

Cobalt nanoparticles supported on alumina nanofibers (Co/Al2O3): Cost effective catalytic system for the hydrolysis of methylamine borane

Amongst different amine-borane derivatives, methylamine-borane (CH₃NH₂BH₃) seems to be one of the capable aspirants in the storing of hydrogen attributable to its high hydrogen capacity, stability and aptitude to generate hydrogen through its catalytic hydrolysis reaction under ambient conditions. In this research paper, we report that cobalt nanoparticles supported on alumina nanofibers (Co/Al₂O₃) are acting as active nanocatalyst for catalytic hydrolysis of methylamine-borane. Co/Al₂O₃ nanocatalyst was fabricated by double-solvent method followed with wet-chemical reduction, and was characterized by utilizing various spectroscopic methods and imaging techniques. The results gathered from these analyses showed that the formation Al₂O₃ nanofibers supported cobalt(0) nanoparticles with a mean diameter of 3.9 ± 1.2 nm. The catalytic feat of these cobalt nanoparticles was scrutinized in the catalytic hydrolysis of methylamine-borane by considering their activity and durability performances. They achieve releasing of 3.0 equivalent of H₂ via methylamine-borane hydrolysis at room temperature (initial TOF = 297 mol H₂/mol metal × h). Along with activity the catalytic durability of Co/Al₂O₃ was also studied by carrying out recyclability tests and it was found that these supported cobalt nanoparticles have good durability during the course of the catalytic recycles so that Co/Al₂O₃ preserves almost its innate activity at 5th catalytic recycle. The studies presented here also contains kinetic investigation of Co/Al₂O₃ catalyzed methylamine borane hydrolysis depending on the temperature, cobalt and methylamine borane concentrations, which were used to define rate expression and the activation energy of the catalytic reaction.     

Investigating a HEX membrane reactor for CO2 methanation using a Ni/Al2O3 catalyst: A CFD study

In this contribution, viability of processing of the flue gas streams as a source of carbon dioxide for the thermo-catalytic conversion was investigated. For this purpose, a Ni/Al₂O₃ commercial catalyst with known chemical kinetics was utilized. Moreover, a transient mathematical model for dynamic catalyst deactivation was developed and validated with experimental results available in the open literature. The developed model was then utilized to understudy an air-cooled membrane reactor. Different tube configurations were understudied and compared to choose the conditions under which high conversion was feasible. Sensitivity analysis revealed that, the space velocity, cooling rate, and feed distribution were all considered to be critical factors. It was revealed that, the presence of membrane resulted in higher conversion through the undertaken reactor. It made it possible to enhance reaction yield of non-membrane reactor through evenly distributing hydrogen along its length. A designed heat-exchanger (HEX) membrane reactor achieved 99% CO₂ conversion when the coolant flow rate was reached to 10% of the coolant gravimetric flow rate, feed space velocity was set at 100 h⁻¹ and the feed pressure was set at 10 bars.     

Characterization and evaluation of mesoporous high surface area promoted Ni- Al2O3 catalysts in CO2 methanation

In this research, mesoporous high surface area Ni-Al₂O₃ catalysts promoted with different transition metals (Cr, Fe, Mn, Cu, and Co) were synthesized via ultrasound-assisted co-precipitation method and their performance was explored in CO₂ methanation process. The promoters can affect the textural and catalytic properties of the Ni-Al₂O₃ catalysts to some extent. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction with hydrogen (H₂-TPR), and N₂ adsorption-desorption (BET) were used for the characterization of the prepared samples. From the BET results, it was found that the incorporation of 5 wt% of the promoter into Ni-Al₂O₃ catalysts caused a decrease in the surface area, NiAl₂O₄ crystalline size and an increase in the mean pore diameter and total pore volume. Among the samples, the catalyst modified by Mn, exhibited the higher catalytic activity and selectivity towards CH₄, especially at low temperatures (200–350 °C). These results could be explained by highest Ni active sites dispersion of this catalyst and enhancement of the catalyst reducibility at the low temperatures. The effect of Mn content was also evaluated and the results revealed that the Ni-Al₂O₃ sample modified with 3 wt% Mn with the highest BET surface area and the lowest crystalline size possessed the best catalytic performance. To further investigate the influence of ultrasonic irradiation, the optimal catalyst was prepared with a conventional co-precipitation method and its textural and catalytic properties were compared with those obtained for the catalyst prepared with the ultrasonic assisted coprecipitation method. Also, 25Ni-3Mn-Al₂O₃ catalyst showed a stable performance at 350 °C for 10 h in the CO₂ methanation reaction.     

Influence of reduction temperature on Ni particle size and catalytic performance of Ni/Mg(Al)O catalyst for CO2 reforming of CH4

Hydrotalcite-derived Ni/Mg(Al)O is promising for CH₄–CO₂ reforming. However, the catalysts reported so far suffer from sever coking at low temperatures. In this work, we demonstrate that a significant improvement of coke-resistance of Ni/Mg(Al)O can be achieved by fine tuning the Ni particle size through adjusting the reduction condition of catalyst. Ni particles having average size within 4.0–7.1 nm are in situ generated by reducing the catalyst at a selected temperature within 923–1073 K. Controllability of Ni particle size is related to the formation of Mg(Ni,Al)O solid solution upon hydrotalcite decomposition. It is found that the catalyst reduced at 973 K exhibits high activity, stability, and coke-resistance even at reaction temperature as low as 773 K. In contrast, the catalyst reduced at 923 K has low activity and deactivates due to Ni oxidation, while those reduced at 1023 and 1073 K suffer from sintering and severe coking. STEM and O₂-TPO reveal that coke deposition is directly proportional to the Ni particle size but becomes negligible at a size below 6.2 nm. It is evidenced that a critical size of about 6 nm is required to inhibit coking effectively. CO₂ temperature-programmed surface reaction indicates that the deposited carbon on small Ni particles can be easily removed by the CO₂ activated at the Ni–Mg(Al)O interfaces, accounting for the better resistance to coking.     

Process optimization of DBD plasma dry reforming of methane over Ni/La2O3MgAl2O4 using multiple response surface methodology

In this study, 10% Ni/La₂O₃MgAl₂O₄ nano-flake catalyst was synthesized, characterized and tested in a catalytic dielectric barrier discharge (DBD) plasma for dry reforming of methane (DRM). With design of experiment (DoE), the influence of process parameters namely (1) total feed flow rate (ml min⁻¹), (2) feed ratio (CO₂/CH₄), (3) input power (W) and (4) catalyst loading (g) were examined using multiple response surface methodology (RSM) through a four-factor, five-level central composite design (CCD). Second-order regression models were applied for evaluating the interaction between the process parameters and responses. Input power (X₃) and total feed flow rate (X₁) were the two most influential process parameters followed by catalyst loading (X₄) and feed ratio (X₂). The experimental and predicted results from the optimum conditions fitted-well with less than ±5% margin of error. The possible dynamic interactions between the process variables were elucidated. The optimum values are feed flow rate = 18.8 ml min⁻¹, feed ratio = 1.05, input power = 125.6 W and catalyst loading = 0.6 g. At these conditions, the predicted CH₄ and CO₂ conversions are 79.86% and 84.03%, respectively. The H₂ and CO yields are predicted as 41.37% and 40.47%, respectively while H₂/CO ratio is above unity. The calculated EE from the RSM model is predicted as 0.135 mmol kJ⁻¹. Low carbon deposition observed on the spent catalyst is attributed to the highly basic and oxidative nature of the La₂O₃ co-supported catalyst.     

Determining optimum conditions for hydrogen production from glucose by an anaerobic culture using response surface methodology (RSM)

Hydrogen fermentation is a very complex process and is greatly influenced by many factors. Previous studies have demonstrated that temperature, pH and substrate are important factors controlling biological H₂ production. Response surface methodology with central composite design was used in this study to optimize H₂ production from glucose by an anaerobic culture. The individual and interactive effects of pH, temperature and glucose concentration on H₂ production were also evaluated. The optimum conditions for maximum H₂ yield of 1.75 mol-H₂ mol-glucose⁻¹ were found as temperature 38.8 °C, pH 5.7 and glucose concentration 9.7 g L⁻¹. The linear effects of temperature and pH as well as their quadratic effects on H₂ yield were significant, while the interactive effects of three parameters were minor.     

Production of hydrogen via steam reforming of acetic acid over Ni and Co supported on La2O3 catalyst

Nickel (Ni)-cobalt (Co) supported on lanthanum (III) oxide (La₂O₃) catalyst was prepared via impregnation technique to study the steam reformation of acetic acid for hydrogen generation by using one-step fixed bed reactor. Moreover, in order to specify the physical and the chemical attributes of the catalyst, X-ray diffraction (XRD), nitrogen physisorption, temperature-programmed reduction (TPR), temperature-programmed desorption of ammonia and carbon dioxide (TPD-NH₃ and CO₂), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA) methods were employed. The nitrogen physisorption analysis showed that the presence of Co on Ni/La₂O₃ improved the textural properties of the catalyst by increasing the surface area, the pore diameter and the pore volume of the catalyst. This improved the dispersion of metal particle and caused a reduction in the size of metal particle, and consequently, increased the catalytic activity, as well as the resistance to coke formation. On top of that, the condensation and the dehydration reactions during acetic acid steam reforming created carbon deposition on acidic site of the catalyst, which resulted in the deactivation of catalyst and the formation of coke. Besides, in this study, Ni/La₂O₃ contributed to a high acetic acid conversion (100%) at 700 °C, but it produced more coking compared to Ni–Co/La₂O₃ and Co/La₂O₃ catalysts.     

Preferential CO oxidation on Ru/Al2O3 catalyst: An investigation by considering the simultaneously involved methanation

The CO removal with preferential CO oxidation (PROX) over an industrial 0.5% Ru/Al₂O₃ catalyst from simulated reformates was examined and evaluated through considering its simultaneously involved oxidation and methanation reactions. It was found that the CO removal was fully due to the preferential oxidation of CO until 383 K. Over this temperature, the simultaneous CO methanation was started to make a contribution, which compensated for the decrease in the removal due to the decreased selectivity of PROX at higher temperatures. This consequently kept the effluent CO content as well as the overall selectivity estimated as the ratio of the removed CO amount over the sum of the consumed O₂ and formed CH₄ amounts from apparently increasing with raising reaction temperature from 383 to 443 K when the CO₂ methanation was yet not fully started. At these temperatures the tested catalyst enabled the initial CO content of up to 1.0 vol.% to be removed to several tens of ppm at an overall selectivity of about 0.4 from simulated reformates containing 70 vol.% H₂, 30 vol.% CO₂ and with steam of up to 0.45 (volume) of dry gas. Varying space velocity in less than 9000 h⁻¹ did not much change the stated overall selectivity. From the viewpoint of CO removal the article thus concluded that the methanation activity of the tested Ru/Al₂O₃ greatly extended its working temperatures for PROX, demonstrating actually a feasible way to formulate PROX catalysts that enable broad windows of suitable working temperatures.     

Performance optimization of microbial electrolysis cell (MEC) for palm oil mill effluent (POME) wastewater treatment and sustainable Bio-H2 production using response surface methodology (RSM)

Microbial electrolysis cells (MECs) are a new bio-electrochemical method for converting organic matter to hydrogen gas (H₂). Palm oil mill effluent (POME) is hazardous wastewater that is mostly formed during the crude oil extraction process in the palm oil industry. In the present study, POME was used in the MEC system for hydrogen generation as a feasible treatment technology. To enhance biohydrogen generation from POME in the MEC, an empirical model was generated using response surface methodology (RSM). A central composite design (CCD) was utilized to perform twenty experimental runs of MEC given three important variables, namely incubation temperature, initial pH, and influent dilution rate. Experimental results from CCD showed that an average value of 1.16 m³ H₂/m³ d for maximum hydrogen production rate (HPR) was produced. A second-order polynomial model was adjusted to the experimental results from CCD. The regression model showed that the quadratic term of all variables tested had a highly significant effect (P < 0.01) on maximum HPR as a defined response. The analysis of the empirical model revealed that the optimal conditions for maximum HPR were incubation temperature, initial pH, and influent dilution rate of 30.23 ^°C, 6.63, and 50.71%, respectively. Generated regression model predicted a maximum HPR of 1.1659 m³ H₂/m³ d could be generated under optimum conditions. Confirmation experimentation was conducted in the optimal conditions determined. Experimental results of the validation test showed that a maximum HPR of 1.1747 m³ H₂/m³ d was produced.     

Impacts of metal loading in Ni/attapulgite on distribution of the alkalinity sites and reaction intermediates in CO2 methanation reaction

Both metal sites and alkaline sites are essential parameters for a catalyst used in methanation of CO₂. This study investigated the impacts of the relative abundance of metal sites and alkaline sites on the catalytic performances of nickel-based catalyst with attapulgite, a natural mineral, as the support. The results showed that the increase of nickel loading to attapulgite significantly decreased the abundance of alkaline sites, remarkably enhanced the catalytic activity, and suppressed the formation of CO. The in situ DRIFTS characterization of the CO₂ methanation indicated that the alkaline sites favored formation of the oxygen-containing reaction intermediates such as CO1, –OH, 1CO₂, formate, carbonate and bicarbonate species. In comparison, metallic nickel species promoted their further hydrogenation to form CH₄. Besides the absorption/activation of 1CO₂ was more preferable on surface of metallic nickel, but not on the alkaline sites. The availability of the alkaline sites was not as important as the metallic nickel species for preparation of an efficient catalyst for CO₂ methanation.     

Water soluble nickel(0) and cobalt(0) nanoclusters stabilized by poly(4-styrenesulfonic acid-co-maleic acid): Highly active, durable and cost effective catalysts in hydrogen generation from the hydrolysis of ammonia borane

This paper reports the in-situ generation and catalytic activity of nickel(0) and cobalt(0) nanoclusters stabilized by poly(4-styrene sulfonic acid-co-maleic acid), PSSA-co-MA, in the hydrolysis of ammonia borane (AB). PSSA-co-MA stabilized nickel(0) (PSMA-Ni) and cobalt(0) nanoclusters (PSMA-Co) having average particle size of 2.1 ± 0.6 and 5.3 ± 1.6 nm, respectively, were generated by in-situ reduction of nickel(II) chloride or cobalt(II) chloride in an aquoues solution of NaBH₄/H₃NBH₃ in the presence of PSSA-co-MA. The in-situ generated nanoclusters were isolated from the reaction solution and characterized by UV-Vis, TEM, XRD and FT-IR techniques. Compared with the previous catalyst systems, PSMA-Ni and PSMA-Co are found to be highly active catalysts for hydrogen generation from the hydrolysis of AB with the turnover frequency values of 10.1 min⁻¹ for Ni and 25.7 min⁻¹ for Co. They are also very stable during the hydrolysis of AB providing 22450 and 17650 turnovers, respectively. The results of mercury poisoning experiments reveal that PSMA-Ni and PSMA-Co are heterogeneous catalysts in the hydrolysis of AB. Herein, we also report the results of a detailed kinetic study on the hydrogen generation from the hydrolysis of AB catalyzed by PSMA-Ni and PSMA-Co depending on catalyst concentration, substrate concentration, and temperature along with the activation parameters of catalytic hydrolysis of AB calculated from the kinetic data.