High-performance hybrid supercapacitor based on the porous copper cobaltite/cupric oxide nanosheets as a battery-type positive electrode material

In this work, CuCo₂O₄/CuO nanosheets (NSs) and CuCo₂O₄ oblique prisms (OPs) were synthesized at 130 °C with different amounts of hexamethyltetramine (HMTA) and reaction time through a hydrothermal method, and followed by an annealing treatment of precursors in air. The CuCo₂O₄/CuO NSs with 40 nm in thickness possessed a large specific surface area of 43.34 m² g⁻¹ and a mean pore size of 18.14 nm. The electrochemical tests revealed that the CuCo₂O₄/CuO NSs were belonged to the battery-type electrode material and exhibited a specific capacity of 395.55 C g⁻¹ at the current density of 1 A g⁻¹, higher than 258.16 C g⁻¹ for CuCo₂O₄ OPs. A hybrid supercapacitor (HSC) was assembled with activated carbon (AC) as negative electrode and CuCo₂O₄-based materials as positive electrode. The CuCo₂O₄/CuO NSs//AC HSC exhibited a high energy density of 30.18 Wh kg⁻¹ at a power density of 869.62 W kg⁻¹, and showed a fantastic cycling performance with 105.22% capacity retention over 5000 cycles. In contrast, the CuCo₂O₄ OPs//AC HSC delivered an energy density 26.27 Wh kg⁻¹ at 916.74 W kg⁻¹. These impressive electrochemical properties indicate that CuCo₂O₄/CuO NSs may serve as a promising electrode material for the highly capable hybrid supercapacitors in the near future.     

CuCo2O4–NiO heterostructure catalysts for hydrogen production from ammonia borane

Ammonia borane (NH₃BH₃, AB) has been considered as one of the most attractive candidates for chemical hydrogen-storage materials and chemical hydrogen generation materials. Development of low-cost and high-performance catalysts for hydrogen generation from AB is highly desirable, which is still a huge challenge. Hollow sphere CuCo₂O₄ promotes the catalytic hydrolysis of AB due to its unique hollow sphere shape and the synergistic effect of Co and Cu elements. In this study, a heterogeneous structured catalyst containing NiO and CuCo₂O₄ was developed by a simple and low-cost method in order to improve the catalytic performance of CuCo₂O₄. Initially, CuCo₂O₄ with hollow sphere structure was synthesized by hydrothermal method, and then NiO were deposited onto CuCo₂O₄ by impregnation-calcination method to form a heterogeneous structure. The CuCo₂O₄–NiO catalyst showed good catalytic activity for the hydrolysis of AB. The catalytic performance of CuCo₂O₄–NiO was then optimised by controlling the concentration of the impregnated salt solution, and the optimised catalytic performance was 1.42 times that of pure CuCo₂O₄ with a HER value of 870 mL_H2g_cat⁻¹min⁻¹. This low-cost CuCo₂O₄–NiO obtained by impregnation-calcination method is valuable for catalytic hydrogen production from AB.     

CuO–NiO/Co3O4 hybrid nanoplates as highly active catalyst for ammonia borane hydrolysis

Dehydrogenation of hydrogen-rich chemicals, such as ammonia borane (AB), is a promising way to produce hydrogen for mobile fuel cell power systems. However, the practical application has been impeded due to the high cost and scarcity of the catalysts. Herein, a low-cost and high-performing core-shell structured CuO–NiO/Co₃O₄ hybrid nanoplate catalytic material has been developed for the hydrolysis of AB. The obtained hybrid catalyst exhibits a high catalytic activity towards the hydrolysis of AB with a turnover frequency (TOF) of 79.1 mol_H2 mol cat⁻¹ min⁻¹. The apparent activation energy of AB hydrolysis on CuO–NiO/Co₃O₄ is calculated to be 23.7 kJ.mol⁻¹. The synergistic effect between CuO–NiO and Co₃O₄ plays an important role in the improvement of the catalytic performance. The development of this high-performing and low-cost CuO–NiO/Co₃O₄ hybrid catalytic material can make practical applications of AB hydrolysis at large-scale possible.     

Simple synthesis of honeysuckle-like CuCo2O4/CuO composites as a battery type electrode material for high-performance hybrid supercapacitors

In this paper, porous CuCo₂O₄/CuO composites with novel honeysuckle-like shape (CuCo₂O₄/CuO HCs) have been prepared for the first time by a simple hydrothermal method and followed with an additional annealing process in air. The unique CuCo₂O₄/CuO HCs consisted of dense and slender petals with length of 1.3–1.5 μm and width of about 50 nm, and possessed a specific surface area of 36.09 m² g^?1 with main pore size distribution at 10.63 nm. When used as the electrode materials for supercapacitors, the CuCo₂O₄/CuO HCs exhibited excellent electrochemical performances with a high specific capacity of 350.69 C g^?1 at 1 A g^?1, a rate capability of 78.6% at 10 A g^?1, and 96.2% capacity retention after 5000 cycles at a current density of 5 A g^?1. In addition, a hybrid supercapacitor (CuCo₂O₄/CuO HCs//AC HSC) was assembled using the CuCo₂O₄/CuO HCs as positive electrode and activated carbon (AC) as negative electrode. The HSC device delivered a specific capacity of 187.85 C g^?1 at 1 A g^?1 and a superior cycling stability with 104.7% capacity retention after 5000 cycles at 5 A g^?1, and possessed a high energy density of 41.76 W h kg^?1 at a power density of 800.27 W kg^?1. These outstanding electrochemical performances manifested the great potential of CuCo₂O₄/CuO HCs as a promising battery-type electrode material for the next-generation advanced supercapacitors with high-performance.     

Co/CuO–NiO–Al2O3 catalyst for hydrogen generation from hydrolysis of NaBH4

This paper presents hydrogen generation measurements from the hydrolysis of NaBH₄ aqueous solutions catalyzed by Co doping on single, bimetallic and trimetallic oxide supports (Co/CuO, Co/NiO, Co/Al₂O₃, Co/NiO–Al₂O₃, Co/CuO–Al₂O_3, and Co/CuO–NiO–Al₂O₃). Support materials are synthesized by the co-precipitation method. Then, Co is doped into support materials by the impregnation method. It is found that Co/CuO–NiO–Al₂O₃ catalyst exhibited high reaction activity with a maximum hydrogen generation rate (HGR) of 2067.2 ml min^?1 g_cat^?1 at 25 °C. The effect of temperature of the solution, Co amount, and recyclability of the catalyst on hydrogen generation with Co/CuO–NiO–Al₂O₃ catalyst is investigated in detail. In addition, the highest HGR for Co/CuO–NiO–Al₂O₃ catalyst is obtained at 55 °C as 6460.0 ml min^?1 g_cat^?1. The activation energy is calculated to be 31.59 kJ mol^?1 using Co/CuO–NiO–Al₂O₃ catalyst. Co/CuO–NiO–Al₂O₃ catalyst exhibits zero-order reaction kinetics concerning NaBH₄ concentration. In addition, the Co/CuO–NiO–Al₂O₃ catalyst provided high reusability after 5 cycles.     

A study into syngas production from catalytic steam reforming of palm oil mill effluent (POME): A new treatment approach

This paper reports on the novel application of catalytic steam reforming process to convert palm oil mill effluent (POME) into syngas over a 20wt%Ni/80wt%Al₂O₃ catalyst. The catalyst possessed high degree of crystallinity and was impurity-free, judging from the obtained XRD pattern. Furthermore, the BET specific surface area of catalyst was low (2.09 m² g⁻¹), consistent with smooth surface captured by the FESEM images. CO₂-desorption and NH₃-desorption profiles showed a presence of both acid and basic sites on the surface of catalyst. In the absence of catalyst, about 7.0% reduction of chemical oxygen demand (COD) was achieved at 6.0 mL h⁻¹ flow rate of POME, reforming temperature of 873 K and 20 mL min⁻¹ of N₂-flow. Significantly, the COD reduction shot up to 93.7% in the presence of catalyst and liquid-hourly-space-velocity (LHSV) of POME of 90 mL h⁻¹ g_cat⁻¹ at 873 K. The corresponding biochemical oxygen demand (BOD) reduction recorded was 93.8%. However, normalized carbon loss indicates that a high LHSV would favour carbon deposition. In addition to high LHSV, the carbon deposition was also influenced by reaction temperature. High reaction temperature has reduced carbon deposition, as well as organics removal. COD reduction was 99.41% and BOD reduction was 99.52% at 1173 K when LHSV was 60 mL h⁻¹ g_cat⁻¹. In the gas phase, four species were consistently detected, viz. H₂, CO₂, CO and CH₄, with H₂ as the major component. The H₂ selectivity increased with both LHSV and reaction temperature.     

Metal-organic frameworks (MOFs) and MOFs-derived CuO@C for hydrogen generation from sodium borohydride

Hydrogen gas has been considered as one of the promising sources of energy. Thus, several strategies including the hydrolysis of hydrides have been reported for hydrogen production. However, effective catalysts are highly required to improve the hydrogen generation rate. Two dimensional metal-organic frameworks (copper-benzene-1,4-dicarboxylic, CuBDC), and CuBDC-derived CuO@C were synthesized, characterized and applied as catalysts for hydrogen production using the hydrolysis and methanolysis of sodium borohydride (NaBH₄). CuBDC, and CuO@C display hydrogen generation rate of 7620, and 7240 mlH₂·g_cat⁻¹· min⁻¹, respectively for hydrolysis. While, CuBDC offers hydrogen generation rate of 9060 mlH₂·g_cat⁻¹· min⁻¹ for methanolysis. Both catalysts required short reaction time, and showed good recyclability. The materials may open new venues for efficient catalyst for energy-based applications.     

Ruthenium supported on nitrogen-doped porous carbon for catalytic hydrogen generation from NH3BH3 hydrolysis

In this paper, ruthenium supported on nitrogen-doped porous carbon (Ru/NPC) catalyst is synthesized by a simple method of in situ reduction using ammonia borane (AB) as reducing agent. The composition and structure of Ru/NPC catalyst are systematically characterized. This catalyst can efficiently catalyze the hydrolysis of AB. The hydrogen production reaction is completed within about 90 s at a temperature of 298 K and the maximum rate of hydrogen production is 3276 ml·s⁻¹·g⁻¹ with a reduced activation energy of 24.95 kJ·mol⁻¹. The turnover frequency (TOF) for hydrogen production is about 813 mol_H2·mol_Ru⁻¹·min⁻¹. Moreover, this catalyst can be recycled with a well-maintained performance. After five cycles, the maximum rate of hydrogen generation is maintained at 2206 ml·s⁻¹·g⁻¹, corresponding to 67.3% of the initial catalytic activity. Our results suggest that Ru/NPC prepared by in situ reduction is a highly efficient catalyst for hydrolytic dehydrogenation of AB.     

Examination of the catalytic effect of Ni,NiCr, and NiV catalysts prepared as thin films by magnetron sputtering process in the hydrolysis of sodium borohydride

In this study, nickel, nickel-chromium alloy, and nickel-vanadium alloy were coated to form a thin film on the slides prepared by magnetron sputtering process, which were used as a catalyst for the hydrolysis of alkaline sodium borohydride. Factors, such as the temperature of the solution, amount of the catalyst, initial pH of the solution and the performance of these catalysts on hydrogen generation rate were investigated using response surface methodology. Moreover, the catalysts were characterized using XRD and FE-SEM/EDS analyses. Utilizing the obtained optimum conditions of the response surface methodology estimation, the maximum hydrogen generation rate was 35,071 mL min⁻¹ g_NiV⁻¹ from NiV catalyst at 60 °C, pH 6, and 1.75 g catalyst conditions. Under the same experiment conditions, the maximum hydrogen generation rates of Ni and NiCr catalyst systems are 28,362 mL min⁻¹ g_Ni⁻¹, and 30,608 mL min⁻¹ gNiCr⁻¹, respectively.     

Methanol steam reforming over highly efficient CuO–Al2O3 nanocatalysts synthesized by the solid-state mechanochemical method

CH₃OH steam reforming is an attractive way to produce hydrogen with high efficiency. In this study, CuO.xAl₂O₃ (x = 1, 2, 3, and 4) were fabricated based on the solid-state route, and the calcined samples were employed in methanol steam reforming at atmospheric pressure and in the temperature range of 200–450 °C. The results revealed that all samples have a high BET area (173–275 m² g⁻¹), and their crystallinity was reduced by increasing the alumina content in the catalyst formulation. The catalytic activity tests showed that the CH₃OH conversion and H₂ selectivity decreased by rising the Al₂O₃·CuO molar ratio. The methanol conversion enhanced from 13% to 85% by increasing the reaction temperature from 200 °C to 450 °C over the CuO·Al₂O₃ catalyst, due to the higher reducibility of this catalyst at lower temperatures compared to other prepared samples. The influence of calcination temperature (300–500 °C), GHSV (28,000–48000 ml h⁻¹. g⁻¹_cat), feed ratio (C:W = 1:1 to 1:9), and reduction temperature (250–450 °C) was also determined on the yield of the chosen sample. The results revealed that the maximum methanol conversion decreased from 90 to 79% by raising the calcination temperature from 300 to 500 °C due to the reduction of surface area and sintering of species at high calcination temperatures.     

CuO–Ru0.3@Co3O4 nanocomposites act as a tandem catalyst for dehydrogenation of ammonia borane and hydrogenation of nitrobenezene

The development of catalysts with high activity for tandem reaction are all the ways pursued by chemists. Herein, CuO–Ru_0.3@Co₃O₄ has been synthesized and used as efficient tandem catalyst to promote the release of hydrogen from hydrolytic dehydrogenation of ammonia borane (AB) to catalyze the hydrogenation of nitrobenezenes (NBs). The catalyst exhibits the TOF of 29.87 min^?1 and provides the apparent activation energy of 45.2 kJ mol^?1 for the hydrolytic dehydrogenation of AB. Additionally, benefited from the magnetic separation capability, up to 99% of its initial catalytic activity is retained after four catalytic cycles.     

Partial oxidation of dimethyl ether by air into synthesis gas over Pt- and Rh/Ce0.75Zr0.25O2–δ catalysts

Dimethyl ether partial oxidation (DME PO) by air was studied over composite oxide Ce_0.75Zr_0.25O₂ supported Pt and Rh catalysts at temperatures 300–650 °C under atmospheric pressure, WHSV = 10 L·g_cat⁻¹·h⁻¹ and DME/O₂ molar ratio of 2. The BET, XRD, TEM and TPO techniques were used for catalyst characterization. Thermodynamic equilibrium product distribution of DME PO was calculated and used as reference data for interpreting the experimental results. Both catalysts demonstrated stable performance and coking resistance at DME PO. At 650 °C the catalysts provided complete conversion of DME and О₂ into a gas mixture of composition close to the thermodynamic equilibrium one. Synthesis gas productivity was >10 L·g_cat⁻¹·h⁻¹, its concentration in the outlet gas mixture exceeded 50 vol % that is quite suitable for solid oxide fuel cell feeding applications.     

Ammonia decomposition over SiO2-supported Ni–Co bimetallic catalyst for COx-free hydrogen generation

NH₃ decomposition over non-noble catalyst to generate CO_x-free H₂ has attracted great attention in recent years. In this work, fumed SiO₂-supported Ni, Co and Ni–Co bimetallic catalysts are synthesized by using a co-impregnation method and evaluated for NH₃ decomposition, which shows that the bimetallic catalysts exhibit better catalytic activity than the monometallic ones. This enhanced activity observed on bimetallic catalyst can be largely attributed to the more appropriate catalyst metal-N binding energy resulting from the synergistic effect between Ni and Co in the formed Ni–Co alloy. Among the synthesized catalysts, Ni₅Co₅/SiO₂ synthesized with the Ni/Co molar ratio of 5:5 achieves 76.8% NH₃ conversion under a GHSV of 30,000 mL h⁻¹ g⁻¹_cat at 550 °C and shows the best catalytic activity, which can be further improved by doping with K (78.1% NH₃ conversion at 30,000 mL h⁻¹ g⁻¹_cat), and the obtained Ni₅Co₅/SiO₂–K also shows excellent catalytic stability.     

TiO2–CdS supported CuNi nanoparticles as a highly efficient catalyst for hydrolysis of ammonia borane under visible-light irradiation

TiO₂–CdS nanotubes (NTs) were used for the first time as a support to load metal nanoparticles (NPs) for the hydrolysis of ammonia borane (AB) which is a new strategy. The TiO₂–CdS NTs support was first synthesized using a hydrothermal method, and then the CuNi NPs were loaded using a liquid-phase reduction method. The synthesized samples were characterized by XRD, SEM-EDS, TEM, XPS, ICP, UV–Vis, and PL analyses. The characterization results show that the CuNi NPs existed in the form of an alloy with a size of ~1.2 nm and uniformly dispersed on the support. Compared with their single metal counterparts, the bimetallic CuNi-supported catalysts showed a higher catalytic activity in the hydrolysis of AB under visible-light irradiation: Cu_0·45Ni_0·55/TiO₂–CdS catalyst had the fastest hydrogen evolution rate with a high conversion frequency (TOF) of 25.9 mol_H2·mol_cat⁻¹ min⁻¹ at 25 °C and low activation energy of 32.8 kJ mol⁻¹. Cu_0.45Ni_0.55/TiO₂–CdS catalyst showed good recycle performance, maintaining 99.3% and 85.6% of the original hydrogen evolution rate even after five and ten recycles, respectively. Strong absorption of visible light, improved electron–hole separation efficiency, and metal synergy between Cu and Ni elements played a crucial role in improving the catalytic hydrolysis performance of AB. The catalyst prepared in this study provides a new strategy for the application of photocatalysts.     

Synthesis of cobalt-doped catalyst for NaBH4 hydrolysis using eggshell biowaste

In the present study, a cobalt-doped catalyst was prepared from chicken eggshell powder (CEP) biowaste to be used in the hydrolysis of sodium borohydride (NaBH₄). In the presence of the prepared catalyst (CEP_cat), possible effects of the parameters of NaOH concentration (%), catalyst amount (g), NaBH₄ concentration (%), process temperature (^oC) and reusability affecting the hydrolysis of sodium borohydride were examined. The CEP_cat obtained was characterized with FT-IR, TGA, XRD, SEM and EDX analyses. The hydrogen generation rate (HGR) was determined as 432 mL g_Co⁻¹ min⁻¹ in the presence of 1 g CEP_cat, a CoO/CaO ratio of 10/90 and 1% NaBH₄ concentration. The activation energy of the NaBH₄ hydrolysis reaction was calculated as 16.78 kJ mol⁻¹. After 16 reuses of the CEP_cat there was no significant decrease in the hydrogen volume. Compared to the first use while there was an increase in the HGR. These results showed that the CEP_cat prepared has a significant advantage over other catalysts for use in NaBH₄ hydrolysis.     

One-step synthesis of CuCo2O4-Sm0.2Ce0.8O1.9 nanofibers as high performance composite cathodes of intermediate-temperature solid oxide fuel cells

One-dimensional nanostructured CuCo₂O₄-Sm_0.2Ce_0.8O_1.9 (SDC) nanofibers are prepared by the electrospinning method and one step sintering as a cathode with low polarization resistance for intermediate temperature solid oxide fuel cells (IT-SOFC). The CuCo₂O₄-SDC nanofibers cathodes form a porous network structure and have large triple-phase boundaries. Correspondingly, the electrochemical performance of the CuCo₂O₄-SDC nanofibers composite cathodes shows significantly improve, achieving the polarization resistance of 0.061 Ω cm² and the maximum power densities of 976 mW·cm⁻² at 750 °C. Thus, these results suggest that CuCo₂O₄-SDC nanofiber could be a highly active cathode material for IT-SOFCs.     

A highly active and stable Pt modified molybdenum carbide catalyst for steam reforming of dimethyl ether and the reaction pathway

To improve the stability of molybdenum carbide catalysts in dimethyl ether steam reforming (DSR), the inactivation mechanism and the performance of Pt modified catalyst has been investigated. The Mo₂C oxidation induced by H₂O is verified to be the main reason of catalytic deactivation. After modified with Pt, the H₂ production rate and selectivity are greatly enhanced, reaches 1605 μmol min⁻¹·g_cat⁻¹ at 350 °C, in comparison to that of the Mo₂C/Al₂O₃ catalyst. Moreover, the 2%Pt–Mo₂C/Al₂O₃ catalyst is more stable with only 20% activity loss after 50 h on stream compares to the 73% activity loss in 12 h with Mo₂C/Al₂O₃ catalyst. By means of in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the enhancement brought by Pt is ascribed to the consumption acceleration of intermediate oxygen species on catalyst surface and the decline of onset temperature of DSR reaction. It is expected that these findings can lead us to more practical molybdenum carbide catalysts in DSR.     

CuCo2S4 integrated multiwalled carbon nanotube as high-performance electrocatalyst for electroreduction of nitrogen to ammonia

Ammonia synthesis based on electrocatalytic nitrogen reduction reaction (NRR) by using renewable sources of energy under ambient conditions has attracted wide research attentions. Herein, we report that the noble-metal-free CuCo₂S₄/multiwalled carbon nanotube nanocomposite, which is synthesized via a facile one-step hydrothermal and sulfuration approach, can work as the high active and durable catalyst for electrocatalytic NRR. This nanocomposite achieves a high NH₃ yield of 137.5 μg h⁻¹ mg_cat⁻¹ and a high Faradaic efficiency of 8.7% at −0.5 V vs reversible hydrogen electrode (RHE) in 0.1 M Na₂SO₄ solution, which outperforms CuCo₂S₄ counterpart and most reported NRR catalysts. These results reveal that the MWCNT in nanocomposite not only suppresses the aggregation of CuCo₂S₄ nanoparticles and maximizes the exposure of active sites, but also contributes to the synergistic effect between CuCo₂S₄ nanoparticles and MWCNT, and facilitates the interfacial reaction kinetics.     

Highly dispersed cobalt nanoparticles onto nitrogen-doped carbon nanosheets for efficient hydrogen generation via catalytic hydrolysis of sodium borohydride

Porous carbon nanostructures are promising supports for stabilizing the highly dispersed metal nanoparticles and facilitating the mass transfer during the reaction, which are critical to achieve the high efficiency of hydrogen generation from sodium borohydride dehydrogenation. Herein, the catalytically active porous architectures are simply prepared by using 2-methylimidazole and melamine as reactive sources. The structural and compositional characterizations reveal the coexistence of metallic cobalt and N-doped carbon in porous architectures. Electron microscopy observations indicate that the synthesized products are smartly constructed from the carbon nanosheets with densely dispersed Co nanoparticles. Due to the notable structural features, the prepared Co@NC-600 sample presents the highly efficient activity for catalytic hydrolysis of NaBH₄ with a hydrogen generation rate of 2574 mL min⁻¹ g_cat⁻¹ and an activation energy of 47.6 kJ mol⁻¹. The catalytically active metallic Co and suitable support-effect of N-doped carbon are responsible for catalytic dehydrogenation.     

Apricot Kernel shell waste treated with phosphoric acid used as a green,metal-free catalyst for hydrogen generation from hydrolysis of sodium borohydride

In this study, grinded apricot kernel shell (GAKS) biobased waste was used for the first time as a cost-effective, efficient, green and metal-free catalyst for hydrogen generation from the hydrolysis reaction of sodium borohydride (NaBH₄). For the hydrogen production by NaBH₄ hydrolysis reaction, GAKS was treated with various acids (HCl, HNO₃, CH₃COOH, H₃PO₄), salt (ZnCl₂) and base (KOH). As a result, the phosphoric acid (H₃PO₄) demonstrated better catalytic activity than other chemical agents. The hydrolysis of NaBH₄ with the GAKS-catalyst (GAKS_cat) was studied depending on different parameters such as acid concentration, furnace burning temperature and time, catalyst amount, NaBH₄ concentration and hydrolysis reaction temperature. The obtained GAKS_cat was characterized by ICP-MS, elemental analysis, TGA, XRD, FT-IR, Boehm, TEM and SEM analyses and was evaluated for its catalytic activity in the hydrogen production from the hydrolysis reaction of NaBH₄. According to the results, the optimal H₃PO₄ percentage was found as 15%. The maximum hydrogen generation rate from the hydrolysis of NaBH₄ with the GAKS_cat was calculated as 20,199 mL min⁻¹ g_cat⁻¹. As a result, it can be said that GAKS treated with 15% H₃PO₄ as a catalyst for hydrogen production is an effective alternative due to its high hydrogen production rate.