Ni-hydrotalcite loading on carbon as co-catalyst for fermentative hydrogen production

The influence of Ni-hydrotalcite (HT) loading on the activity and stability of Ni-HT supported on activated carbon (Ni-HT/AC) was investigated for fermentative hydrogen production. The basic sites of Ni-HT loading on AC support significantly boosted the catalytic performance with the initial faster rate. The combined function catalyst of Ni-HT/AC facilitates the rapid decomposition of saccharides and high selectivity to fructose that attained the maximum hydrogen production within 24 h. The optimum dose of Ni-HT/AC at 8.33 g/L showed a 25.84% increment over the control. In addition, shortening the lagging phase time at 1.50 h was achieved. The high adsorption capacity of lactic acid was induced with the basic sites of Ni-HT/AC. However, a deactivation of the Ni-HT/AC during prolonged fermentation was associated with metabolites formation, causing the leaching of Mg²⁺ ions from the surface of AC supported Ni-HT and reducing surface basicity of Ni-HT/AC.     

MOFs in photoelectrochemical water splitting: New horizons and challenges

Growing energy consumption with the augmentation in universal population to more than nine billion by 2050 and exhausting fossil fuel reserves necessitates a harsh revolution from non-renewable energy reservoirs to renewable energy reservoirs with zero carbon emission. In the present scenario, solar energy prompted photoelectrochemical (PEC) water splitting or “Artificial Photosynthesis” via light gripping semiconductor material, originates out as the most promising methodology in accomplishing the global energy crisis. Recent studies have amply demonstrated the potential of metal-organic frameworks (MOF) towards PEC applications. They are porous crystalline coordination polymers assembled through an appropriate choice of metal ions and multidentate organic ligands. Owing to their structural regularity and synthetic tunability, MOFs integration with PEC is considered in terms of enhancing and broadening light absorption, providing active sites and directing charge transfer dynamics. Here, we have explored MOFs role in PEC and classified them into different categories such as photosensitizers, co-catalysts, counter electrode, template and also for imparting additional stability to the electrode system. MOFs mediated PEC water splitting is promising but is still rare and in its infancy. Therefore, it is pertinent and timely to take stock of the advancements made and develop insight on the use of MOFs, as an emerging solution for the problems encountered in PEC. This review covers the basics of MOF & mainly describes various case studies done during last 10 years and providing adequate impetus to researchers for critically assessing the recent advances and challenges that are faced by scientists and researchers at large.     

Two dimensional porous Ni12P5 sheet modified Mn0.5Cd0.5S for efficient photo-catalytic hydrogen production

In this paper, solid solution Mn_0.5Cd_0.5S (MCS) nanocrystals is modified by two-dimensional (2D) porous Ni₁₂P₅ sheet to form Ni₁₂P₅/MCS composite, which shows photo-catalytic hydrogen production rate as high as 63.22 mmol g^?1 h^?1. Compared with pure Mn_0.5Cd_0.5S, the hydrogen production performance is nearly 9 times improved. As a non-noble metal co-catalyst, the 2D structure and unique electronic properties of Ni₁₂P₅ not only promoted the absorption of light, but also effectively inhibited the recombination process of photo-generated carriers. The successful preparation of Ni₁₂P₅/MCS composite provided an effective way for improving the photo-catalytic performance of semiconductor materials.     

Br?nsted酸性离子液体催化双酚芴的合成

以1-甲基咪唑、1,3-丙磺酸内酯、硫酸、磷酸、四氟硼酸、对甲苯磺酸为原料,合成4种Br?nsted酸性离子液体(ILs),通过FTIR、NMR和TG对其结构进行了表征,同时采用UV-vis测定了离子液体的酸度H0。将离子液体应用于双酚芴(BHPF)的合成反应中,离子液体的酸度H0≤1.94时有催化作用,H0≤1.69的ILs催化剂有应用价值。采用单变量优化法考察了反应参数对9-芴酮和苯酚缩合反应的影响,确定较优反应条件为:苯酚、9-芴酮和IL1的物质的量比为6∶1∶0.125,IL1和助催化剂巯基乙酸的物质的量比为5∶2,反应温度110℃,反应时间6 h。在上述条件下,考察了4种离子液体催化剂对双酚芴合成反应的催化效果,使用IL1、IL2、IL4催化反应时,9-芴酮转化率均为100%,双酚芴的选择性约为87%。此外,离子液体IL1连续使用5次催化效果无明显降低。     

Facile fabrication of nickel/porous g-C3N4 by using carbon dot as template for enhanced photocatalytic hydrogen production

Ni/porous g-C₃N₄ was prepared by high temperature thermal polymerization process using carbon dots as soft template and photodeposition. With nickel nanoparticles supported as co-catalyst, the hydrogen evolution reaction (HER) activity of the photocatalyst has been significantly enhanced under visible light, which is up to 1273.58 μmol g⁻¹ h⁻¹, superior to pristine g-C₃N₄ (4.12 μmol g⁻¹ h⁻¹). This is attributed to the inhibited recombination of photogenerated electron-hole pairs and the much better electron transport efficiency. The formed porous structure of carbon nitride could facilitate light utilization and together with nickel nanoparticles, better charge separation can be realized which are proved by the photoluminescence, time-resolved photoluminescence spectra, transient photocurrent measurements and electrochemical impendence spectroscopy. This work provides a useful route to obtain less expensive and efficient photocatalyst containing no noble metals for hydrogen production.     

Enhanced photoelectrochemical performance of 2D core-shell WO3/CuWO4 uniform heterojunction via in situ synthesis and modification of Co-Pi co-catalyst

In order to enhance the photoelectrochemical (PEC) performance of tungsten oxide (WO₃), it is critical to overcome the problems of narrow visible light absorption range and low carrier separation efficiency. In this work, we firstly prepared the 2D plate-like WO₃/CuWO₄ uniform core-shell heterojunction through in-situ synthesis method. After modification with the amorphous Co-Pi co-catalyst, the ternary uniform core-shell structure photoanode achieved a photocurrent of 1.4 mA/cm² at 1.23 V vs. RHE, which was about 6.67 and 1.75 times higher than that of pristine WO₃ and 2D uniform core-shell heterojunction, respectively. Furthermore, the onset potential of 2D WO₃/CuWO₄/Co-Pi core-shell heterojunction occurred a negatively shifts of about 20 mV. Experiments illuminated that the enhanced PEC performance of WO₃/CuWO₄/Co-Pi photoanode was attributed to the broader light absorption, reduced carrier transfer barrier and increased carrier separation efficiency. The work provides a strategy of maximizing the advantages of core-shell heterojunction and co-catalyst to achieve effective PEC performance.     

CuOCr2O3 core-shell structured co-catalysts on TiO2 for efficient photocatalytic water splitting using direct solar light

Synthesis of core-shell structured CuOCr₂O₃ nanoparticles as co-catalyst to improve the photocatalytic hydrogen evolution performance of TiO₂ was demonstrated. The effect of co-catalyst loading on TiO₂ and the nature of the reactor was found to be more significant for H₂ production under direct solar light. The formation of 9.3 nm Cr₂O₃ shell over CuO core in the CuOCr₂O₃ nanostructured co-catalyst was confirmed using transmission electron microscopy. A very high H₂ production rate of 82.39 and 70.4 mmol h^?1 g^?1_cat was observed with quartz and pyrex reactors under direct solar light of irradiation 96–100 mW/cm², respectively. This is almost three times higher than that of bare TiO₂ under similar experimental conditions. The core-shell co-catalyst loaded on TiO₂ by simple mechanical mixing method which is useful for bulk scale synthesis in practical applications. The observed high H₂ production was explained with plausible mechanism where the synergic effect of CuOCr₂O₃ co-catalyst loaded TiO₂ surface that reduces the effective charge carriers recombination and impeded backward reaction by the Cr₂O₃ thin layer. The presence of Cu²⁺ and absence of Cu⁺ and metallic Cu was confirmed using XPS analysis. The effect of co-catalyst loading and sacrificial agent concentration on the photocatalytic hydrogen production was also reported. The stability of the CuOCr₂O₃ core-shell NPs loaded TiO₂ photocatalyst under the direct solar light was examined by continuous cycling for three days and it was found to be 81 and 70% of photocatalyst activity is retained after 3 days in the quartz and pyrex reactor systems, respectively.     

A systematic comparative study of the efficient co-catalyst-free photocatalytic hydrogen evolution by transition metal oxide nanofibers

The efficiencies of a series of hydrogen evolving catalysts based on metal oxide nanofibers (NiO, Co₃O₄, Mn₃O₄) are investigated for the photocatalytic hydrogen evolution from water without using any co-catalyst under the visible light irradiation by using triethanolamine (TEOA) as an electron donor and Eosin-Y (EY) dye as a photosensitizer. It is found that the photocatalytic hydrogen evolution activities follow the order as: Mn₃O₄<Co₃O₄<NiO (196 μmolg^?1h^?1, 5552 μmolg^?1h^?1, 7757 μmolg^?1h^?1, respectively). Moreover, the catalytic behavior of these nanofibers on the hydrogen production has been also compared to bulk forms of NiO, Co₃O₄ and Mn₃O₄ by producing hydrogen 937 μmolg^?1h^?1, 901 μmolg^?1h^?1 and 135 μmolg^?1h^?1, respectively. The nanofiber structures demonstrated much higher photocatalytic activity than bulk forms due to the effect of the increased surface to volume ratio deduced from the fibrous character. The photocatalytic plausible pathway for the hydrogen production is also discussed.     

Selective aerobic oxidation of p-cresol with co-catalysts between metalloporphyrins and metal salts

A green and efficient method for the selective aerobic oxidation of p-cresol to p-hydroxybenzaldehyde catalyzed by co-catalysts between metalloporphyrins and metal salts was investigated and developed. The relationship between the synergistic catalytic effects and the composition as well as amount of co-catalysts was investigated. Moreover, the influence of different reaction conditions was studied in details. A high p-cresol conversion(N 99%) and p-hydroxybenzaldehyde selectivity(83%) were obtained using only 1.125 × 10~(-5) mol T(p-CH_3 O)PPFe~(III)Cl-Co(OAc)_2 used under mild, optimized reaction conditions. A possible mechanism for the reaction was also proposed. This work would be meaningful and instructive for the further researches and applications of co-catalyst system on oxidation of cresols and could give some enlightenment on the selectively catalytic oxidation of the side-chain alkyls of aromatics.     

Investigation into hydrolysis and alcoholysis of sodium borohydride in ethanol–water solutions in the presence of supported Co–Ce–B catalyst

The efficacies of attapulgite clay (ATC)-, titanium dioxide (TiO₂)- and silica gel (SG)-supported cobalt–cerium–boron (Co–Ce–B) substances as catalysts were investigated for the alcoholysis and hydrolysis of sodium borohydride (NaBH₄) in ethanol–water solutions. Ce served as a helpful co-catalyst among the prepared Co–Ce–B catalysts, and the catalytic activity decreased in the following sequence: TiO₂-supported > ATC-supported > SG-supported > unsupported. The effects of Ce/(Co+Ce) molar ratio, ethanol concentration, reaction temperature, NaBH₄ concentration and NaOH concentration on the hydrogen production rate were investigated. For the ATC-supported catalyst, when the Ce/(Co+Ce) molar ratio was 10%, the catalyst exhibited the best catalytic activity. Optimal NaBH₄ concentration, NaOH concentration and ethanol concentration to promote hydrogen generation rate was around 8 wt.%, 15 wt.% and 30 wt.%, respectively. It can be found that the addition of ATC greatly improved the recycle ability of the catalysts in the multi-cycle tests. The surface morphology of the catalysts before and after the recycle tests was studied from SEM images. The compositions of the catalysts were determined by XRD and EDS analyses. The occurrence of NaB(OH)₄ in the alcoholysis by-product provided pertinent indications of ethanol recovery after the tests. The value of activation energy in the hydrogen generation process in the presence of ATC-supported Co–Ce–B catalyst was calculated to be 29.51 kJ/mol. An overall kinetic equation was also proposed.