Chemoselective decarboxylation of ceiba oil to diesel-range alkanes over a red mud based catalyst under H2-free conditions.

Concerns over global greenhouse gas emissions such as CO x and NO x as well as the depletion of petroleum fossil resources have motivated humankind to seek an alternative energy source known as green diesel. In this study, green diesel was produced via a deoxygenation (DO) reaction of ceiba oil under a H2-free atmosphere over Ni modified red mud-based catalysts, which have been synthesized via a precipitation - deep-deposition assisted autoclave method. The obtained catalyst was further characterized by XRF, XRD, BET, FTIR, TPD-NH3, FESEM, and TGA. Based on the catalytic activity test, all Ni/RMO x catalysts facilitated greater DO activity by yielding 83-86% hydrocarbon yield and 70-85% saturated diesel n-(C15 + C17) selectivity. Ni/RMO3 was the best catalyst for deoxygenizing the ceiba oil owing to the existence of a high acidic strength (12717.3 µmol g-1) and synergistic interaction between Fe-O and Ni-O species, thereby producing the highest hydrocarbon yield (86%) and n-(C15 + C17) selectivity (85%). According to the reusability study, the Ni/RMO3 could be reused for up to six consecutive runs with hydrocarbon yields ranging from 53% to 83% and n-(C15 + C17) selectivity ranging from 62% to 83%.

Imidazole-rich copper peptides as catalysts in xenobiotic degradation.

Laccases, oxidative copper-enzymes found in fungi and bacteria were used as the basis in the design of nona- and tetrapeptides. Laccases are known to be excellent catalysts for the degradation of phenolic xenobiotic waste. However, since solvent extraction of laccases is environmentally-unfriendly and yields obtained are low, they are less preferred compared to synthetic catalysts. The histidine rich peptides were designed based on the active site of laccase extracted from Trametes versicolor through RCSB Protein Data Bank, LOMETS and PyMol software. The peptides were synthesized using Fmoc-solid phase peptide synthesis (SPPS) with 30-40% yield. These peptides were purified and characterized using LC-MS (purities >75%), FTIR and NMR spectroscopy. Synthesized copper(II)-peptides were crystallized and then analyzed spectroscopically. Their structures were elucidated using 1D and 2D NMR. Standards (o,m,p-cresol, 2,4-dichlorophenol) catalysed using laccase from Trametes versicolor (0.66 U/mg) were screened under different temperatures and stirring rate conditions. After optimizing the degradation of the standards with the best reaction conditions reported herein, medications with phenolic and aromatic structures such as ibuprofen, paracetamol (acetaminophen), salbutamol, erythromycin and insulin were screened using laccase (positive control), apo-peptides and copper-peptides. Their activities evaluated using GC-MS, were compared with those of peptide and copper-peptide catalysts. The tetrapeptide was found to have the higher degradation activity towards salbutamol (96.8%) compared with laccase at 42.8%. Ibuprofen (35.1%), salbutamol (52.9%) and erythromycin (49.7%) were reported to have the highest degradation activities using Cu-tetrapeptide as catalyst when compared with the other medications. Consequently, o-cresol (84%) was oxidized by Tp-Cu while the apo-peptides failed to oxidize the cresols. Copper(II)-peptides were observed to have higher catalytic activity compared to their parent peptides and the enzyme laccase for xenobiotic degradation.

Production of green diesel from catalytic deoxygenation of chicken fat oil over a series binary metal oxide-supported MWCNTs.

Deoxygenation processes that exploit milder reaction conditions under H2-free atmospheres appear environmentally and economically effective for the production of green diesel. Herein, green diesel was produced by catalytic deoxygenation of chicken fat oil (CFO) over oxides of binary metal pairs (Ni-Mg, Ni-Mn, Ni-Cu, Ni-Ce) supported on multi-walled carbon nanotubes (MWCNTs). The presence of Mg and Mn with Ni afforded greater deoxygenation activity, with hydrocarbon yields of >75% and n-(C15 + C17) selectivity of >81%, indicating that decarboxylation/decarbonylation (deCOx) of CFO is favoured by the existence of high amount of lower strength strong acidic sites along with noticeable strongly basic sites. Based on a series of studies of different Mg and Mn dosages (5-20 wt%), the oxygen free-rich diesel-range hydrocarbons produced efficiently by Ni10-Mg15/MWCNT and Ni10-Mn5/MWCNT catalysts yielded >84% of hydrocarbons, with n-(C15 + C17) selectivity of >85%. The heating value of the green diesel obtained complied with the ultra-low sulphur diesel standard.

Development of bimetallic nickel-based catalysts supported on activated carbon for green fuel production.

In this work, the catalytic deoxygenation of waste cooking oil (WCO) over acid-base bifunctional catalysts (NiLa, NiCe, NiFe, NiMn, NiZn, and NiW) supported on activated carbon (AC) was investigated. A high hydrocarbon yield above 60% with lower oxygenated species was found in the liquid product, with the product being selective toward n-(C15 + C17)-diesel fractions. The predominance of n-(C15 + C17) hydrocarbons with the concurrent production of CO and CO2, indicated that the deoxygenation pathway proceeded via decarbonylation and decarboxylation mechanisms. High deoxygenation activity with better n-(C15 + C17) selectivity over NiLa/AC exposed the great synergistic interaction between La and Ni, and the compatibility of the acid-base sites increased the removal of oxygenated species. The effect of La on the deoxygenation reaction performance was investigated and it was found that a high percentage of La species would be beneficial for the removal of C-O bonded species. The optimum deoxygenation activity of 88% hydrocarbon yield with 75% n-(C15 + C17) selectivity was obtained over 20% of La, which strongly evinced that La leads to a greater enhancement of the deoxygenation activity. The NiLa/AC reusability study showed consistent deoxygenation reactions with 80% hydrocarbon yield and 60% n-(C15 + C17) hydrocarbon selectivity within 6 runs.

Biosensor Based on Tyrosinase Immobilized on Graphene-Decorated Gold Nanoparticle/Chitosan for Phenolic Detection in Aqueous.

In this research work, electrochemical biosensor was fabricated based on immobilization of tyrosinase onto graphene-decorated gold nanoparticle/chitosan (Gr-Au-Chit/Tyr) nanocomposite-modified screen-printed carbon electrode (SPCE) for the detection of phenolic compounds. The nanocomposite film was constructed via solution casting method. The electrocatalytic activity of the proposed biosensor for phenol detection was studied using differential pulse voltammetry (DPV) and cyclic voltammetry (CV). Experimental parameters such as pH buffer, enzyme concentration, ratio of Gr-Au-Chit, accumulation time and potential were optimized. The biosensor shows linearity towards phenol in the concentration range from 0.05 to 15 µM with sensitivity of 0.624 µA/µM and the limit of detection (LOD) of 0.016 µM (S/N = 3). The proposed sensor also depicts good reproducibility, selectivity and stability for at least one month. The biosensor was compared with high-performance liquid chromatography (HPLC) method for the detection of phenol spiked in real water samples and the result is in good agreement and comparable.

Effect of Gelatin-Stabilized Copper Nanoparticles on Catalytic Reduction of Methylene Blue.

The synthesis of copper nanoparticles was carried out with gelatin as a stabilizer by reducing CuSO4.5H2O ions using hydrazine. Ascorbic acid and aqueous NaOH were also used as an antioxidant and pH controller, respectively. The effects of NaOH, hydrazine, and concentration of gelatin as stabilizer were studied. The synthesized copper nanoparticles were characterized by UV-vis spectroscopy, XRD, zeta potential measurements, FTIR, EDX, FESEM, and TEM. The formation of CuNPs@Gelatin is initially confirmed by UV-vis spectroscopic analysis with the characteristic band at 583 nm. XRD and TEM reports revealed that CuNPs@Gelatin (0.75 wt.%) is highly crystalline and spherical in shape with optimum average size of 4.21 ± 0.95 nm. FTIR studies indicated the presence of amide group on the surface of the CuNPs indicating the stability of CuNPs which is further supported by zeta potential measurements with the negative optimum value of -37.90 ± 0.6 mV. The CuNPs@G4 showed a good catalytic activity against methylene blue (MB) reduction using NaBH4 as a reducing agent in an aqueous solution. The best enhanced properties of CuNPs@G4 were found for the 0.75 wt.% gelatin concentration. Thermodynamic parameters (ΔH and ΔS) indicate that under the studied temperature, the reduction of MB by CuNPs@G4 is not feasible and had endothermic in nature.

High Coke-Resistance Pt/Mg1-xNixO Catalyst for Dry Reforming of Methane.

A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50-80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions.

High activity redox catalysts synthesized by chemical vapor impregnation.

The use of precious metals in heterogeneous catalysis relies on the preparation of small nanoparticles that are stable under reaction conditions. To date, most conventional routes used to prepare noble metal nanoparticles have drawbacks related to surface contamination, particle agglomeration, and reproducibility restraints. We have prepared titania-supported palladium (Pd) and platinum (Pt) catalysts using a simplified vapor deposition technique termed chemical vapor impregnation (CVI) that can be performed in any standard chemical laboratory. These materials, composed of nanoparticles typically below 3 nm in size, show remarkable activity under mild conditions for oxidation and hydrogenation reactions of industrial importance. We demonstrate the preparation of bimetallic Pd-Pt homogeneous alloy nanoparticles by this new CVI method, which show synergistic effects in toluene oxidation. The versatility of our CVI methodology to be able to tailor the composition and morphology of supported nanoparticles in an easily accessible and scalable manner is further demonstrated by the synthesis of Pdshell-Aucore nanoparticles using CVI deposition of Pd onto preformed Au nanoparticles supported on titania (prepared by sol immobilization) in addition to the presence of monometallic Au and Pd nanoparticles.

Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles.

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.