Engineering biphasic hybrid phosphide nanowires as efficient electrocatalyst for hydrogen evolution reaction: Experimental and theoretical insights

Development of highly efficient and cheap electrocatalysts towards the hydrogen evolution reaction (HER) is of great importance for electrochemical water splitting. Herein, hybrid Cu/NiMo-P nanowires on the copper foam were successfully fabricated via a simple two-step method. The hierarchically structured Cu/NiMo-P exhibits large surface areas and rapid electron transfer ability, leading to enhanced catalytic activity. The as-prepared Cu/NiMo-P electrodes need overpotentials of 34 mV and 130 mV to obtain 10 mA cm^?2 for HER in acidic and alkaline solutions, respectively. Density functional theory (DFT) calculations reveal that the Cu/NiMo-P hybrid has a more thermo-neutral hydrogen adsorption free energy and enhanced charge transfer ability as well.     

Removal of lead(Pb(Ⅱ))and zinc(Zn(Ⅱ))from aqueous solution using coal fly ash(CFA)as a dual-sites adsorbent

Coal fly ash(CFA)is composed of minerals containing some oxides in crystalline phase(i.e.,quartz and mullite),as well as unburned carbon as mesoporous material,thus enabling CFA to act as a dual-sites adsorbent with unique properties.This work focused on the adsorption of Pb(Ⅱ)and Zn(Ⅱ)from binary system,a mixture containing two metal ion solutions present simultaneously,onto NaOH-modified CFA(MCFA).Several adsorption tests were conducted to evaluate the effect of several parameters,includ-ing pH and contact times.The experiment results indicated that chemical treatment of CFA with NaOH increased pore volume from 0.021 to 0.223 cm3 g-1.In addition,it could also enhance the availability of functional groups on both minerals and unburned carbon,resulting in almost 100％Pb(Ⅱ)and 97％Zn(Ⅱ)adsorbed.The optimum pH for adsorption system was pH=3 and quasi-equilibrium occurred in 240 minutes.Equilibrium data from the experimental results were analyzed using Modified Extended Langmuir(MEL)and Competitive Adsorption Langmuir-Langmuir(CALL)isotherm models.The analysis results showed that the CALL isotherm model could better describe the Pb(Ⅱ)and Zn(Ⅱ)adsorption pro-cess onto MCFA in binary system compared with MEL isotherm model.     

Olive mill wastewaters decontamination based on organo-nano-clay composites

Green composites for environmental applications were successfully prepared by intercalation of the biosurfactant Quillaja saponin onto montmorillonite mineral clay on varying pH and surfactant/clay ratio. Equilibrium adsorption isotherms were constructed and the system was characterized by performing TGA and XRD analyses.The efficiency of the surfactant-modified clay in the removal of the organic content present in olive mill wastewaters (OMW) was evaluated by means of spectrophotometric measurements. The interest for this cogent issue comes from the consideration that, despite their high pollutant content, OMW can be considered as a potential resource of several organic compounds which can be recovered for a wide array of pharmaceutical and industrial applications. Two different strategies were proposed. In the first one, dried surfactant/clay hybrids were added to the batch samples under continuous stirring, while in the second alternative approach the organoclays were packed in chromatography column filled with multiple alternate layers of sand and organoclay.These studies revealed the efficacy of the methods used and suggested that the modification of the montmorillonite clay substrate significantly improves the performance of the clay.     

Facile fabrication of graphene oxide-polyethylenimine composite and its application for the Cr(VI) removal

A binary composite consisting of graphene oxide (GO) and polyethylenimine (PEI) was fabricated by a facile physical mixing. Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FE-SEM), thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and Zeta potential were used to characterize the prepared graphene oxide-polyethylenimine composite (GOPC). A series of experiments were carried out to investigate the effects of some important parameters, such as molecular weight of PEI, pH, time and temperature, on the adsorption efficiency of GOPC. Due to the high amine density of GOPC, its adsorption for Cr(VI) occurred more easily at lower pH mainly via electrostatic interaction. The adsorption process matched well with the Langmuir isotherm model and the pseudo-second-order kinetic model. The maximum adsorption capacity from the Langmuir model was 370.37 mg/g at pH 2.0 and 45°C for GOPC. Thermodynamic parameters revealed spontaneous and endothermic nature of the Cr(VI) adsorption onto GOPC. The main adsorption mechanism of GOPC toward Cr(VI) was electrostatic interaction. The adsorption-desorption experiments suggested GOPC was easily recycled and its stable adsorption capacity endowed it great potential as an adsorbent of Cr(VI) from wastewater.     

Immobilization of surface non-affinitive protein onto a metal surface by an external electric field

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Cold-start performance of an ammonia-fueled spark ignition engine with an on-board fuel reformer

This work demonstrated the first-ever cold-start operation of an ammonia (NH₃)-fueled four-cylinder spark ignition engine with an on-board fuel reformer, applying autothermal reforming. In this system, an electrically heated NH₃-air mixture was provided to a reforming catalyst and approximately 3 s was found to elapse between the start of engine rotation and the onset of combustion. Stable fast idle operation in conjunction with a cold start was realized with a H₂-to-NH₃ molar ratio of 2:1. Nearly zero NH₃ emissions were achieved during cold start and fast idle until the engine warmed up, by adsorbing unburned NH₃ passing through a three-way catalyst before the catalyst was sufficiently warmed up. The NH₃ adsorption capacity of this system could be regenerated during the engine warm-up when the engine was running under lean conditions.     

Hydrogen adsorption of O/N-rich hierarchical carbon scaffold decorated with Ni nanoparticles: Experimental and computational studies

Hierarchical carbon scaffold (HCS) with multi-porous structures, favoring hydrogen diffusion and physisorption is doped with 2–10 wt % Ni for storing hydrogen at ambient temperature. Due to N- and O-rich structure of melamine-formaldehyde resin used as carbon precursor, homogeneous distribution of heteroatoms (N and O) in HCS is achieved. 2 wt % Ni-doped HCS shows the highest hydrogen capacity up to 2.40 wt % H₂ (T = 298 K and p (H₂) = 100 bar) as well as excellent reversibility of 18.25 g H₂/L and 1.25 wt % H₂ (T = 298 K and p (H₂) = 50 bar) and electrical production from PEMFC stack up to 0.7 Wh upon eight cycles. Computations and experiments confirm strong interactions between Ni and heteroatoms, leading to uniform distribution small particles of Ni. This results in enhancing reactive surface area for hydrogen adsorption and preventing agglomeration of Ni nanoparticles upon cycling. Ni K-edge XANES spectra simulated from the optimized structure of Ni-doped N/O-rich carbon using DFT calculations are consistent with the experimental spectra and suggest electron transfer from Ni to hydrogen to form Ni–H bond upon adsorption. Considering low desorption temperature (323 K), not only chemisorbed hydrogen is involved in adsorption mechanisms but also physisorption and spillover of hydrogen.     

Amination of biochar surface from watermelon peel for toxic chromium removal enhancement

Watermelon peel residues were used to produce a new biochar by dehydration method. The new biochar has undergone two methods of chemical modification and the effect of this chemical modification on its ability to adsorb Cr(VI) ions from aqueous solution has been investigated. Three biochars, Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, were made from watermelon peel via dehydration with 50% sulfuric acid to give Melon-B followed by oxidation with ozone and amination using ammonium hydroxide to give Melon-BO-NH_2 or Triethylenetetramine(TETA) to give Melon-BO-TETA. The prepared biochars were characterized by BET, BJH,SEM, FT-IR, TGA, DSC and EDAX analyses. The highest removal percentage of Cr(VI) ions was 69% for Melon-B,98% for Melon-BO-NH_2 and 99% for Melon-BO-TETA biochars of 100 mg·L~(-1) Cr(VI) ions initial concentration and 1.0 g·L~(-1) adsorbents dose. The unmodified biochar(Melon-B) and modified biochars(Melon-BO-NH_2 and Melon-BO-TETA) had maximum adsorption capacities(Qm) of 72.46, 123.46, and 333.33 mg·g~(-1), respectively.The amination of biochar reduced the pore size of modified biochar, whereas the surface area was enhanced.The obtained data of isotherm models were tested using different error function equations. The Freundlich,Tempkin and Langmuir isotherm models were best fitted to the experimental data of Melon-B, Melon-BO-NH_2 and Melon-BO-TETA, respectively. The adsorption rate was primarily controlled by pseudo-second–order rate model. Conclusively, the functional groups interactions are important for adsorption mechanisms and expected to control the adsorption process. The adsorption for the Melon-B, Melon-BO-NH_2 and Melon-BO-TETA could be explained for acid–base interaction and hydrogen bonding interaction.     

Amino-functionalized magnetic bacterial cellulose/activated carbon composite for Pb2+ and methyl orange sorption from aqueous solution

A new nanostructured amino-functionalized magnetic bacterial cellulose/activated carbon(BC/AC)composite bioadsorbent(AMBCAC)was prepared for removal of Pb~(2+)and methyl orange(MO)from aqueous solution.The results demonstrated that the equilibrium adsorption capacity(q_e)for Pb~(2+)obviously increases by 2.14 times after introduction of amino groups,the optimum p H for Pb~(2+)and MO adsorption was 5.0 and 3.0,respectively,and the q_eof AMBCAC was 161.78 mg g~(-1)for Pb~(2+)and 83.26 mg g~(-1)for MO under the optimal conditions in this investigation.The kinetics and adsorption isotherm data of the sorption process were well fitted by pseudo-second-order kinetic model and Langmuir isotherm respectively.The thermodynamic results(the Gibbs free energy change G0,the enthalpy change H0,the entropy change S0)implied that the adsorption process of Pb~(2+)and MO was feasible,endothermic and spontaneous in nature.These results support that the AMBCAC composite developed in this work can provide a cheap and efficient way for easy removal of both Pb~(2+)and MO as a promising adsorbent candidate for wastewater treatment.