Characterization of the performances of an innovative heat-exchanger/reactor

The use of heat exchanger/reactors (HEX/reactors) is a promising way to overcome the barrier of poor heat transfer in batch reactors. However to reach residence time long enough to complete the chemistry, low Reynolds number has to be combined with both a plug flow behaviour and the intensification of heat and mass transfers. This work concerns the experimental approach used to characterize an innovative HEX/reactor. The pilot is made of three process plates sandwiched between five utility plates. The process stream flows in a 2 mm corrugated channel. Pressure drop and residence time distribution characterizations aim at studying the flow hydrodynamics. Identified Darcy correlations point out the transition between laminar and turbulent flow around a Reynolds number equal to 200. Moreover the flow behaves like a quasi-plug flow (Pe > 185). The heat transfer and mixing time have also been investigated. The ratio between the reaction kinetics and the mixing time is over 100 and the intensification factor ranges from 5000 to 8000 kW m⁻³ K⁻¹. As a consequence, no limitations were identified which allows the implementation of an exothermic reaction. It has been successfully performed under severe temperature and concentration conditions, batchwise unreachable. Thus, it highlights the interest of using this continuous HEX/reactor.     

Fiber reinforced mortar affected by alkali-silica reaction: A study by synchrotron microtomography

Alkali-Silica reaction (ASR) is a physicochemical process that can deteriorate concrete and is a recurring engineering problem. In this study three different cylindrical samples affected by ASR were prepared: a plain mortar and two composite mortars containing fibers (polypropylene and a polymer hybrid), which were analyzed at the microtomography (μCT) beamline 8.3.2 at the Advanced Light Source (ALS). In general, three different features were observed during the 136 day observation period: (1) aggregate dissolution, (2) crack propagation from inside the aggregate, through the cement matrix, and at the ITZ, and (3) the alkali-silica gel filling cracks and voids. In addition, accelerated mortar bar tests were utilized to observe ASR's expansive effect in the plain and composite mortars, and the fibers' ability to restrain expansion due to ASR.     

Effects of oxidised linoleic acid on the formation of Nε‐carboxymethyl‐lysine and Nε‐carboxyethyl‐lysine in Maillard reaction system

This study investigated the effects of oxidised linoleic acid (18:2) on N^ε‐carboxymethyl‐lysine (CML) and N^ε‐carboxyethyl‐lysine (CEL) formation in Maillard reaction systems. Model systems of lysine/glucose (L/G), lysine/18:2 (L/18:2), lysine/18:2/glucose (L/18:2/G), myofibrillar protein/glucose (MFP/G), MFP/18:2 and MFP/18:2/G were maintained at 37 °C for 6 weeks. The results showed that CML/CEL contents in L/G (6.99 and 0.96 mmol mol^?1 lysine, respectively) were significantly higher than those in L/18:2/G (1.43 and 0.41 mmol mol^?1 lysine, respectively), and there is a small amount of CML/CEL generation in L/18:2. However, the CML/CEL levels in MFP/G (197.2 and 83.8 ng mg^?1 protein, respectively) were markedly lower than those in MFP/18:2/G (283.2 and 118.5 ng mg^?1 protein, respectively). 18:2 favours the formation of CML/CEL in MFP/18:2/G, not in L/18:2/G. All these findings indicated that the role of 18:2 on CML/CEL formation in Maillard reaction system was complex, and depended on CML/CEL formation rate and substrate types (lysine or lysine residue in protein).     

Acquiring real kinetics of reactions in the inhibitory atmosphere containing product gases using micro fluidized bed

This study proposed an isotope-tagging method to investigate reactions under the atmosphere of product gas. To illustrate this method, the calcination kinetics of calcium carbonate Ca¹³CO₃ in CO₂ atmospheres were investigated by monitoring ¹³CO₂ produced using a micro fluidized bed reaction analyzer (MFBRA). The results demonstrated that the presence of CO₂ in reaction atmosphere increases the apparent activation energy. The increase in the apparent activation energy is, however, significantly overestimated by the thermogravimetric analyzer (TGA) because of the excessive suppression by stagnated product gas inside the sample crucible. Comparatively, the apparent activation energy increases with CO₂ from the MFBRA due primarily to the thermal equilibrium limitation, because the gas diffusion in the MFBRA is essentially eliminated. It is thus concluded that the MFBRA is quite capable of acquiring the real kinetics of reactions in such inhibitory atmospheres.     

Solution blow spun nickel oxide/carbon nanocomposite hollow fibres as an efficient oxygen evolution reaction electrocatalyst

The development of efficient electrocatalysts for slow reaction of the oxygen evolution reaction (OER) is fundamental for viability of the electrochemical water splitting technologies. Here we report for the first time the synthesis of NiO/carbon hollow fibres (NiO-HF) by the Solution Blow Spinning (SBS) technique, and a study of their catalytic activity towards the OER in alkaline medium. The hollow fibres were obtained with ca. 300 nm in diameter consisting of agglomerated NiO nanoparticles with an average size of 50 nm which is close to the tubular wall thickness. The formation mechanism of the hollow structure was discussed. It was revealed that the carbon from polyenic branch of polyvinylpyrrolidone (PVP) resists the firing treatment and acts as an agglomerating agent, thus ensuring a conductive and percolating path between NiO nanoparticles along the fibres. A battery of electrochemical tests of NiO-HF supported by commercial Ni foam reveals excellent electrochemical activity for OER in 1 M KOH, in comparison with reference NiO nanoparticles (NiO-NP, diameter ca. 23 nm). NiO-HF attains an overpotential of 340 mV vs. RHE at a current density of 10 mA cm⁻², which is amongst the lowest values reported in the literature for undoped NiO. Chronopotentiometry reveals stable NiO-HF electrodes over 15 h under an electrolysis current of 25 mA cm⁻². Microscopic analysis shows that the fibrillar morphology is completely preserved after the electrolysis test. The remarkable performance of the NiO-HF catalyst is ascribed to the enhanced electronic conductivity resulting from the interpenetrating NiO-HF/carbon microstructure.     

Recent progress of anode catalysts and their support materials for methanol electrooxidation reaction

This review paper summarizes the recent progress of anode catalysts for methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs). The electrocatalytic activities of the noble and noble-free catalysts in different electrolyte media are compared and discussed. Noble-free catalysts exhibit high activity in alkaline medium, whereas Pt-based catalysts are the most active MOR catalysts in acidic medium. The types of catalyst support materials for DMFC anodes are also discussed and further divided into carbonaceous and non-carbonaceous materials. The ion and electron transport through the support materials and their effects on the overall performance are elaborated. Lastly, this paper highlights the major challenges in achieving the optimum DMFC performance from the aspect of tailoring the properties of MOR electrocatalysts to pave its way for commercialisation.     

Highly active and stable bi-functional NiCoO2 catalyst for oxygen reduction and oxygen evolution reactions in alkaline medium

Single step solution combustion technique was used to synthesize NiO, Co₃O₄ and NiCoO₂ mixed metal oxide with good crystallinity and uniform properties. XRD spectrum indicates the existence of cubic NiCoO₂ phase without any impurities. SEM results indicate the presence of porous structures in all the three cases, a typical characteristic of combustion synthesized samples, which is due to the evolution of gases during the synthesis process. TEM along with the phase mapping shows the presence of well dispersed elements Ni, Co and O throughout the sample. All the three catalysts were evaluated for their bifunctionality towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline medium. NiCoO₂ shows the highest number of electron transfer in the overall reaction mechanism with the maximum kinetic current density of 12.3 mA/cm². The kinetics of NiCoO₂ towards ORR and OER was analyzed using Tafel plot and compared with the mono-metal oxides. The catalytic stability was evaluated for 24 h using continuous chronoamperometric (CA) runs, where NiCoO₂ shows exceptionally stable performance without any significant decay in current. The highest activity of NiCoO₂ could be due to the presence of higher oxidation states of Ni and Co and because of the existence of the oxygen defects acting as active sites for the oxygen adsorption/desorption during the electrocatalytic reactions. Based on the activity and stability trends, NiCoO₂ is found to be a promising bifunctional oxygen electrocatalyst for long-term applications.     

Ultrathin MoSSe alloy nanosheets anchored on carbon nanotubes as advanced catalysts for hydrogen evolution

The activity of transition metal dichalcogenides (TMD) toward hydrogen evolution reaction (HER) derives from the active sites at the edges, but the basal surface still remain catalytic insert. Herein, ultrathin MoSSe alloy nanosheets array on multiwalled carbon nanotubes (MWCNTs) to form a core shell structure via a simple solvothermal process. These three-dimensional (3D) MoSSe hybrids show a high activity in hydrogen evolution reaction (HER) with a small Tafel slope of 38 mV dec⁻¹ and a low overpotential of 102 mV at 10 mA cm⁻². In addition, their HER activity remains remarkably stable without significant decay after 100 h polarization. Such superior catalytic HER activity springs from the 3D hierarchical heterostructure, which is abundant of catalytic edge sites, and the alloy effect between S and Se, which will create huge defects and strain to form vacancy sites on the basal plane. This strategy may open a new avenue toward the development of nonprecious high-performance HER catalysts.     

Spinel CoFe2O4 supported by three dimensional graphene as high-performance bi-functional electrocatalysts for oxygen reduction and evolution reaction

Spinel CoFe₂O₄ supported on three dimensional graphene (3DG) is prepared by hydrothermal reaction, which is denoted as CoFe₂O₄/3DG. The 3DG is prepared by the templated method, where coal tar pitch (CTP) and MgO are used as the carbon source and the template, respectively. The microstructure and composition of the resultant have been investigated by X-ray diffraction as well as X-ray photoelectron spectroscopy indicating the formation of spinel CoFe₂O₄ and composite of CoFe₂O₄/3DG. The multilayer structure of 3DG and CoFe₂O₄/3DG is also examined by the Raman spectra. Electrochemically, CoFe₂O₄/3DG shows high-performance half-wave potential is 0.80 V vs. RHE in O₂-saturated 0.1 M KOH, which is compared to 20 wt% Pt/C. When evaluated for OER activity, CoFe₂O₄/3DG obtains a low overpotential 1.63 V vs. RHE (at j = 10 mA cm⁻²), which is 180 mV better than 20 wt% Pt/C. Moreover, it possesses excellent durability superior to 20 wt% Pt/C.     

N,P-co-doped carbon coupled with CoP as superior electrocatalysts for hydrogen evolution reaction and overall water splitting

To achieve high activity and stability for both hydrogen and oxygen evolution reactions through the non-precious-metal based electrocatalysts is still facing the great challenge. Herein, we demonstrate a facile strategy to prepare CoP nanoparticles (NPs) loaded on N, P dual-doped carbon (NPC) electrocatalysts with high concentration N and P dopants through a pyrolysis-deposition-phosphidation process. The great bifunctional electrocatalytic activity for both HER (the overpotential of 98 mV and 86 mV at 10 mA cm⁻² in both 0.5 M H₂SO₄ and 1 M KOH electrolytes, respectively) and OER (the overpotential of 300 mV at 10  mA cm⁻² in 1 M KOH electrolyte) were achieved. When CoP@NPC hybrid was used as two electrodes in the 1 M KOH electrolyte system for overall water splitting, the needed cell potential for achieving the current density of 10 mA cm⁻² is 1.6 V, and it also showed superior stability for HER and OER after 10 h’ test with almost negligible decay. Experimental results revealed that the P atoms in CoP were the active sites for HER and the CoP@NPC hybrid showed excellent bifunctional electrocatalytic properties due to the synergistic effects between the high catalytic activity of CoP NPs and NPC, in which the doping of N and P in carbon led to a stronger polarization between Co and P in CoP, promoting the charge transfer from Co to P in CoP, enhancing the catalytic activity of P sites and Co sites in CoP for HER and OER, respectively. Specifically, the improvements could result from the changed charge state, the increased active specific surface area, and the facilitated reaction kinetics by N, P co-doping and admixture. This work provides a high-efficient, low-cost and stable electrocatalyst for overall water splitting, and throws light on rational designing high performance electrocatalysts.