A high-throughput chaotic advection microreactor for preparation of uniform and aggregated barium sulfate nanoparticles

A high-throughput (105.5 g/h) passive four-stage asymmetric oscillating feedback microreactor using chaotic mixing mechanism was developed to prepare aggregated Barium sulfate (BaSO₄) particles of high primary nanoparticle size uniformity. Three-dimensional unsteady simulations showed that chaotic mixing could be induced by three unique secondary flows (i.e., vortex, recirculation, and oscillation), and the fluid oscillation mechanism was examined in detail. Simulations and Villermaux–Dushman experiments indicate that almost complete mixing down to molecular level can be achieved and the prepared BaSO₄ nanoparticles were with narrow primary particle size distribution (PSD) having geometric standard deviation, σ_g, less than 1.43 when the total volumetric flow rate Q_total was larger than 10 ml/min. By selecting Q_total and reactant concentrations, average primary particle size can be controlled from 23 to 109 nm as determined by microscopy. An average size of 26 nm with narrow primary PSD (σ_g = 1.22) could be achieved at Q_total of 160 ml/min.     

Co?N graphene encapsulated cobalt catalyst for H2O2 decomposition under acidic conditions

Hydrogen peroxide (H₂O₂) has been listed as one of the 100 most important chemicals in the world. However, huge amount of residual H₂O₂ is hard to timely decomposed into O₂ and H₂O under acidic condition, easily resulting in explosion hazard. Here, we reported a core–shell structure catalyst, that is graphene with Co N structure encapsulated Co nanoparticles. Co N graphene shell serves as the active site for the H₂O₂ decomposition, and Co core further enhance this decomposition. Benefiting from it, the H₂O₂ decomposition were close to 100% after 6 cycles without pH adjustment, which increased 6 orders of magnitude compared with no catalyst. At the same time, the O₂ generation reached 99.67% in 2 h with little metal leaching, and ·OH has been greatly inhibited to only 0.08%. This work can cleanly remove H₂O₂ with little deep oxidation and protect the process of H₂O₂ utilization to achieve a safer world.     

A kinetic model involving oxidation and volatilization in SiC-B4C-xAl2O3 ceramics system

In this paper, a new kinetic model considering both oxidation and volatilization kinetics is established and applied to analyze the oxidation of SiC-B₄C-xAl₂O₃ ceramics and other systems in various oxidation conditions. The effects of diffusion area and volume changes during the oxidation process are considered in this model. The physical meaning of each parameter in this model is explicit and simple. According to this model, the diffusion coefficient of species and the corresponding diffusion activation energy are easily available. The practicability of this model is well verified by the experimental data of SiC-B₄C-xAl₂O₃ and other systems oxidized under different conditions. In addition, the practice shows that the model is applicable not only to the systems where oxidation and volatilization coexist, but also to the system where only oxidation plays a major role. We hope the model proposed in this work can be used in other materials with more complex environments.     

Self-construction of pea-like Cu/Cu2S Mott-Schottky electrocatalyst for the oxygen evolution reaction

The speed of the oxygen evolution reaction seriously affects the hydrogen production efficiency of water electrolysis. Hence it is crucial to develop efficient and durable OER electrocatalysts. Construction of heterojunction catalysts is also one of the strategies to develop efficient catalysts. In this paper, a pea-like Cu/Cu₂S–C3 Mott?Schottky electrocatalyst was self-constructed by vapor deposition, while CF (copper foam) was used as substrate material and copper source, and thiourea was served as sulfur source. The built-in electric field is formed at the metal-semiconductor interface, which endows it with promising electrocatalytic performance. As the working electrode, the overpotentials of Cu/Cu₂S–C3 required to reach the current density of 10 and 50 mA cm^?2 were about 170 and 335 mV. The impact of the Mott-Schottky structure on the catalyst was also reflected in stability. The i-t tests of the sample Cu/Cu₂S–C3 were carried out under 10 and 60 mA cm^?2 and performed well.     

Application of piezoelectric quartz for self-cleaning membrane preparation

Separation membranes that are prepared from piezoelectric ceramics can generate ultrasound on-line to maintain surface cleanliness. Here, a lead-free piezoelectric support is presented consisting of quartz. The Na₂O and Al₂O₃ were employed as sintering aids to improve the mechanical performance of piezoelectric quartz support while avoid the formation of no-piezoelectric cristobalite. A ZrO₂-based thin microfiltration membrane layer was applied on the optimized support. The membrane structure, thus obtained had an average pore size and ultrasonic emission of 270 nm and 5.1 mV, respectively. The stationary permeance of the membrane in the treatment of oil-in-water emulsion was 163 L m^?2?h^?1?bar^?1 (LMH/bar). With the application of alternating voltages of 60 V and 100 V, the permeance increased to 198 and 225 LMH/bar, respectively, and the oil rejection was maintained above 97%. The in-situ ultrasound directly acted on membrane surface, so it removed more fouling resistance at lower power than the external one.     

Spin-state regulating of cobalt assisted by iron doping and coordination for enhanced oxygen evolution reaction

Customizing catalysts from the electronic structure, such as spin state, is an effective but challenging strategy for oxygen evolution reaction (OER). Herein, an ultrafine Co–Fe material highly dispersed on nitrogen carbide matrix is fabricated by coordination polymer and self-templating method to scrutinize the impact of spin state of Co on OER through Fe doping. The optimized catalyst shows boosted OER performance, which only requires overpotential of 333 mV at 10 mA cm^?2, outperforming other control samples and commercial RuO₂. The elevated local spin states of Co by Fe doping lead to charge transfer acceleration and fast generation of oxygenated intermediates, which is proved to account for the OER elevation. In addition, the long-term stability of Co–Fe material is guaranteed by the strong coordination of Co/Fe to the melamine-formaldehyde resin, which is used to adsorb metal ions, contributing to the high dispersion of active sites during the OER process.     

Self-optimized and renewable Ni–Co alloy@Co–Co2C catalyst for higher alcohols synthesis from syngas

Higher alcohols synthesis (HAS) from syngas (CO/H₂) has attracted widespread attention, while the low selectivity and poor stability of the catalysts mainly stumbled its industrial application. In the work, Ni–Co alloy nanoparticles (NPs) derived from Co_1-xNi_xAl₂O₄ loaded on the SiO₂ with large specific surface area were prepared; and during reaction, the highly dispersed Ni–Co alloys were self-optimized to Ni–Co alloy@Co–Co₂C. Importantly, Ni–Co alloy@Co–Co₂C can be regenerated through oxidation - reduction - self-optimization process. Characteristic results indicated that the structural liberalization during the reaction process inhibited the loss of Ni, regulated and balanced the dual active sites of the catalyst and the Ni–Co alloys were regenerated after the re-oxidation and re-reduction process. The optimized catalyst exhibited excellent catalytic performance, including a high total selectivity to alcohols of 39.3% and an excellent catalytic stability at 250 °C, 3.5 MPa (H₂/CO = 2) and a space velocity of 6000 mL (g_cat h)^?1. In addition, the Ni–Co alloy@Co–Co₂C catalyst after stability test could recover its original catalytic performance after re-oxidation and re-reduction. The renewable characteristics and superior catalytic performance of Ni–Co alloy@Co–Co₂C made the catalyst to be one of the potential industrial catalysts for HAS.     

Scalloped nickel/iron vanadium oxide-coated vanadium dioxides based on chemical etching-induced reconstruction strategy for efficient oxygen evolution

Developing highly efficient and stable noble metal-free electrocatalysts with excellent catalytic surface for oxygen evolution reactions (OER) is an essential link for stimulating hydrogen generation from water electrolysis. Herein, the scalloped nickel/iron vanadium oxide coated vanadium dioxide (named as VO₂@NFVO) has been successfully decorated via a urea-induced chemical etching-reconstruction process in the alkaline solution containing Fe²⁺ and Ni²⁺. Corresponding experimental measurements clearly show that favorable chemical etching occurs with the formation of new phases (eg, Ni₃V₂O₈, FeVO₄), which make it expose a large number of active sites and regulate the electron density of the active center, thus thereby dramatically enhancing the electrocatalytic performance by promoting electron transfer and optimizing the adsorption energy of reaction intermediates. Under optimized condition, the obtained VO₂@NFVO delivers excellent activity merely with smaller overpotential of 290 mV at 10 mA cm^?2, outperforming benchmark RuO₂ catalyst in an alkaline solution. Moreover, its superior durability is verified by chronoamperometry testing. This simple etching-reconstruction strategy opens a new avenue for the preparation of vanadium-based electrocatalysts.     

A Ti3C2Tx-carbon black-acrylic epoxy coating for 304SS bipolar plates with enhanced corrosion resistant and conductivity

A conducting and anticorrosive coating is crucial for the application of metal bipolar plates (BP) in proton exchange membrane fuel cell (PEMFC). In this work, a Ti₃C₂T_x (T)-carbon black (C)-acrylic epoxy (AE) coating is prepared on 304 stainless steel (SS) with enhanced corrosion resistance and conductivity. The corrosion resistance of the T-C-AE coating is investigated in a 0.5 M H₂SO₄ solution as compared to the AE, T, and T-AE coatings. The T-C-AE coated 304SS exhibits the strongest corrosion resistance with the most positive corrosion potential and the lowest corrosion current density of 0.00673 μA cm^?2 in all the samples, while retaining intact and compact surface morphology with the lowest metal ion dissolution even after immersed for 720 h. The addition of Ti₃C₂T_x and carbon black into the AE matrix greatly decreases interfacial contact resistance (ICR), and the T-C-AE coating achieves a low ICR of 15.5 mΩ cm^?2 under 140 N cm^?2 compaction force. The excellent anticorrosion performance is mainly attributed to the physical barrier and the cathodic protection provided by the stacked Ti₃C₂T_x (MXene) nanosheets in the T-C-AE coating. This eco-friendly, conducting, and anticorrosive T-C-AE coating has a good application prospect on SS BP of PEMFC.     

Simply constructed highly dispersed cobalt nanoparticles in diverse N-doped graphitic carbon with remarkable performances for water electrolysis

Metal/carbon composite materials are highly promising electrocatalysts for water electrolysis. In this work, three composites of metal cobalt nanoparticles highly dispersed in N-doped carbon materials were facilely constructed by pyrolysis of different phenylenediamine based Schiff base-Co complexes (PDBs). Interestingly, the composites derived from PDBs based on different phenylenediamine exhibited different morphologies. The superior case is that rodlike composite catalyst was derived from o-phenylenediamine based PDBs. The obtained catalyst exhibited remarkable performances for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER), as well as overall water electrolysis. Only 172 and 289 mV of overpotentials and 1.57 V of cell voltage were exhibited at 10 mA cm^?2 for HER, OER and water splitting in 1.0 M KOH, respectively. The catalyst also displayed robust stability and high Faraday efficiency, and thus are potential high-performance catalyst for commercial water electrolysis.