Search

As a high-active metal-free electrocatalyst for NH 3 production via NO reduction reaction, honeycomb carbon nanofiber achieves an NH 3 yield of 22.35 μmol h−1 cm−2 with a high Faradaic efficiency of 88.33%. [Display omitted] Electrocatalytic NO reduction is a promising technology for ambient NO removal with simultaneous production of highly value-added NH 3. Herein, we report that honeycomb carbon nanofiber coated on carbon paper acts as an efficient metal-free catalyst for ambient electroreduction of NO to NH 3. In 0.2 M Na 2 SO 4 solution, such catalyst achieves an NH 3 yield of 22.35 μmol h−1 cm−2 with a high Faradaic efficiency of up to 88.33%. Impressively, it also shows excellent stability for 10-h continuous electrolysis. Theoretical calculations reveal that the most active center of functional groups is –OH group for NO reduction with a low energy barrier (ΔG of 0.29 eV) for the potential-determining step (*NO + H → *HNO). [ABSTRACT FROM AUTHOR]

[Display omitted] Engineering platinum-free catalysts for hydrogen evolution reaction (HER) with high activity and stability is essential for electrochemical hydrogen production. In this paper, we report the synthesis of cobalt-doped AlNi 3 /NiO (Co-AlNi 3 /NiO) electrode with three-dimensional nanoporous structure via chemical dealloying method. Density functional theory (DFT) calculations reveal that Co-AlNi 3 /NiO can accelerate water adsorption / dissociation and optimize adsorption–desorption energies of H* intermediates, thus improving the intrinsic HER activity. Both the introduction of Co and Al can efficiently ameliorate the electronic density around Ni sites of NiO and AlNi 3 , which can effectively reduce the energy barrier towards Volmer–Heyrovsky reaction and thus synergistically promote the hydrogen evolution. Benefiting from the large electrochemical active surface area, high electrical conductivity and electronic effect, the nanoporous Co-AlNi 3 /NiO catalyst exhibits remarkable HER activity with an overpotential of 73 mV at a current density of 10 mA cm−2 in alkaline condition, outperforming most of the reported non-precious metal catalysts. The nanoporous Co-AlNi 3 /NiO catalyst can operate continuously over 1000 h at high current densities with a robust stability. This work provides a new vision for the development of low-cost and efficient electrocatalysts for energy conversion applications. [ABSTRACT FROM AUTHOR]

Pb SA -Cu/PC with a three-dimensional structure was demonstrated as an efficient CO 2 reduction catalyst to formate. Pb inhibited the formation of COOH*, reduced the energy barrier of rate determining step in the formate formation process, and achieved 97% high formate selectivity. [Display omitted] • Pb SA100 -Cu/CP catalyst is developed by an economical and low-energy method. • The FE formate is 97 % with a partial current density of 27.9 mA cm−2 at − 0.9 V. • The catalyst exhibits ultra-long stability for more than 60 h. • The synergistic action of Pb SA and Cu atoms lowers the RDS for CO 2 RR to fromate. • Single-atom Pb induces Cu charge redistribution and inhibits the formation of COOH*. Exploring highly selective and stable electrocatalysts is of great significance for the electrochemical conversion of CO 2 into fuel. Herein, a three-dimensional (3D) nanostructure catalyst was developed by doping Pb single-atom (Pb SA) in-situ on carbon paper (Pb SA100 -Cu/CP) through a low-energy and economical method. The designed catalyst exhibited abundant active sites and was beneficial to CO 2 adsorption, activation, and subsequent conversion to fuel. Interestingly, Pb SA100 -Cu/CP showed a prominent Faraday efficiency (FE) of 97 % at –0.9 V versus reversible hydrogen electrode (vs. RHE) and a high partial current density of 27.9 mA·cm−2 for formate. Also, the catalyst remained significantly stable for 60 h during the durability test. The reaction mechanism was investigated by density functional theory (DFT), demonstrating that the doping Pb SA induced the electrons redistribution, promoted the formate generation, reduced the rate-determining step (RDS) energy barrier, and inhibited the hydrogen evolution reaction. The study aims to provide a new strategy for developing of single-atom catalysts with high selectivity and stability, which will help reduce environmental pressure and alleviate energy problems. [ABSTRACT FROM AUTHOR]

[Display omitted] The 2H-MoS 2 /nitrogen-doped carbon (2H-MoS 2 /NC) composite is a promising anode material for potassium-ion batteries (PIBs). Various transition metal doping has been adopted to optimize the poor intrinsic electronic conductivity and lack of active sites in the intralayer of 2H-MoS 2. However, its optimization mechanisms have not been well probed. In this paper, using Cobalt (Co) as an example, we aim to investigate the influence of transition metal doping on the electronic and mechanical properties and electrochemical performance of 2H-MoS 2 /NC via first-principles calculation. Co doping is found to be effective in improving the electronic conductivity and the areas of active sites on different positions (C surface, interface, and MoS 2 surface) of 2H-MoS 2 /NC. The increased active sites can optimize K adsorption and diffusion capability/processes, where general smaller K adsorption energies and diffusion energy barriers are found after Co doping. This helps improve the rate performance. Especially, the pyridinic N (pyN), pyrrolic N (prN), and graphitic N (grN) are first unveiled to respectively work best in K kinetic adsorption, diffusion, and interfacial stability. These findings are instructive to experimental design of high rate 2H-MoS 2 /NC electrode materials. The roles of different N types provide new ideas for optimal design of other functional composite materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • The carbonized recycled melamine sponge obtained excellent low-cost porous matrix. • FeNi@NCS shows lower reaction potential and higher electron transfer ability on UOR. • Successfully assembled the DBHPFC using urine as fuel. • DUHPFC presents excellent open circuit voltage. The direct urea fuel cell (DUFC) is a power generation equipment with urea-rich wastewater or urine as fuel source. It has the unique ability to purify sewage while simultaneously generating electricity, making it a highly efficient and environmentally friendly option. In this paper, pomegranate seed-like Ni nano-blocks and Fe nanosheets were synthesized by electrodeposition and chemical reduction and attached to the carbonized melamine sponge matrix. The N -doped carbon sponge (NCS) provided a large number of polyhedral holes, which allowed for efficient gas escape through channels. The combination of Fe reduces the initial urea oxidation potential, reaction activation energy and reaction resistance. The synthesized FeNi supported on N -doped carbon sponge composite (FeNi@NCS) has a catalytic current density of 625 mA cm−2 and a Tafel slope of 42.51 mV dec−1 for urea electrooxidation reaction (UOR). Assembling the direct urine-hydrogen peroxide fuel cell (DUrHPFC) resulted in the highest performance output. The open circuit voltage (OCV) was 0.98 V, and the peak power density reached 9.61 mW cm−2. The results show that the prepared catalyst provides an opportunity to solve the problems that hinder the development of urea green cycle at present. [ABSTRACT FROM AUTHOR]

[Display omitted] Photocatalysis provides a new way for synchronous H 2 production and organic synthesis at normal temperature and pressure, usually, water and organic substrate function as sources of hydrogen protons and organic products, which are complex and limited by two half-reactions. Employing alcohols as reaction substrates to simultaneously produce H 2 and valuable organics in a redox cycle is worthy studying, to which catalyst design at atomic level holds the key. In this paper, Co elements doped Cu 3 P (CoCuP) quantum dots (QDs) are prepared and coupled with ZnIn 2 S 4 (ZIS) nanosheets to form a 0D/2D p-n nanojunction which can effectively boost aliphatic and aromatic alcohols activation to simultaneously produce H 2 and corresponding ketones (or aldehydes). The optimal CoCuP/ZIS composite demonstrated the highest activity for dehydrogenation of isopropanol to acetone (17.77 mmol⋅g−1⋅h−1) and H 2 (26.8 mmol⋅g−1⋅h−1), which was 2.40 and 1.63 times higher than that of Cu 3 P/ZIS composite, respectively. Mechanistic investigations revealed that such high-performance originated from the accelerated electron transfer of the formed p-n junction and the thermodynamic optimization caused by the Co dopant which was the active site of oxydehydrogenation as a prerequisite step for isopropanol oxidation over the surface of the CoCuP/ZIS composite. Besides that, coupling of the CoCuP QDs can lower the dehydrogenation activation energy of isopropanol to form a key radical intermediate of (CH 3) 2 CHO* for improving the activity of simultaneous production of H 2 and acetone. This strategy provides an overall reaction strategy to obtain two meaningful products (H 2 and ketones (or aldehydes)) and deeply explores the integrated redox reaction of alcohol as substrate for high solar-chemical energy conversion. [ABSTRACT FROM AUTHOR]

[Display omitted] In emulsification-polymerisation avoiding monomer escape from emulsion droplets is the key to successful encapsulation. So far, it is believed that (1) a hydrophobe needs to be included and (2) free-micelles of surfactant need to be depleted. However, these criteria do not always work. The paper explores the critical role of the chemical potential difference between the inside and outside of the emulsion droplet for successful encapsulation. Crossflow membrane emulsification was used to produce uniform droplets of 1–2 µm of solutions of 3-iodoprop-2-yn-1-yl butylcarbamate (a biocide), castor oil (hydrophobe) in methyl 2-methylprop-2-enoate (monomer) into aqueous solutions with a large amount of free-micelles of surfactant. The encapsulation was followed by polymerisation. The size distribution of microcapsule from different formula were examined. The biocide encapsulation depends on castor oil content: >12% (full); 6–12% (either full or partial); <6% (minor). Results show a critical molar fraction ratio of the monomer in the droplet to water in the aqueous phase that provides a definitive criterion to assure size retention and full encapsulation. This critical value corresponds to an energy barrier of 116 J/mol to prevent the monomer escaping. This finding is proposed to be used as an advanced rule to guide precision formulation for desired microencapsulation. [ABSTRACT FROM AUTHOR]

Determining capillary pressures and permeation resistances of multiphase seepage in porous-type reservoirs is crucial. The dynamic contact angle (CA) is one of the critical parameters used to calculate capillary pressures and permeation resistances. Under reservoir conditions, dynamic CAs are rate-independent of the triple-phase contact line velocity. Calculating rate-independent dynamic CAs remains challenging and is the main focus of this paper. An experimental system was designed to capture the dynamic CAs of liquid-fluid displacements in microscale polydimethylsiloxane (PDMS) microchannels. These microchannels were 20 × 80 μm or 20 × 40 μm in height and width. The capillary numbers (Ca) were controlled to satisfy the conditions of Ca < 4 × 10−5 for liquid-air displacements and Ca < 3.5 × 10−7 for liquid-liquid displacements. Since pinning forces were consistent at the receding interface and the advancing interface, energy barriers exhibited symmetry. However, CA hysteresis exhibited asymmetry. Based on our experiments, a linear regime of hysteresis was developed and verified to be consistent with others' experiments. The relation can be used to calculate hysteresis strengths and rate-independent CAs. This model was also compared with the fractal model. The hysteresis factor in this model can be derived using the Wenzel factor r and the Cassie fraction ϕ s. [ABSTRACT FROM AUTHOR]

The wetting of a solid by a liquid is a thermally-activated molecular rate process, which may be investigated by studying the temperature-dependence of the dynamic contact angle at standard experimental scales. We use the plunging-tape method and a low-powered microscope to measure the dynamic contact angle of di- n -butyl phthalate (DBP) on poly(ethylene terephthalate) (PET) tape over a very wide speed range of 0.003–100 cm/s at 5 temperatures from 15 °C to 55 °C. The molecular-kinetic theory of dynamic wetting (the MKT) is then used to interpret the data, which span angles from 8° to near 180°. The MKT successfully accounts for the temperature-dependence of the dynamic contact angle, yielding rational values for key parameters including the activation free energy of wetting. Arrhenius-like behavior is also demonstrated. These results would appear to confirm that, at the molecular-scale, dynamic wetting is a thermally-activated rate process and that the influence of temperature is not restricted simply to its effect on surface tension and viscosity. The data show a discontinuity at dynamic contact angles between 60° and 90° that implies a velocity-dependent change in the wetting mechanism. We attribute this to the chemical heterogeneity of the PET surface, which contains both polar and non-polar groups. The parameters obtained by applying the MKT suggest that the interactions of DBP with these groups determine, respectively, the dynamics observed below and above the transition. The sum of the activation free energies of wetting on either side of the transition is close to the total thermodynamic work of adhesion of DBP to PET. [ABSTRACT FROM AUTHOR]