Rapid Synthesis of Nickel Boride/Graphene by Microwave Thermal Shock and its Application in Hydrogen Evolution Reaction

The urgent demand for sustainable and clean energy has promoted the development of water splitting. Herein, metal borides assisted synthesis of graphene-based material (Ni-B/G) has been carried out by facile and fast microwave heating method and applied to hydrogen evolution reaction (HER) in alkaline solution. The Ni-B combining with 2D graphene give rise to highly efficient HER performance with low overpotential of 187 mV at current density of 10 mA cm−2. In addition, it exhibits good stability and retains 76% of current density after continuous oxygen release. The excellent performance is ascribed to the synergetic effect of Ni-B and graphene. The Ni-B not only acts as initiator to adsorb microwave energy but also works as active centre of catalyst. The high conductivity and large specific area of graphene offer accessible contact between electrolyte and intermediates. Therefore, Ni-B/G indicates a promising candidate for HER in alkaline media.

Mathematical modelling of thermal microexplosion in a catalyst granule with point sources of heat release

A mathematical model of heat and mass transfer in a spherical catalyst granule is proposed. Exothermic synthesis reactions are carried out on point active centres located inside a porous ceramic granule. From the surface of the granule the heat of catalytic reactions is removed into liquid synthesis products. The rate of a chemical reaction is modelled by a modified Arrhenius law. In contrast to the homogeneous model of a catalytic granule methods for calculating heat transfer processes in a system of point, active centres do not develop. An iterative procedure is suggested to calculate the unknown temperature and concentration of the reagent at the active centre. It is shown that the temperature of the active centres is significantly higher than in the volume of the granule. The results of modelling a thermal explosion with increasing granule size and reactor temperature are presented.

Coordinated Co-NC/CoFe Dual Active Centre Embedded Three-dimensional Ordered Macroporous Framework as Bifunctional Catalyst for Efficient and Stable Zinc-Air Batteries

Developing efficient and stable multifunctional electrocatalyst is very important for zinc-air batteries in practical. Herein, semiconductive spinel CuFe2O4 supported Co-N co-doped carbon (Co-NC) and CoFe alloy nanoparticles were proposed. In this strategy, the three-dimensional ordered macroporous CuFe2O4 support provides rich channels for mass transmission, revealling good corrosion resistance and durability at the same time. ZIF-67 derived Co-NC decoration improves the conductivity of the catalyst. Further, the uniformlydistributed Co-NC and CoFe nanoparticles (C/CF) dramatically promote the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance. Accordingly, C/CF@CuFe2O4 catalyst shows remarkable bifunctional electrocatalytic activity, with an ORR half-wave potential of 0.86 V, and an OER over-potential of 0.46 V at 10 mA cm-2. The zinc-air battery using this catalyst exhibits a power density of 95.5 mW cm-2 and a durable cyclability for over 170 h at a current density of 10 mA cm-2, which implies a great potential in practical application.

RESPONSE OF A HIGH-SPEED WAVE-PIERCING CATAMARAN TO AN ACTIVE RIDE CONTROL SYSTEM

Ride control systems on high-seed vessels are an important design features for improving passenger comfort and reducing motion sickness and dynamic structural loads. To investigate the performance of ride control systems a 2.5m catamaran model based on the 112m INCAT catamaran was tested with an active centre bow mounted T-Foil and two active stern mounted trim tabs. The model was set-up for towing tank tests in calm water to measure the motions response to ride control step inputs. Heave and pitch response were measured when the model was excited by deflections of the T-Foil and the stern tab separately. Appropriate combinations of the control surface deflections were then determined to produce pure heave and pure pitch response. This forms the basis for setting the gains of the ride control system to implement different control algorithms in terms of the heave and pitch motions in encountered waves. A two degree of freedom rigid body analysis was undertaken to theoretically evaluate the experimental results and showed close agreement with the tank test responses. This work gives an insight into the motions control response and forms the basis for future investigations of optimal control algorithms.

Structure of Escherichia coli cytochrome bd-II type oxidase with bound aurachin D

Cytochrome bd quinol:O2 oxidoreductases are respiratory terminal oxidases so far only identified in prokaryotes, including several pathogenic bacteria. Escherichia coli contains two bd oxidases of which only the bd-I type is structurally characterized. Here, we report the structure of the Escherichia coli cytochrome bd-II type oxidase with the bound inhibitor aurachin D as obtained by electron cryo-microscopy at 3 Å resolution. The oxidase consists of subunits AppB, C and X that show an architecture similar to that of bd-I. The three heme cofactors are found in AppC, while AppB is stabilized by a structural ubiquinone-8 at the homologous positions. A fourth subunit present in bd-I is lacking in bd-II. Accordingly, heme b595 is exposed to the membrane but heme d embedded within the protein and showing an unexpectedly high redox potential is the catalytically active centre. The structure of the Q-loop is fully resolved, revealing the specific aurachin binding.

In-situ spectroscopic observation of dynamic-coupling oxygen on atomically dispersed iridium electrocatalyst for acidic water oxidation

Uncovering the dynamics of active sites in the working conditions is crucial to realizing increased activity, enhanced stability and reduced cost of oxygen evolution reaction (OER) electrocatalysts in proton exchange membrane electrolytes. Herein, we identify at the atomic level potential-driven dynamic-coupling oxygen on atomically dispersed hetero-nitrogen-configured Ir sites (AD-HN-Ir) in the OER working conditions to successfully provide the atomically dispersed Ir electrocatalyst with ultrahigh electrochemical acidic OER activity. Using in-situ synchrotron radiation infrared and X-ray absorption spectroscopies, we directly observe that one oxygen atom is formed at the Ir active site with an O-hetero-Ir-N4 structure as a more electrophilic active centre in the experiment, which effectively promotes the generation of key *OOH intermediates under working potentials; this process is favourable for the dissociation of H2O over Ir active sites and resistance to over-oxidation and dissolution of the active sites. The optimal AD-HN-Ir electrocatalyst delivers a large mass activity of 2860 A gmetal−1 and a large turnover frequency of 5110 h−1 at a low overpotential of 216 mV (10 mA cm−2), 480–510 times larger than those of the commercial IrO2. More importantly, the AD-HN-Ir electrocatalyst shows no evident deactivation after continuous 100 h OER operation in an acidic medium.

Transcription initiation at a consensus bacterial promoter proceeds via a 'bind-unwind-load-and-lock' mechanism

Transcription initiation starts with unwinding of promoter DNA by RNA polymerase (RNAP) to form a catalytically competent RNAP-promoter complex (RPO). Despite extensive study, the mechanism of promoter unwinding has remained unclear, in part due to the transient nature of intermediates on path to RPo. Here, using single-molecule unwinding-induced fluorescence enhancement to monitor promoter unwinding, and single-molecule fluorescence resonance energy transfer to monitor RNAP clamp conformation, we analyze RPo formation at a consensus bacterial core promoter. We find that the RNAP clamp is closed during promoter binding, remains closed during promoter unwinding, and then closes further, locking the unwound DNA in the RNAP active-centre cleft. Our work defines a new, 'bind-unwind-load-and-lock' model for the series of conformational changes occurring during promoter unwinding at a consensus bacterial promoter and provides the tools needed to examine the process in other organisms and at other promoters.

Transcription initiation at a consensus bacterial promoter proceeds via a "bind-unwind-load-and-lock" mechanism

Transcription initiation starts with unwinding of promoter DNA by RNA polymerase (RNAP) to form a catalytically competent RNAP-promoter complex (RPO). Despite extensive study, the mechanism of promoter unwinding has remained unclear, in part due to the transient nature of intermediates on path to RPo. Here, using single-molecule unwinding-induced fluorescence enhancement to monitor promoter unwinding, and single-molecule fluorescence resonance energy transfer to monitor RNAP clamp conformation, we analyze RPo formation at a consensus bacterial core promoter. We find that the RNAP clamp is closed during promoter binding, remains closed during promoter unwinding, and then closes further, locking the unwound DNA in the RNAP active-centre cleft. Our work defines a new, bind-unwind-load-and-lock, model for the series of conformational changes occurring during promoter unwinding at a consensus bacterial promoter and provides the tools needed to examine the process in other organisms and at other promoters.