Project description:Herein, we have demonstrated a facile electroless Ni coated nanostructured TiO2 photocatalyst for the first time. More significantly the photocatalytic water splitting shows excellent performance for hydrogen production which is hitherto unattempted. The structural study exhibits majorly the anatase phase along with the minor rutile phase of TiO2. Interestingly, electroless nickel deposited on the TiO2 nanoparticles of size 20 nm shows a cubic structure with nanometer scale Ni coating (1-2 nm). XPS supports the existence of Ni without any oxygen impurity. The FTIR and Raman studies support the formation of TiO2 phases without any other impurities. The optical study shows a red shift in the band gap due to optimum nickel loading. The emission spectra show variation in the intensity of the peaks with Ni concentration. The vacancy defects are pronounced in lower concentrations of Ni loading which shows the formation of a huge number of charge carriers. The electroless Ni loaded TiO2 has been used as a photocatalyst for water splitting under solar light. The primary results manifest that the hydrogen evolution of electroless Ni plated TiO2 is 3.5 times higher (1600 μmol g-1 h-1) than pristine TiO2 (470 μmol g-1 h-1). As shown in the TEM images, nickel is completely electroless plated on the TiO2 surface, which accelerates the fast transport of electrons to the surface. It suppresses the electron-hole recombination drastically which is responsible for higher hydrogen evolution using electroless Ni plated TiO2. The recycling study exhibits a similar amount of hydrogen evolution at similar conditions which shows the stability of the Ni loaded sample. Interestingly, Ni powder loaded TiO2 did not show any hydrogen evolution. Hence, the approach of electroless plating of nickel over the semiconductor surface will have potential as a good photocatalyst for hydrogen evolution.
Project description:The low efficiency of water electrolysis mostly arises from the thermodynamic uphill oxygen evolution reaction. The efficiency can be greatly improved by rationally designing low-cost and efficient oxygen evolution anode materials. Herein, we report the synthesis of Ni-P alloys adopting a facile electroless plating method under mild conditions on nickel substrates. The relationship between the Ni-P properties and catalytic activity allowed us to define the best conditions for the electroless synthesis of highperformance Ni-P catalysts. Indeed, the electrochemical investigations indicated an increased catalytic response by reducing the thickness and Ni/P ratio in the alloy. Furthermore, the Ni-P catalysts with optimized size and composition deposited on Ni foam exposed more active sites for the oxygen evolution reaction, yielding a current density of 10 mA cm-2 at an overpotential as low as 335 mV, exhibiting charge transfer resistances of only a few ohms and a remarkable turnover frequency (TOF) value of 0.62 s-1 at 350 mV. The present study provides an advancement in the control of the electroless synthetic approach for the design and large-scale application of high-performance metal phosphide catalysts for electrochemical water splitting.
Project description:Hydrogen promotion as a clean energy vector could provide an efficient strategy for realizing real decarbonization of the current energy system. Purification steps are usually required in most H2-production processes, providing the use of Pd-based membranes, particularly those supported on porous stainless steel (PSS), important advantages against other alternatives. In this work, new composite membranes were prepared by modifying PSS supports with graphite, as an intermediate layer, before incorporating a palladium film by electroless pore-plating. Fully dense Pd layers were reached, with an estimated thickness of around 17 μm. Permeation measurements were carried out in two different modes: H2 permeation from the inner to the outer side of the membrane (in-out) and in the opposite way (out-in). H2 permeances between 3.24 × 10-4 and 4.33 × 10-4 mol m-2 s-1 Pa-0.5 with αH2/N2 ≥ 10,000 were reached at 350-450 °C when permeating from the outer to the inner surface. Despite a general linear trend between permeating H2 fluxes and pressures, the predicted intercept in (0,0) by the Sieverts' law was missed due to the partial Pd infiltration inside the pores. H2-permeances progressively decreased up to around 33% for binary H2-N2 mixtures containing 40 vol% N2 due to concentration-polarization phenomena. Finally, the good performance of these membranes was maintained after reversing the direction of the permeate flux. This fact practically demonstrates an adequate mechanical resistance despite generating tensile stress on the Pd layer during operation, which is not accomplished in other Pd membranes.
Project description:Graphene on diamond has been attracting considerable attention due to the unique and highly beneficial features of this heterostructure for a range of electronic applications. Here, ultrahigh-vacuum X-ray photoelectron spectroscopy is used for in situ analysis of the temperature dependence of the Ni-assisted thermally induced graphitization process of intrinsic nanocrystalline diamond thin films (65 nm thickness, 50-80 nm grain size) on silicon wafer substrates. Three major stages of diamond film transformation are determined from XPS during the thermal annealing in the temperature range from 300 °C to 800 °C. Heating from 300 °C causes removal of oxygen; formation of the disordered carbon phase is observed at 400 °C; the disordered carbon progressively transforms to graphitic phase whereas the diamond phase disappears from the surface from 500 °C. In the well-controllable temperature regime between 600 °C and 700 °C, the nanocrystalline diamond thin film is mainly preserved, while graphitic layers form on the surface as the predominant carbon phase. Moreover, the graphitization is facilitated by a disordered carbon interlayer that inherently forms between diamond and graphitic layers by Ni catalyst. Thus, the process results in formation of a multilayer heterostructure on silicon substrate.
Project description:This work focused on the computational fluid dynamics (CFD) modeling of H2/N2 separation in a membrane permeator module containing a supported dense Pd-based membrane that was prepared using electroless pore-plating (ELP-PP). An easy-to-implement model was developed based on a source-sink pair formulation of the species transport and continuity equations. The model also included the Darcy-Forcheimer formulation for modeling the porous stainless steel (PSS) membrane support and Sieverts' law for computing the H2 permeation flow through the dense palladium film. Two different reactor configurations were studied, which involved varying the hydrogen flow permeation direction (in-out or out-in). A wide range of experimental data was simulated by considering the impact of the operating conditions on the H2 separation, such as the feed pressure and the H2 concentration in the inlet stream. Simulations of the membrane permeator device showed an excellent agreement between the predicted and experimental data (measured as permeate and retentate flows and H2 separation). Molar fraction profiles inside the permeator device for both configurations showed that concentration polarization near the membrane surface was not a limit for the hydrogen permeation but could be useful information for membrane reactor design, as it showed the optimal length of the reactor.
Project description:The evolution from subtractive to modified semi-additive (mSAP) and semi-additive (SAP) processes has heightened the importance of electroless plated (ELP) copper (Cu) peel strength in the printed circuit board industry. This study introduces a wet process for depositing Cu on liquid crystal polymer (LCP) using advanced electroless plating, incorporating a polyethylenimine (PEI) surfactant, a homemade nano-sized palladium (Pd) activator, and a micro-sculpturing treatment. By adjusting PEI immersion time and substrate roughness in the sub-micrometer domain, the peel strength of the ELP Cu film ranges from under 10 gf/cm to over 600 gf/cm. This wide range meets both low peel strength needs of mSAP peelable Cu foil and the high strength required in SAP. Characterization techniques, including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), water contact angle (WCA) measurements, and fracture analysis, reveal that ELP Cu peel strength is driven by a synergistic effect between molecular interaction and physical anchoring.
Project description:Papain-like protease (PLpro) is a promising therapeutic target against SARS-CoV-2, but its restricted S1/S2 subsites pose an obstacle in developing active site-directed inhibitors. We have recently identified C270 as a novel covalent allosteric site for SARS-CoV-2 PLpro inhibitors. Here we present a theoretical investigation of the proteolysis reaction catalyzed by the wild-type SARS-CoV-2 PLpro as well as the C270R mutant. Enhanced sampling MD simulations were first performed to explore the influence of C270R mutation on the protease dynamics, and sampled thermodynamically favorable conformations were then submitted to MM/PBSA and QM/MM MD simulations for thorough characterization of the protease-substrate binding and covalent reactions. The disclosed proteolysis mechanism of PLpro, as characterized by the occurrence of proton transfer from the catalytic C111 to H272 prior to the substrate binding and with deacylation being the rate-determining step of the whole proteolysis process, is not completely identical to that of the 3C-like protease, another key cysteine protease of coronaviruses. The C270R mutation alters the structural dynamics of the BL2 loop that indirectly impairs the catalytic function of H272 and reduces the binding of the substrate with the protease, ultimately showing an inhibitory effect on PLpro. Together, these results provide a comprehensive understanding at the atomic level of the key aspects of SARS-CoV-2 PLpro proteolysis, including the catalytic activity allosterically regulated by C270 modification, which is crucial to the follow-up inhibitor design and development.
Project description:Flexible energy storage electrodes with high conductivity and capacity are crucial for wearable electronic clothes. Herein, a flexible hierarchical Ni(OH)2/Cu(OH)2 interwoven nanosheets in situ coated on Ni-Cu-P alloy plated cotton fabric textile (NCO/CF), which displays perfect conductive and electrochemical performance, is prepared by electroless deposition and electrochemical oxidation method. While the Ni-Cu-P alloy layer coated on the fabric effectively contributes to excellent mechanical performance and electro-conductivity of the as-prepared NCO/CF electrode, the hierarchical Ni(OH)2/Cu(OH)2 interwoven nanosheets in the oxidation layer effectively lead to a high energy storage performance with a specific areal capacity of 4.7 C cm-2 at a current density of 2 mA cm-2. When the power density of the two-electrode system based on NCO/CF and the carbon cloth (CC) is 2.4 mW cm-2, the energy density is 1.38 mW h cm-2. Furthermore, the flexible solid-state energy storage f-NCO/CF//CC is assembled in a self-powered system and supplies continuous power for electronic devices, demonstrating that NCO/CF is promising to be applied in various energy storage devices to power portable and wearable devices in the future.
Project description:Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications.
Project description:In situ activation-graphitization method based on the atomically dispersed K and Fe in organic salts is developed to synthesize hierarchical porous graphitic carbon by directly pyrolysis potassium citrate and iron citrate. Moreover, (NH4)2C2O4 is also employed as both N dopant and porogen to open up internal structure and regulate pore structure. The inside-out activation leads to the homogeneous reaction and interconnected hierarchical porous structure with few dead pores. Accompanied by high specific surface area, appropriate pore distribution, good conductivity, and N/O functional groups, the sample exhibits high capacitance of 322.6 F g-1 at 0.5 A g-1, good rate capability, and excellent cycling stability with 101.5% capacitance retention after 15,000 cycles. The supercapacitor shows an energy density of 21.3 W h kg-1 at 456.7 W kg-1 in 1 M Na2SO4. Easy synthesis, cost-effective, and environmentally benign, the work provides a promising strategy to produce hierarchical porous graphitic carbon applied in energy storage.