Yi Jia

Defect Graphene as a Trifunctional Catalyst for Electrochemical Reactions

Defects derived by the removal of heteroatoms from graphene are demonstrated, both experimentally and theoretically, to be effective for all three basic electrochemical reactions, e.g., oxygen reduction (ORR), oxygen evolution (OER), and hydrogen evolution (HER). Density function theory calculations further reveal that the different types of defects are essential for the individual electrocatalytic activity for ORR, OER, and HER, respectively.

A Heterostructure Coupling of Exfoliated Ni–Fe Hydroxide Nanosheet and Defective Graphene as a Bifunctional Electrocatalyst for Overall Water Splitting

Herein, the authors demonstrate a heterostructured NiFe LDH-NS@DG10 hybrid catalyst by coupling of exfoliated Ni-Fe layered double hydroxide (LDH) nanosheet (NS) and defective graphene (DG). The catalyst has exhibited extremely high electrocatalytic activity for oxygen evolution reaction (OER) in an alkaline solution with an overpotential of 0.21 V at a current density of 10 mA cm-2 , which is comparable to the current record (≈0.20 V in Fe-Co-Ni metal-oxide-film system) and superior to all other non-noble metal catalysts. Also, it possesses outstanding kinetics (Tafel slope of 52 mV dec-1 ) for the reaction. Interestingly, the NiFe LDH-NS@DG10 hybrid has also exhibited the high hydrogen evolution reaction (HER) performance in an alkaline solution (with an overpotential of 115 mV by 2 mg cm-2 loading at a current density of 20 mA cm-2 ) in contrast to barely HER activity for NiFe LDH-NS itself. As a result, the bifunctional catalyst the authors developed can achieve a current density of 20 mA cm-2 by a voltage of only 1.5 V, which is also a record for the overall water splitting. Density functional theory calculation reveals that the synergetic effects of highly exposed 3d transition metal atoms and carbon defects are essential for the bifunctional activity for OER and HER.

Ultrathin iron-cobalt oxide nanosheets with abundant oxygen vacancies for the oxygen evolution reaction

Electrochemical water splitting is a promising method for storing light/electrical energy in the form of H2 fuel; however, it is limited by the sluggish anodic oxygen evolution reaction (OER). To improve the accessibility of H2 production, it is necessary to develop an efficient OER catalyst with large surface area, abundant active sites, and good stability, through a low-cost fabrication route. Herein, a facile solution reduction method using NaBH4 as a reductant is developed to prepare iron-cobalt oxide nanosheets (Fex Coy -ONSs) with a large specific surface area (up to 261.1 m2 g-1 ), ultrathin thickness (1.2 nm), and, importantly, abundant oxygen vacancies. The mass activity of Fe1 Co1 -ONS measured at an overpotential of 350 mV reaches up to 54.9 A g-1 , while its Tafel slope is 36.8 mV dec-1 ; both of which are superior to those of commercial RuO2 , crystalline Fe1 Co1 -ONP, and most reported OER catalysts. The excellent OER catalytic activity of Fe1 Co1 -ONS can be attributed to its specific structure, e.g., ultrathin nanosheets that could facilitate mass diffusion/transport of OH- ions and provide more active sites for OER catalysis, and oxygen vacancies that could improve electronic conductivity and facilitate adsorption of H2 O onto nearby Co3+ sites.

Seaweed biomass derived (Ni,Co)/CNT nanoaerogels: efficient bifunctional electrocatalysts for oxygen evolution and reduction reactions

Developing earth-abundant, active and stable electrocatalysts which operate in two-electrode rechargeable metal–air batteries, including both oxygen evolution and reduction reactions (OER and ORR), is vital for renewable energy conversion in real application. Here, we demonstrate a three-dimensional (3D) bifunctional nanoaerogel electrocatalyst that exhibits good electrocatalytic properties for both OER and ORR. This material was fabricated using a scalable and facile method involving the pyrolysis of (Ni,Co)/CNT alginate hydrogels derived from sustainable seaweed biomass after an ion exchange process. The bifunctionality for oxygen electrocatalysis as shown by the OER–ORR potential difference (ΔE, the OER and ORR potentials are taken at the current densities of 10 mA cm−2 and −3 mA cm−2 in 0.1 M KOH, respectively) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts. The good performance was attributed to the ternary Ni/NiO/NiCo2O4 catalytic center for charge transfer and 3D hierarchical mesoporous hybrid framework for efficient mass transport. More importantly, the Zn–air battery fabricated with the hybrid nanoaerogel as a bifunctional electrocatalyst displays very high energy efficiency (58.5%) and long-term stability. Prospectively, our present work may pave a new way to develop earth-abundant and low cost high-performance bifunctional electrocatalysts for rechargeable metal–air batteries.

Defective-activated-carbon-supported Mn–Co nanoparticles as a highly efficient electrocatalyst for oxygen reduction

A highly active and durable cathodic oxygen reduction reaction (ORR) catalyst is synthesized by introducing a small amount of Mn-Co spinel into a kind of defective activated-carbon (D-AC) support. It is assumed that the synergetic coupling effects between the unique defects in the D-AC and the loaded Mn-Co spinel facilitate the ORR and enhance its durability.

Three-dimensional NiCo2O4@NiWO4 core–shell nanowire arrays for high performance supercapacitors

Hierarchical NiCo2O4@NiWO4 core–shell nanowire arrays supported on nickel foam have been synthesized via a facile hydrothermal route coupled with a post-thermal treatment. The hydrothermally synthesized NiCo2O4 nanowire arrays serve as the scaffold for anchoring the NiWO4 nanosheets. When evaluated as binder-free electrodes for supercapacitors, the optimized NiCo2O4@NiWO4 hybrid electrode demonstrates remarkable electrochemical performance with a high specific capacitance of 1384 F g−1 at a current density of 1 A g−1 and superior cycling stability (87.6% retention over 6000 cycles at a current density of 5 A g−1). In addition, an asymmetric supercapacitor (ASC) based on the optimized NiCo2O4@NiWO4 electrode and activated carbon is assembled with 6 M KOH as the electrolyte. The as-fabricated ASC device can achieve a maximum high energy density of 41.5 W h kg−1 at a power density of 760 W kg−1. The excellent supercapacitive performance could be ascribed to the unique core–shell architecture and the synergistic effect from the NiCo2O4 nanowires and the ultrathin NiWO4 nanosheets.

Activated carbon becomes active for oxygen reduction and hydrogen evolution reactions

We utilized a facile method for creating unique defects in the activated carbon (AC), which makes it highly active for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). The ORR activity of the defective AC (D-AC) is comparable to the commercial Pt/C in alkaline medium, and the D-AC also exhibits excellent HER activity in acidic solution.

Fluorine‐Doped Porous Single‐Crystal Rutile TiO2 Nanorods for Enhancing Photoelectrochemical Water Splitting

Fluorine-doped hierarchical porous single-crystal rutile TiO(2) nanorods have been synthesized through a silica template method, in which F(-) ions acts as both n-type dopants and capping agents to make the isotropic growth of the nanorods. The combination of high crystallinity, abundant surface reactive sites, large porosity, and improved electronic conductivity leads to an excellent photoelectrochemical activity. The photoanode made of F-doped porous single crystals displays a remarkably enhanced solar-to-hydrogen conversion efficiency (≈0.35 % at -0.33 V vs. Ag/AgCl) under 100 mW cm(-2) of AM=1.5 solar simulator illumination that is ten times of the pristine solid TiO(2) single crystals.

Architecture-controlled synthesis of MxOy (M = Ni, Fe, Cu) microfibres from seaweed biomass for high-performance lithium ion battery anodes

The increasing demand for high performance lithium ion batteries (LIBs) has aroused great interest in developing high specific capacity, cycle performance and rate capability anode materials. Transition metal oxides (TMOs) have attracted much attention as promising anode materials for rechargeable LIBs owing to their high theoretical capacity. Here, a general strategy has been developed to fabricate high-performance fibrous TMO anodes such as elemental Ni doped NiO fibre (NiO/Ni/C-F), yolk–shell structured carbon@Fe2O3 fibre (C@Fe2O3-F), and hollow CuO fibre (CuO-HF) with controllable nanostructures by using alginate microfibres as templates. The key to the formation of various TMO micro-/nano-structures is the templating ability of the natural structure of long alginate molecular chains, where the metal cations can be confined in an “egg-box” via coordination with negatively charged α-L-guluronate blocks. When tested as anode materials for LIB half cells, these fibrous electrodes deliver excellent cycling performance with no capacity decrease after 200 cycles (793 mA h g−1, NiO/Ni/C-F, 0.072 A g−1; 1035 mA h g−1, C@Fe2O3-F, 0.1 A g−1; 670 mA h g−1, CuO-HF, 0.067 A g−1), and demonstrate great rate performance at different current densities. This finding highlights a general, green and eco-friendly strategy for the scale-up production of potential high-performance TMO anodes for LIBs.

Enhanced photodynamic therapy of mixed phase TiO2(B)/anatase nanofibers for killing of HeLa cells

Photodynamic therapy (PDT), which is a procedure that uses photosensitizing drug to apply therapy selectively to target sites, has been proven to be a safe treatment for cancers and conditions that may develop into cancers. Nano-sized TiO2 has been regarded as potential photosensitizer for UV light driven PDT. In this study, four types of TiO2 nanofibers were prepared from proton tri-titanate (H2T3O7) nanofiber. The as-obtained nanofibers were demonstrated as efficient photosensitizers for PDT killing of HeLa cells. MTT assay and flow cytometry (FCM) were carried out to evaluate the biocompatibility, percentage of apoptotic cells, and cell viability. The non-cytotoxicity of the as-prepared TiO2 nanofibers in the absence of UV irradiation has also been demonstrated. Under UV light irradiation, the TiO2 nanofibers, particularly the mixed phase nanofibers, displayed much higher cell-killing efficiency than Pirarubicin (THP), which is a common drug to induce the apoptosis of HeLa cells. We ascribe the high cellkilling efficiency of the mixed phase nanofibers to the bandgap edge match and stable interface between TiO2(B) and anatase phases in a single nanofiber, which can inhibit the recombination of the photogenerated electrons and holes. This promotes the charge separation and transfer processes and can produce more reactive oxygen species (ROS) that are responsible for the killing of HeLa cells.