Jijun Zhao

Metal–Organic‐Framework‐Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity.

Hole Defects and Nitrogen Doping in Graphene: Implication for Supercapacitor Applications

One great challenge for supercapacitor is to achieve high energy capacity and fast charge/discharge rates simultaneously. Porous graphene with large surface area is a promising candidate for electrode materials of supercapacitor. Using first-principles calculations and non-equilibrium Greens function technique, we have explored the formation energies, mechanical properties, diffusion behaviors and electrical conductance of graphene sheets with various hole defects and/or nitrogen doping. Interestingly, graphene sheets with pyridinic-like holes (especially hexagonal holes) can be more easily doped with nitrogen and still retain the excellent mechanical properties of pristine graphene that is beneficial for the long cycle life. Porous graphene electrode with moderate hole diameter of 4.2-10 Å facilitates efficient access of electrolyte and exhibit excellent rate capability. In addition, doping with nitrogen as electron donors or proton attractors leads to charge accumulation and generates higher pseudocapacitance. Transmission coefficients of N-doped graphene sheets with pyridinic-like holes are only moderately reduced with regard to that of pristine graphene and are insensitive to the detailed geometry parameters. Overall, N-doped graphene with pyridinic-like holes exhibits exciting potentials for high performance energy storage in supercapacitor devices.

Enhanced piezoelectric effect in Janus group-III chalcogenide monolayers

Piezoelectricity is a unique material property that converts mechanical energy into electricity or vice versa. Starting from the group-III monochalcogenide monolayers, we design a series of derivative Janus structures for piezoelectric materials, including Ga2SSe, Ga2STe, Ga2SeTe, In2SSe, In2STe, In2SeTe, GaInS2, GaInSe2, and GaInTe2. Our first-principles calculations show that these Janus structures are thermodynamically and dynamically stable. They have a bandgap in the range of 0.89–2.03 eV, lower than those of the perfect monolayers, and Ga2STe, Ga2SeTe, In2STe, and In2SeTe monolayers are direct gap semiconductors. They possess piezoelectric coefficients up to 8.47 pm/V, over four times the maximum value obtained in perfect group-III monochalcogenide monolayers. Moreover, the broken mirror symmetry of these Janus structures induces out-of-plane dipolar polarization, yielding additional out-of-plane piezoelectric coefficients of 0.07–0.46 pm/V. The enhanced piezoelectric properties enable the developme...

Oxidation Resistance of Monolayer Group-IV Monochalcogenides

Ridged, orthorhombic two-dimensional (2D) group-V elemental and group IV-VI compound analogues of phosphorene provide a versatile platform for nanoelectronics, optoelectronics, and clean energy. However, phosphorene is vulnerable to oxygen in ambient air, which is a major obstacle for its applications. Regarding this issue, here we explore the oxidation behavior of monolayer group-IV monochalcogenides (GeS, GeSe, SnS, and SnSe), in comparison to that of phosphorene and arsenene by first-principles calculations. We find superior oxidation resistance of the monolayer group-IV monochalcogenides, with activation energies for the chemisorption of O2 on the 2D sheets in the range of 1.26-1.60 eV, about twice of the values of phosphorene and arsenene. The distinct oxidation behaviors of monolayer group-IV monochalcogenides and group-V phosphorene analogues originate from their different bond natures. Moreover, the chemisorption of a moderate amount of oxygen atoms does not severely deteriorate the electronic band structures of the monolayer group-IV monochalcogenides. These results shine light on the utilization of the monolayer group-IV monochalcogenides for next-generation 2D electronics and optoelectronics with high performance and stability.

Nitrogen-Doped Graphene on Transition Metal Substrates as Efficient Bifunctional Catalysts for Oxygen Reduction and Oxygen Evolution Reactions

Composites of transition metal and carbon-based materials are promising bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and are widely used in rechargeable metal-air batteries. However, the mechanism of their enhanced bicatalytic activities remains elusive. Herein, we construct N-doped graphene supported by Co(111) and Fe(110) substrates as bifunctional catalysts for ORR and OER in alkaline media. First-principles calculations show that these heterostructures possess a large number of active sites for ORR and OER with overpotentials comparable to those of noble metal benchmark catalysts. The catalytic activity is modulated by the coupling strength between graphene and the metal substrates, as well as the charge distribution in the graphitic sheet, which is delicately mediated by N dopants. These theoretical results uncover the key parameters that govern the bicatalytic properties of hybrid materials and help prescribe the principles for designing multifunctional electrocatalysts of high performance.

Monolayer group-III monochalcogenides by oxygen functionalization: a promising class of two-dimensional topological insulators

Monolayer group-III monochalcogenides (MX, M = Ga, In; X = S, Se, Te), an emerging category of two-dimensional (2D) semiconductors, hold great promise for electronics, optoelectronics and catalysts. By first-principles calculations, we show that the phonon dispersion and Raman spectra, as well as the electronic and topological properties of monolayer MX can be tuned by oxygen functionalization. Chemisorption of oxygen atoms on one side or both sides of the MX sheet narrows or even closes the band gap, enlarges work function, and significantly reduces the carrier effective mass. More excitingly, InS, InSe, and InTe monolayers with double-side oxygen functionalization are 2D topological insulators with sizeable bulk gap up to 0.21 eV. Their low-energy bands near the Fermi level are dominated by the px and py orbitals of atoms, allowing band engineering via in-plane strains. Our studies provide viable strategy for realizing quantum spin Hall effect in monolayer group-III monochalcogenides at room temperature, and utilizing these novel 2D materials for high-speed and dissipationless transport devices.2D materials: Tailoring properties with oxygen functionalizationOxygen functionalization can be used to tune the electronic and topological properties of group-III monolayer monochalcogenide materials. Jijun Zhao at the Dalian University of Technology, Yugui Yao at the Beijing Institute of Technology and colleagues performed first-principles calculations showing that chemisorption of oxygen atoms on one or both sides of 2D group-III monochalcogenides, which were experimentally observed in 2013, can be used to tune their properties. In particular, it reduces the gap, increases the work function, and reduces the effective mass of the carriers. InS, InSe and InTe with oxygen atoms chemisorbed on both sides become 2D topological insulators with a sizable bulk band gap. Because these oxidized materials are naturally protected from further oxidation and surface degradation, they can provide a platform for observing exotic effects, in particular the quantum spin Hall effect, at room temperature.

Atomic Sulfur Anchored on Silicene, Phosphorene, and Borophene for Excellent Cycle Performance of Li–S Batteries

Dissolution of intermediate lithium polysulfides (LiPS) is an inevitable obstacle for the solid sulfur-based cathode in Li-S batteries. For the first time, herein, atomic sulfur is incorporated into silicene, phosphorene, and borophene to intrinsically eliminate the dissolution of LiPS. The small molecular sulfur species are anchored on the silicene surface with stronger Si-S interaction than the P-S and B-S ones. Meanwhile, a high atomic sulfur coverage (63.1 wt %) is achieved in silicene and concomitantly stabilizes the silicene layer. For the S3-covered silicene, a high theoretical capacity of 857 mA h g-1 is achieved with slight dissolution of LiPS originated from the loss of interior S atoms that are not directly bound with silicene surface. By realizing the elemental S2 coverage on silicene with large surface area, the Li+ ions can react fast with the S2 species, leading to a high theoretical capacity of 891 mA h g-1 without dissolution and migration of the intermediate LiPS. Most interestingly, the discharge products of atomic layer of lithium sulfides on silicene surface exhibit completely different behaviors from the traditional discharge products of solid Li2S, which can function as effective adsorption and activation sites for the conversion of LiPS from long chain to short chain by accelerated redox reaction. The present study gains some key insights into how the atomic sulfur contributes to the intrinsic shuttle inhibition and offers a feasible way to design the atomic sulfur-based cathode materials of Li-S batteries with better electrochemical performance.

Chemically Engineering Magnetic Anisotropy of 2D Metalloporphyrin

Abstract Continuous miniaturization of magnetic units in spintronics devices inspires efforts to search for novel 2D magnetic materials with giant magnetic anisotropy energy (MAE). Through systematic first‐principles calculations, large MAE of 24 meV in W or Re embedded 2D polyporphyrin frameworks is found. Interestingly, the MAE can be enhanced up to 60 meV, through replacing the hydrogen atoms on the edges of the Re based 2D polyporphyrin framework by hydroxyl and amino radicals. Analysis of the electronic structures reveals that the enhancement of MAE is mainly attributed to charge redistributions and energy shifts of Re 5d orbitals induced by the functional radicals. The findings pave a new and feasible way for tailoring the magnetic properties of magnetic organic materials to fulfill the criteria for applications in spintronics devices at high temperature.

2D lateral heterostructures of group-III monochalcogenide: Potential photovoltaic applications

Solar photovoltaics provides a practical and sustainable solution to the increasing global energy demand. Using first-principles calculations, we investigate the energetics and electronic properties of two-dimensional lateral heterostructures by group-III monochalcogenides and explore their potential applications in photovoltaics. The band structures and formation energies from supercell calculations demonstrate that these heterostructures retain semiconducting behavior and might be synthesized in laboratory using the chemical vapor deposition technique. According to the computed band offsets, most of the heterojunctions belong to type II band alignment, which can prevent the recombination of electron-hole pairs. Besides, the electronic properties of these lateral heterostructures can be effectively tailored by the number of layers, leading to a high theoretical power conversion efficiency over 20%.

Screening and Design of Novel 2D Ferromagnetic Materials with High Curie Temperature above Room Temperature

Two-dimensional (2D) intrinsic ferromagnets with high Curie temperature ( TC) are desirable for spintronic applications. Using systematic first-principles calculations, we investigate the electronic and magnetic properties of 22 monolayer 2D materials with layered bulk phases. From these candidates, we screen out five ferromagnetic monolayer materials belonging to three types of structures: type i (ScCl, YCl, LaCl), type ii (LaBr2), and type iii (CrSBr). Type i is a kind of metallic ferromagnetic material, whereas LaBr2 and CrSBr of type ii and iii are small-bandgap ferromagnetic semiconductors with TC near room temperature. Moreover, the ferromagnetic CrSBr monolayer possesses a large magnetic moment of ∼3 μB per Cr atom, originating from its distorted octahedron coordination. The robust ferromagnetism of the CrSBr monolayer is ascribed to the halogen-mediated (Cr-Br-Cr) and chalcogen-mediated (Cr-S-Cr) superexchange interactions; then, an isoelectronic substitution strategy is proposed to tailor the magnetic coupling strength. Hence, monolayer structures of CrSI, CrSCl, and CrSeBr with notably enhanced Curie temperature up to 500 K as well as favorable formation energy are designed. The moderate interlayer binding energy and high TC make these monolayer ferromagnetic materials feasible for experimental synthesis and attractive as 2D spintronic devices.