Shifeng Jin

Deep-Ultraviolet Nonlinear Optical Materials: Na2Be4B4O11 and LiNa5Be12B12O33

Deep-UV coherent light generated by nonlinear optical (NLO) materials possesses highly important applications in photonic technologies. Beryllium borates comprising anionic planar layers have been shown to be the most promising deep UV NLO materials. Here, two novel NLO beryllium borates Na2Be4B4O11 and LiNa5Be12B12O33 have been developed through cationic structural engineering. The most closely arranged [Be2BO5]∞ planar layers, connected by the flexible [B2O5] groups, have been found in their structures. This structural regulation strategy successfully resulted in the largest second harmonic generation (SHG) effects in the layered beryllium borates, which is ~1.3 and 1.4 times that of KDP for Na2Be4B4O11 and LiNa5Be12B12O33, respectively. The deep-UV optical transmittance spectra based on single crystals indicated their short-wavelength cut-offs are down to ~170 nm. These results demonstrated that Na2Be4B4O11 and LiNa5Be12B12O33 possess very promising application as deep-UV NLO crystals.

Observation of superconductivity at 30∼46K in AxFe2Se2 (A = Li, Na, Ba, Sr, Ca, Yb, and Eu)

New iron selenide superconductors by intercalating smaller-sized alkali metals (Li, Na) and alkaline earths using high-temperature routes have been pursued ever since the discovery of superconductivity at about 30 K in KFe2Se2, but all have failed so far. Here we demonstrate that a series of superconductors with enhanced Tc = 30∼46 K can be obtained by intercalating metals, Li, Na, Ba, Sr, Ca, Yb, and Eu in between FeSe layers by the ammonothermal method at room temperature. Analysis on their powder X-ray diffraction patterns reveals that all the main phases can be indexed based on body-centered tetragonal lattices with a∼3.755–3.831 Å while c∼15.99–20.54 Å. Resistivities show the corresponding sharp transitions at 45 K and 39 K for NaFe2Se2 and Ba0.8Fe2Se2, respectively, confirming their bulk superconductivity. These findings provide a new starting point for studying the properties of these superconductors and an effective synthetic route for the exploration of new superconductors as well.

Cobalt carbide nanoprisms for direct production of lower olefins from syngas

Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The ‘Fischer–Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson–Schulz–Flory distribution, which is characterized by a maximum C2–C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2–C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

Electronic and Morphological Dual Modulation of Cobalt Carbonate Hydroxides by Mn Doping toward Highly Efficient and Stable Bifunctional Electrocatalysts for Overall Water Splitting

Developing bifunctional efficient and durable non-noble electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is highly desirable and challenging for overall water splitting. Herein, Co-Mn carbonate hydroxide (CoMnCH) nanosheet arrays with controllable morphology and composition were developed on nickel foam (NF) as such a bifunctional electrocatalyst. It is discovered that Mn doping in CoCH can simultaneously modulate the nanosheet morphology to significantly increase the electrochemical active surface area for exposing more accessible active sites and tune the electronic structure of Co center to effectively boost its intrinsic activity. As a result, the optimized Co1Mn1CH/NF electrode exhibits unprecedented OER activity with an ultralow overpotential of 294 mV at 30 mA cm-2, compared with all reported metal carbonate hydroxides. Benefited from 3D open nanosheet array topographic structure with tight contact between nanosheets and NF, it is able to deliver a high and stable current density of 1000 mA cm-2 at only an overpotential of 462 mV with no interference from high-flux oxygen evolution. Despite no reports about effective HER on metal carbonate hydroxides yet, the small overpotential of 180 mV at 10 mA cm-2 for HER can be also achieved on Co1Mn1CH/NF by the dual modulation of Mn doping. This offers a two-electrode electrolyzer using bifunctional Co1Mn1CH/NF as both anode and cathode to perform stable overall water splitting with a cell voltage of only 1.68 V at 10 mA cm-2. These findings may open up opportunities to explore other multimetal carbonate hydroxides as practical bifunctional electrocatalysts for scale-up water electrolysis.

Superconducting Phases in Potassium-Intercalated Iron Selenides

The ubiquitous coexistence of majority insulating 245 phases and minority superconducting (SC) phases in A(x)Fe(2-y)Se(2) (A = K, Cs, Rb, Tl/Rb, Tl/K) formed by high-temperature routes makes pure SC phases highly desirable for studying the intrinsic properties of this SC family. Here we report that there are at least two pure SC phases, K(x)Fe(2)Se(2)(NH(3))(y) (x ≈ 0.3 and 0.6), determined mainly by potassium concentration in the K-intercalated iron selenides formed via the liquid ammonia route. K(0.3)Fe(2)Se(2)(NH(3))(0.47) corresponds to the 44 K phase with lattice constant c = 15.56(1) Å and K(0.6)Fe(2)Se(2)(NH(3))(0.37) to the 30 K phase with c = 14.84(1) Å. With higher potassium doping, the 44 K phase can be converted into the 30 K phase. NH(3) has little, if any, effect on superconductivity. Thus, the conclusions should apply to both K(0.3)Fe(2)Se(2) and K(0.6)Fe(2)Se(2) SC phases. K(0.3)Fe(2)Se(2)(NH(3))(0.47) and K(0.6)Fe(2)Se(2)(NH(3))(0.37) stand out among known superconductors as their structures are stable only at particular potassium doping levels, and hence the variation of T(c) with doping is not dome-like.

Unraveling the storage mechanism in organic carbonyl electrodes for sodium-ion batteries.

Na-O layer provides Na+ diffusion pathway and storage site, whereas benzene layer provides e−conduction pathway and redox center. Organic carbonyl compounds represent a promising class of electrode materials for secondary batteries; however, the storage mechanism still remains unclear. We take Na2C6H2O4 as an example to unravel the mechanism. It consists of alternating Na-O octahedral inorganic layer and π-stacked benzene organic layer in spatial separation, delivering a high reversible capacity and first coulombic efficiency. The experiment and calculation results reveal that the Na-O inorganic layer provides both Na+ ion transport pathway and storage site, whereas the benzene organic layer provides electron transport pathway and redox center. Our contribution provides a brand-new insight in understanding the storage mechanism in inorganic-organic layered host and opens up a new exciting direction for designing new materials for secondary batteries.

Stable Oxoborate with Edge‐Sharing BO4 Tetrahedra Synthesized under Ambient Pressure

Analysis of an atom s coordination and the linkage of polyhedra is of vital importance for understanding crystal structures, especially considering our general inability to forecast structure types for new systems of elements. As a general rule, the presence of shared edges or faces of polyhedra in a coordinated structure is common for large cations, but scarcely seen for high-valence low coordinated small cations. This conclusion is the main thrust of the Pauling s third and fourth rules and is especially strict for compounds such as borates, 6] silicates, and phosphates. Until now, edge-sharing of those cation–oxygen (cation = B, Si, P) polyhedra was considered impossible except under extreme conditions. Unlike silicon and carbon, boron has the ability to bind to either three or four oxygen atoms to form a BO3 triangle or a BO4 tetrahedron. Polymerization of those B O blocks can give omnifarious types of anion groups (the BO3 and BO4 groups can occur isolated or linked in the form of rings, chains, layers, or networks) and endow over 1000 borate compounds with amazing structural diversity from triclinic symmetry to cubic symmetry. 11] On the basis of the borate structures discovered, Ross and Edwards in 1967 postulated that B O groups can only link to each other through common corners, not by edge-sharing or face-sharing. This hypothesis reduced the number of possible fundamental building blocks (FBB, the repeat B O block of the structure) greatly, making it possible for subsequent researchers to develop concise theories and clearer nomenclature for the unique borate structural chemistry. The hypothesis is valid except under extreme conditions. In 2002, Huppertz and van der Eltz claimed first violation of this hypothesis as they synthesized Dy4B6O15 under high pressure (HP) (8 GPa, 1000 K). Since then, several more edge-sharing HP borates have been synthesized under high-pressure/high-temperature conditions; thus, the appearance of edge-sharing BO4 is a significant phenomenon for distinguished HP borates. Herein, we present a novel borate KZnB3O6 synthesized under ambient pressure which is built from edge-sharing BO4 tetrahedra and is stable up to its melting point. Our work demonstrates that high pressure is not an indispensable prerequisite for the formation of edge-sharing BO4 polyhedra, and that the original hypothesis should be reexamined. KZnB3O6 was synthesized through solid-state reaction in air with K2CO3, H3BO3, and ZnO powders as the starting materials. The compound thus obtained is airand waterstable. The crystal structure was solved and refined on the basis of single-crystal data, which confirms the title compound to be the first ambient pressure borate with the edgesharing BO4 tetrahedra. Figure 1 shows the structure, in which the metal–borate framework is built up from corner-sharing B6O12 and Zn2O6 blocks, and weakly bonded K ions are

Graphene covered SiC powder as advanced photocatalytic material

Graphene covered SiC powder (GCSP) has been fabricated by well established method of high temperature thermal decomposition of SiC. The structural and photocatalystic characteristics of the prepared GCSP were investigated and compared with that of the pristine SiC powder. Under UV illumination, more than 100% enhancement in photocatalystic activity is achieved in degradation of Rhodamine B (Rh B) by GCSP catalyst than by pristine SiC powder. The possible mechanisms underlining the observed results are discussed. The results suggested that GCSP as a composite of graphene based material has great potential for use as a high performance photocatalyst.

Towards intrinsic magnetism of graphene sheets with irregular zigzag edges

The magnetism of graphene has remained divergent and controversial due to absence of reliable experimental results. Here we show the intrinsic magnetism of graphene edge states revealed based on unidirectional aligned graphene sheets derived from completely carbonized SiC crystals. It is found that ferromagnetism, antiferromagnetism and diamagnetism along with a probable superconductivity exist in the graphene with irregular zigzag edges. A phase diagram is constructed to show the evolution of the magnetism. The ferromagnetic ordering curie-temperature of the fundamental magnetic order unit (FMOU) is 820 ± 80 K. The antiferromagnetic ordering Neel temperature of the FMOUs belonging to different sublattices is about 54 ± 2 K. The diamagnetism is similar to that of graphite and can be well described by the Kotosonovs equation. Our experimental results provide new evidences to clarify the controversial experimental phenomena observed in graphene and contribute to a deeper insight into the nature of magnetism in graphene based system.

Exploring FeSe-based superconductors by liquid ammonia method

Our recent progress on the preparation of a series of new FeSe-based superconductors and the clarification of SC phases in potassium-intercalated iron selenides are reviewed here. By the liquid ammonia method, metals Li, Na, Ca, Sr, Ba, Eu, and Yb are intercalated in between FeSe layers and form superconductors with transition temperatures of 30 K~46 K, which cannot be obtained by high-temperature routes. In the potassium-intercalated iron selenides, we demonstrate that at least two SC phases exist, KxFe2Se2(NH3)y (x ≈ 0.3 and 0.6), determined mainly by the concentration of potassium. NH3 has little, if any, effect on superconductivity, but plays an important role in stabilizing the structures. All these results provide a new starting point for studying the intrinsic properties of this family of superconductors, especially for their particular electronic structures.