Chemical control of superconducting properties of (Y, Ca)(Sr, Ba)2Cu2.7Ga0.3O7?δ

The partial substitution of Ga at the Cu(1) (chain) sites of the YBa₂Cu₃O₇ structure allows synthesis at ambient pressure of Ba-free analogs, e.g., YSr₂Cu_2.7Ga_0.3O_7– . Materials with this composition have been found to be nonsuperconducting, but superconductivity has been induced by one or more of the following methods: Ca substitutions at the Y site; Ba substitutions at the Sr site; annealing in high-pressure oxygen. The influence of these chemical manipulations onT _c has been monitored and all methods have been found to enhanceT _c . The electronic effects of Ba substitutions have been deduced indirectly using powder neutron diffraction, and such substitutions appear to result in a redistribution of hole density into the Cu(1) sites from the superconducting CuO₂ planes.     

Single-crystal growth and anisotropic electrical properties of (La1?xCax)2CaCu2O6

Large single crystals of (La_1–x Ca _x )₂CaCu₂O₆ were synthesized by the travelling solvent floating zone (TSFZ) technique. The dimension of the grown boules was typically 4 mm×30 mm long with thec-axis perpendicular to the growth direction. After oxygen loading at 1080°C in 400 atm of O₂, they became superconductive with a sharp transition at around 50 K. The resistivity was metallic both along thec-axis and within theab-plane, with an anisotropy ratio of ²( _c/ _ab ) 50 which is almost independent of temperature. Details of the crystal growth, heat treatment procedures, and the results of electrical and magnetic property measurements are presented.     

Synthesis, composition, and structure of superconducting (Y, Ca)Sr, Ba)2Cu2GaO7?δ

The superconducting properties of Y_1–y Ca _y Sr₂Cu₂GaO_7– have been examined and related to the Ca content,y, and the use of annealing treatments at 350 bar oxygen. Superconductivity withT _c up to 41 K was found only for high-pressure-annealed samples, and the structural effects of Ca substitution and high-pressure treatment were examined using powder neutron diffraction. Small but significant changes in Cu-Cu and Cu-O distances were found and suggest that the Cu ions are more highly charged in superconducting samples. Partial substitution of Ba for Sr was found to be possible (up to 20%) to give samples which, after annealing in high-pressure oxygen, were superconducting at temperatures up to 68 K.     

Doped/Undoped A1-A2 Typed Copolymers as ETLs for Highly Efficient Organic Solar Cells

The electron transport layer (ETL) is a critical component in achieving high device performance and stability in organic solar cells. Conjugated polyelectrolytes (CPEs) have become an attractive alternative due to film-forming properties and ease of preparation. However, p-type CPEs generally exhibit poor charge mobility and conductivity, incorporation of electron-withdrawing units forming alternated D-A conjugated backbone can make up for these deficiencies. Herein, the ratio of electron withdrawing moieties are further increased and two poly(A1-alt-A2) typed PIIDNDI-Br and PDPPNDI-Br based on the combination of naphthalene diimide (NDI) with isoindigo (IID) or diketopyrrolopyrrole (DPP) via direct arylation polycondensation are synthesized. These CPEs possess excellent alcohol solubility, a suitable lowest unocuppied molecular orbital energy level, and work function tunability. Surprisingly, the incorporation of IID and DPP units generate distinct self-doping behaviors, which are confirmed by UV–vis absorption and ESR spectra. However, no matter doped or undoped, both CPEs present better charge-transporting properties and conductivity when utilized as ETLs. The PIIDNDI-Br and PDPPNDI-Br display good universal compatibility with the blend of PM6:Y6 and PM6:L8-BO, and PCEs of 18.32% and 18.36% are obtained, respectively, which also present excellent storage stability. In short, the combination of two different acceptors demonstrates an efficient strategy to design highly efficient ETLs for high performance photovoltaic devices.     

Bifunctional Edge-Rich Nitrogen Doped Porous Carbon for Activating Oxygen and Sulfur

Oxygen reduction reaction (ORR) and sulfur reduction reaction (SRR) play key roles in advanced batteries. However, they both suffer from sluggish reaction kinetics. Here, an interesting nitrogen doped porous carbon material that can simultaneously activate oxygen and sulfur is reported. The carbon precursor is a nitrogen containing covalent organic framework (COF), constituting periodically stacked 2D sheets. The COF structure is well preserved upon pyrolysis, resulting in the formation of edge-rich porous carbon with structure resembling stacked holey graphene. The nitrogen containing groups in the COF are decomposed into graphitic and pyridinic nitrogen during pyrolysis. These edge sites and uniform nitrogen doping endow the carbon product with high intrinsic catalytic activities toward ORR and SRR. The COF derived carbon delivers outstanding performances when assembling as cathodes in the Li-S and Li-O₂ batteries. Simultaneous activation of oxygen and sulfur also enables a new battery chemistry. A proof-of-concept Li-S/O₂ hybrid battery is assembled, delivering a large specific capacity of 2,013 mAh g⁻¹. This study may inspire novel battery designs based on oxygen and sulfur chemistry.     

Reducing Hysteresis and Enhancing Performance of Perovskite Solar Cells Using Low‐Temperature Processed Y‐Doped SnO2 Nanosheets as Electron Selective Layers

Despite the rapid increase of efficiency, perovskite solar cells (PSCs) still face some challenges, one of which is the current–voltage hysteresis. Herein, it is reported that yttrium‐doped tin dioxide (Y‐SnO₂) electron selective layer (ESL) synthesized by an in situ hydrothermal growth process at 95 °C can significantly reduce the hysteresis and improve the performance of PSCs. Comparison studies reveal two main effects of Y doping of SnO₂ ESLs: (1) it promotes the formation of well‐aligned and more homogeneous distribution of SnO₂ nanosheet arrays (NSAs), which allows better perovskite infiltration, better contacts of perovskite with SnO₂ nanosheets, and improves electron transfer from perovskite to ESL; (2) it enlarges the band gap and upshifts the band energy levels, resulting in better energy level alignment with perovskite and reduced charge recombination at NSA/perovskite interfaces. As a result, PSCs using Y‐SnO₂ NSA ESLs exhibit much less hysteresis and better performance compared with the cells using pristine SnO₂ NSA ESLs. The champion cell using Y‐SnO₂ NSA ESL achieves a photovoltaic conversion efficiency of 17.29% (16.97%) when measured under reverse (forward) voltage scanning and a steady‐state efficiency of 16.25%. The results suggest that low‐temperature hydrothermal‐synthesized Y‐SnO₂ NSA is a promising ESL for fabricating efficient and hysteresis‐less PSC.     

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte

Nitrogen and sulfur‐codoped graphene composites with Co₉S₈ (NS/rGO‐Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO₂ catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only ?0.193 V to reach 10 mA cm^?2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half‐wave potential in ORR and the potential to reach 10 mA cm^?2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm^?2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S‐codoped rGO, and Co₉S₈ nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions.     

Cobalt Phosphide Coupled with Heteroatom‐Doped Nanocarbon Hybrid Electroctalysts for Efficient,Long‐Life Rechargeable Zinc–Air Batteries

Metal phosphides and heteroatom‐doped carbons have been regarded as promising candidates as bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, both have suffered from stability issues during repeated ORR and OER operations in zinc–air batteries (ZABs). Herein, this study reports a versatile cobalt‐based hybrid catalyst with a 1D structure by integrating the metal‐organic framework‐derived conversion approach and an in situ crosslinking method. Among them, the 1D hybrid catalyst composed of ultrasmall cobalt phosphide nanoparticles supported by nitrogen‐, sulfur‐, phosphorus‐doped carbon matrix shows remarkable bifunctional activity close to that of the benchmark precious‐metal catalysts along with an excellent durability in the full potential range covering both the OER and ORR. The overall overpotential of the rechargeable ZABs can be greatly reduced with this bifunctional hybrid catalyst as an air‐electrode, and the cycling stability outperforms the commercial Pt/C catalyst. It is revealed that the cobalt phosphide nanoparticles are in situ converted to cobalt oxide under the accelerated conditions during OER (and/or ORR) of the ZABs and reduces the anodic current applied to the carbon. This contributes to the stability of the carbon material and in maintaining the high initial catalytic properties of the hybrid catalyst.