Artificial Heterointerfaces with Regulated Charge Distribution of Ni Active Sites for Urea Oxidation Reaction.

In contrast to the thermodynamically unfavorable anodic oxygen evolution reaction, the electrocatalytic urea oxidation reaction (UOR) presents a more favorable thermodynamic potential. However, the practical application of UOR has been hindered by sluggish kinetics. In this study, hierarchical porous nanosheet arrays featuring abundant Ni-WO3 heterointerfaces on nickel foam (Ni-WO3/NF) is introduced as a monolith electrode, demonstrating exceptional activity and stability toward UOR. The Ni-WO3/NF catalyst exhibits unprecedentedly rapid UOR kinetics (200 mA cm-2 at 1.384 V vs. RHE) and a high turnover frequency (0.456 s-1), surpassing most previously reported Ni-based catalysts, with negligible activity decay observed during a durability test lasting 150 h. Ex situ X-ray photoelectron spectroscopy and density functional theory calculations elucidate that the WO3 interface significantly modulates the local charge distribution of Ni species, facilitating the generation of Ni3+ with optimal affinity for interacting with urea molecules and CO2 intermediates at heterointerfaces during UOR. This mechanism accelerates the interfacial electrocatalytic kinetics. Additionally, in situ Fourier transform infrared spectroscopy provides deep insights into the substantial contribution of interfacial Ni-WO3 sites to UOR electrocatalysis, unraveling the underlying molecular-level mechanisms. Finally, the study explores the application of a direct urea fuel cell to inspire future practical implementations.

Enabling Internal Electric Field in Heterogeneous Nanosheets to Significantly Accelerate Alkaline Hydrogen Electrocatalysis.

Efficient bifunctional hydrogen electrocatalysis, encompassing both hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR), is of paramount significance in advancing hydrogen-based societies. While non-precious-metal-based catalysts, particularly those based on nickel (Ni), are essential for alkaline HER/HOR, their intrinsic catalytic activity often falls short of expectations. Herein, an internal electric field (IEF) strategy is introduced for the engineering of heterogeneous nickel-vanadium oxide nanosheet arrays grown on porous nickel foam (Ni-V2 O3 /PNF) as bifunctional electrocatalysts for hydrogen electrocatalysis. Strikingly, the Ni-V2 O3 /PNF delivers 10 mA cm-2 at an overpotential of 54 mV for HER and a mass-specific kinetic current of 19.3 A g-1 at an overpotential of 50 mV for HOR, placing it on par with the benchmark 20% Pt/C, while exhibiting enhanced stability in alkaline electrolytes. Density functional theory calculations, in conjunction with experimental characterizations, unveil that the interface IEF effect fosters asymmetrical charge distributions, which results in more thermoneutral hydrogen adsorption Gibbs free energy on the electron-deficient Ni side, thus elevating the overall efficiency of both HER and HOR. The discoveries reported herein guidance are provided for further understanding and designing efficient non-precious-metal-based electrocatalysts through the IEF strategy.

Heteroatom-Induced Accelerated Kinetics on Nickel Selenide for Highly Efficient Hydrazine-Assisted Water Splitting and Zn-Hydrazine Battery.

Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production. Rational design of bifunctional electrocatalysts, which can simultaneously accelerate hydrogen evolution reaction (HER)/hydrazine oxidation reaction (HzOR) kinetics, is the key step. Herein, we demonstrate the development of ultrathin P/Fe co-doped NiSe2 nanosheets supported on modified Ni foam (P/Fe-NiSe2) synthesized through a facile electrodeposition process and subsequent heat treatment. Based on electrochemical measurements, characterizations, and density functional theory calculations, a favorable "2 + 2" reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated. P/Fe-NiSe2 thus yields an impressive electrocatalytic performance, delivering a high current density of 100 mA cm-2 with potentials of - 168 and 200 mV for HER and HzOR, respectively. Additionally, P/Fe-NiSe2 can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine (Zn-Hz) battery, making it promising for practical application.

Rational Synthesis of Core-Shell-Structured Nickel Sulfide-Based Nanostructures for Efficient Seawater Electrolysis.

Versatile electrocatalysis at higher current densities for natural seawater splitting to produce hydrogen demands active and robust catalysts to overcome the severe chloride corrosion, competing chlorine evolution, and catalyst poisoning. Hereto, the core-shell-structured heterostructures composed of amorphous NiFe hydroxide layer capped Ni3 S2 nanopyramids which are directly grown on nickel foam skeleton (NiS@LDH/NF) are rationally prepared to regulate cooperatively electronic structure and mass transport for boosting oxygen evolution reaction (OER) performance at larger current densities. The prepared NiS@LDH/NF delivers the anodic current density of 1000 mA cm-2 at the overpotential of 341 mV in 1.0 m KOH seawater. The feasible surface reconstruction of Ni3 S2 -FeNi LDH interfaces improves the chemical stability and corrosion resistance, ensuring the robust electrocatalytic activity in seawater electrolytes for continuous and stable oxygen evolution without any hypochlorite production. Meanwhile, the designed Ni3 S2 nanopyramids coated with FeNi2 P layer (NiS@FeNiP/NF) still exhibit the improved hydrogen evolution reaction (HER) activity in 1.0 m KOH seawater. Furthermore, the NiS@FeNiP/NF||NiS@LDH/NF pair requires cell voltage of 1.636 V to attain 100 mA cm-2 with a 100% Faradaic efficiency, exhibiting tremendous potential for hydrogen production from seawater.

Activity Promotion of Core and Shell in Multifunctional Core-Shell Co2 P@NC Electrocatalyst by Secondary Metal Doping for Water Electrolysis and Zn-Air Batteries.

Developing cost-efficient multifunctional electrocatalysts is highly critical for the integrated electrochemical energy-conversion systems such as water electrolysis based on hydrogen/oxygen evolution reactions (HER/OER) and metal-air batteries based on OER/oxygen reduction reactions (ORR). The core-shell structured materials with transition metal phosphide as the core and nitrogen-doped carbon (NC) as the shell have been known as promising HER electrocatalysts. However, their oxygen-related electrocatalytic activities still remain unsatisfactory, which severely limits their further applications. Herein an effective strategy to improve the core and shell performances of core-shell Co2 P@NC electrocatalysts through secondary metal (e.g., Fe, Ni, Mo, Al, Mn) doping (termed M-Co2 P@M-N-C) is reported. The as-synthesized M-Co2 P@M-N-C electrocatalysts show multifunctional HER/OER/ORR activities and good integrated capabilities for overall water splitting and Zn-air batteries. Among the M-Co2 P@M-N-C catalysts, Fe-Co2 P@Fe-N-C electrocatalyst exhibits the best catalytic activities, which is closely related to the configuration of highly active species (Fe-doping Co2 P core and Fe-N-C shell) and their subtle synergy, and a stable carbon shell for outstanding durability. Combination of electrochemical-based in situ Fourier transform infrared spectroscopy with extensive experimental investigation provides deep insights into the origin of the activity and the underlying electrocatalytic mechanisms at the molecular level.

Mesoporous CdxZn1-xS with abundant surface defects for efficient photocatalytic hydrogen production.

The practical application of photocatalytic water splitting for hydrogen evolution hinges on the development of high-efficient and low-cost photocatalysts. Defects engineering has emerged as a promising strategy to enhance photocatalytic activity effectively. Herein, a facile and versatile co-precipitation method is proposed to fabricate mesoporous Cd-Zn-S solid solutions (E-CdxZn1-xS) with abundant surface defects by the inorganic salts formed in the reaction system as self-template. Compared with Cd-Zn-S solid solutions (W-Cd0.65Zn0.35S) prepared by the traditional co-precipitation method, the enhanced specific surface area and abundant surface defects endow E-Cd0.65Zn0.35S with more accessible active sites and effective separation of electron-hole pairs for the photocatalytic water splitting reaction. The E-Cd0.65Zn0.35S solid solution exhibits hydrogen evolution rate of 5.2 mmol h-1 g-1 without loading noble metal as cocatalyst under visible light, which is 1.13 times higher than that of W-Cd0.65Zn0.35S sample. The present work provides a simple, low-cost and prospective strategy for the synthesis of defective Cd-Zn-S solid solutions, and it also delivers guidance to design and develop the advanced visible-light photocatalyst in the future.

Endowing TADF luminophors with AIE properties through adjusting flexible dendrons for highly efficient solution-processed nondoped OLEDs.

The amalgamation of thermally activated delayed fluorescence (TADF) and aggregation-induced emission (AIE) properties, termed AIE-TADF, is a promising strategy to design novel robust luminescent materials. Herein, we transform 2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile (5CzBN) from an ACQ molecule into an AIEgen by simply decorating the 5CzBN core with alkyl chain-linked spirobifluorene dendrons. By increasing the number of flexible dendrons, these materials can not only show obvious AIE-TADF characteristics and uniform film morphology, but can also exhibit better resistance to isopropyl alcohol, which are beneficial to fully solution-processed OLEDs. Notably, 5CzBN-PSP shows great device efficiency with an external quantum efficiency (EQE), current efficiency and power efficiency of 20.1%, 58.7 cd A-1 and 46.2 lm W-1, respectively and achieved record-breaking efficiency in solution-processed nondoped OLEDs based on AIE emitters. This work demonstrates a general approach to explore new efficient emitters by the marriage of AIE and TADF which could potentially improve their performance in various areas.

Waterlogging accelerates the loss of soil organic carbon from abandoned paddy fields in the hilly terrain in subtropical China.

Paddy soils have been widely recognized as important carbon sinks. However, paddy field abandonment is increasing in the hilly area in subtropical China. Soil waterlogging and weed burning are common practices in abandoned paddy fields, which could affect vegetation cover and carbon sequestration. An rice cultivation experiment was ceased in 2006, and four new treatments were applied as waterlogging (W), drainage (D), waterlogging combined with burning (WB), and drainage combined with burning (DB). Waterlogging altered the vegetation cover and caused an associated change in biomass. Paspalum paspaloides, Murdannia triquetra, and Bidens frondosa dominated W and WB plots, and Microstegium vimineum and Bidens frondosa dominated D and DB plots. Abandonment of paddy fields led to a rapid decrease in soil organic carbon (SOC), and waterlogging accelerates SOC loss which should be attributed mainly to alteration of the vegetation cover. Six years' rice cultivation increased SOC content by 13.5% (2.4 g kg-1) on average. In contrast, six years' abandonment reduced SOC content by 14.5% (3.0 g kg-1) on average. Decline rate of SOC was 0.38, 0.64, 0.30, and 0.65 g kg-1 a-1 for D, W, DB, and WB, respectively. Such results indicate a significant risk of SOC loss from abandoned paddy fields.

N,N'-Di-p-tolyl-ethyl-enediamine.

The asymmetric unit of the title compound, C(16)H(20)N(2), contains two independent mol-ecules. The rings in each mol-ecule are oriented at dihedral angles of 78.94 (3) and 77.76 (3)°.