Ultrafast Quasi-Solid-State Microwave Construction of Spongy Cobalt-Molybdenum Phosphide for Hydrogen Production Over Wide pH Range.

The developed strategies for synthesizing metal phosphides are usually cumbersome and pollute the environment. In this work, an ultrafast (30 s) quasi-solid-state microwave approach is developed to construct cobalt-molybdenum phosphide decorated with Ru (Ru/CoxP-MoP) featured porous morphology with interconnected channels. The specific nanostructure favors mass transport, such as electrolyte bubbles transfer and exposing rich active sites. Moreover, the coupling effects between metallic elements, especially the decorated Ru, also act as a pivotal role on enhancing the electrocatalytic performance. Benefiting from the effects of composition and specific nanostructure, the prepared Ru/CoxP-MoP exhibits efficient HER performance with a current density of 10 mA cm-2 achieved in 1 m KOH, 0.5 m H2SO4, seawater containing 1 m KOH and 1 m PBS, with overpotentials of 52, 59, 55, 90 mV, and coupling with good stability. This work opens a novel and fast avenue to design metal-phosphide-based nanomaterials in energy-conversion and storage fields.

Sulfur-Induced Electronic Optimization of N-Doped Carbon with CoP/Co2P Heterostructure by Precursor Design for Rechargeable Zinc-Air Batteries.

Heteroatom doping and heterostructure construction are the key methods to improve the performance of electrocatalysts. However, developing such catalysts remains a challenging task. Herein, we designed two comparable polymers, phytic acid/thiourea polymer (PATP) and phytic acid/urea polymer (PAUP), as precursors, which contain C, N, S/O, and P by microwave heating. To pinpoint how the introduction of sulfur would affect the electronic structure and catalytic activity, these two polymers were physically blended with CoCo-Prussian blue analogue (CoCo-PBA) and further calcination, respectively. The highly dispersed CoP/Co2P-rich interfacial catalysts anchored on the N,S-codoped or N-doped carbon support were successfully prepared (CoP/Co2P@CNS and CoP/Co2P@CN). The prepared CoP/Co2P@CNS catalyst showed good ORR properties (E1/2 = 0.856 V vs RHE) and OER properties (Ej10 = 1.54 V vs RHE), which were superior to the commercial Pt/C and RuO2 catalysts. The reversible oxygen electrode index (ΔE = Ej10 - E1/2) can reach ∼0.684 V. Meanwhile, the rechargeable zinc-air battery assembled with a CoP/Co2P@CNS catalyst as the air cathode also showed excellent performance, with a charge-discharge cycle stability of up to 900 h. DFT calculations further confirm that the introduction of S atoms can affect the electronic structure and enhance the catalytic activity of C and N atoms on carbon support.

Construction of Quench-Induced Ru-Doped CoNiP Hierarchical Spheres for Hydrogen Evolution at High Current Densities.

Optimizing the electronic configuration improved the electrocatalytic performance of Ru doping. However, efficiently doping Ru and ensuring its stability in the hollow hierarchical structure posed a challenge. This work innovatively utilized the huge temperature difference between calcination and ice water (0 °C) to rapidly dope Ru atoms onto the CoNiP hierarchical spheres. Notably, the Ru-anchored hierarchical spheres enhanced the active area and internal space utilization. In addition, the addition of Ru dopant optimized the electronic structure and hydrogen evolution reaction (HER) kinetics of CoNiP. Surprisingly, Ru-CoNiP only required 250 mV to generate 1 A cm-2, which was 1.5 times that of commercial Pt/C. Moreover, its activation energy (Ea) was 24.3% lower than CoNiP, further confirming that the Ru dopant reduced the energy barrier of alkaline HER. In conclusion, this work proposed a new method for promoting the doping of trace amounts of ruthenium into hierarchical spheres through quenching.

Dense r-Ru/FeCoP heterointerfaces induced by a defect-assisted strategy for ultrastable alkaline overall water splitting.

Simplifying the anchoring process of Ru nanoparticles (NPs) and activating their bifunctional activity are challenges in the construction of Ru-based catalysts. In this work, FeCoP nanosheets anchored by Ru NPs (r-Ru/FeCoP) were innovatively synthesized using an oxygen defect-assisted-gas-phase phosphorization strategy. Surprisingly, the η100 values of r-Ru/FeCoP in the alkaline hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) processes were 0.8 and 0.58 times those of Pt/C and RuO2, respectively. Notably, the rich Ru NPs as HER active sites on r-Ru/FeCoP enhanced the conductivity of the catalyst and promoted the reaction kinetics for HER, while the metal atoms on the FeCoP nanosheets served as OER active sites to accelerate the desorption of O2. The synergy between the two promoted the improvement of overall water splitting efficiency. Overall, this work provides a new approach for the development of low-cost bifunctional catalysts with high Ru utilization.

Quenching-induced anion defects and precise Ru doping on Co3O4/CoN heterostructures for efficient overall water splitting performance.

The difficulty of nitride modification is to develop simple and efficient strategies to induce defects and efficiently capture Ru atoms. With these in mind, this work innovatively constructed a Ru-Co3O4/CoN-L catalyst with abundant anion defects (oxygen vacancies (VO) and nitrogen vacancies (VN)) using the nitridation-quenching-Ru doping strategy. Surprisingly, the porous structure provided more active sites, and the VN and VO were conducive to promoting the anchoring of Ru atoms. These significantly improved the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances of the Ru-Co3O4/CoN/NF-L catalyst. The density functional theory results showed that the anion defects optimized the hydrogen adsorption capacity of the Ru active sites for the HER. Furthermore, Ru dopants and anion defects reduced the OER energy barrier of the Co-active sites, accelerating the HER and OER kinetics. This study proposes a new concept for defect construction and nitride-structure optimization.

Congenital heart disease detection by pediatric electrocardiogram based deep learning integrated with human concepts.

Early detection is critical to achieving improved treatment outcomes for child patients with congenital heart diseases (CHDs). Therefore, developing effective CHD detection techniques using low-cost and non-invasive pediatric electrocardiogram are highly desirable. We propose a deep learning approach for CHD detection, CHDdECG, which automatically extracts features from pediatric electrocardiogram and wavelet transformation characteristics, and integrates them with key human-concept features. Developed on 65,869 cases, CHDdECG achieved ROC-AUC of 0.915 and specificity of 0.881 on a real-world test set covering 12,000 cases. Additionally, on two external test sets with 7137 and 8121 cases, the overall ROC-AUC were 0.917 and 0.907 while specificities were 0.937 and 0.907. Notably, CHDdECG surpassed cardiologists in CHD detection performance comparison, and feature importance scores suggested greater influence of automatically extracted electrocardiogram features on CHD detection compared with human-concept features, implying that CHDdECG may grasp some knowledge beyond human cognition. Our study directly impacts CHD detection with pediatric electrocardiogram and demonstrates the potential of pediatric electrocardiogram for broader benefits.