摘要：Main observation and conclusion Important progress has been made in the development of energetic molecules with high performance by computer-aided molecular design in recent years,but structural novelty of organic scaffolds is *** this work,we propose an intra-ring bridging strategy inspired by the known energetic nitramines to design novel polycyclic and cage energetic *** than 100 energetic structures were designed by introducing the C—C bridges and increasing the ring *** synthesis difficulty is considered besides the two most concerned properties of EMs,energy and *** a comprehensive estimation,a symmetric cage molecule labeled as 8U-30 was finally selected because of its relatively high detonation performance,and comparable impact sensitivity as well as synthetic accessibility with ***,the proposed strategy could be utilized in further molecular design to gain various scaffolds,especially cage structures,for different demands.

摘要：n型硅(n-Si)表面在水溶液中容易被氧化和钝化,导致其在光电化学(PEC)分解水的析氧反应(OER)动力学缓慢。本工作通过欠电位沉积成功地在p^(+)n-Si基底上电沉积了三金属Ni_(0.9)Fe_(0.05)Co_(0.05)保护层。制备的Ni_(0.9)Fe_(0.05)Co_(0.05)/p^(+)n-Si光阳极具有优异的稳定性和PEC水氧化活性,具有相对低的OER起始电位(相对于可逆氢电极电势(RHE)仅为0.938 V),并且在1.23 V ***电位时具有较高的光电流密度(33.1 m A·cm^(-2)),显著优于Ni/p^(+)n-Si光阳极。工作证明了Fe在Ni层的掺杂会在Ni_(0.9)Fe_(0.05)Co_(0.05)/p^(+)n-Si界面处产生较大的能带弯曲,促进界面电荷分离。此外,Co的加入会产生丰富的Ni^(3+)和氧空位(Ov),作为活性位点可以加速OER动力学过程,协同促进PEC过程中的水氧化的活性。令人鼓舞的是,通过将Ni_(0.9)Fe_(0.05)Co_(0.05)/p^(+)n-Si光阳极连接到廉价的硅太阳能电池上,所制备的集成光伏/PEC(PV/PEC)器件实现了无偏压下高达12.0%的太阳制氢能量转换效率。这项工作提供了一种简单的方法来设计高效、稳定的n-Si基光阳极,并对其构效关系有了深刻的理解;这种方法制备的材料在集成低成本PV/PEC器件用于无辅助太阳能驱动水分解方面具有巨大的潜力。

摘要：The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2) reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N_(4)-C)configuration to obtain Ni-X-N_(3)-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni *** these obtained Ni-X-N_(3)-C(X:S,Se,and Te)SACs,Ni-Se-N_(3)-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98% at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2) battery integrated with Ni-Se-N_(3)-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm^(-2) and maintained remarkable rechargeable stability over 20 ***-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N_(4)-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)***,for Ni-Se-N_(3)-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of ^(*)COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.

摘要：A novel metal/semiconductor photocatalyst,Cu nanoparticles(NPs)modified TiO2 hollow spheres(Cu/TiO2),was designed for efficient photocatalytic overall water splitting(POWS)under both ultraviolet(UV)and visible(Vis)*** Cu/TiO2 photocatalyst possesses excellent POWS performance under Vis light at the highest level among the reported TiO2-based ***,the metal/semiconductor junction formed between Cu and TiO2 enables controlled water-oxidation product selectivity(H2O2 or O2)via different reaction pathways regulated by irradiation *** UV light,the electrons excited in TiO2 are captured by Cu NPs through the Cu/TiO2 Schottky interface for H2 production,with the photoholes in TiO2 producing H2O2 through a two-electron process;whilst under Vis light,Cu NPs act as plasmon to inject hot electrons to TiO2 for H2 production,while O2 is produced by hot holes on Cu NPs via a four-electron *** rational design of function-switchable metal/semiconductor junction may be helpful to understand the mechanisms for POWS with desired gas/liquid water-oxidation products.