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Dr. Qi Hu Guomin Li Zhen Han Ziyu Wang Xiaowan Huang Dr. Hengpan Yang Prof. Qianling Zhang Prof. Jianhong Liu Prof. Chuanxin He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(18):3930-3942
Recently, nonmetal doping has exhibited its great potential for boosting the hydrogen evolution reaction (HER) of transition-metal (TM)-based electrocatalysts. To this end, this work overviews the recent achievements made on the design and development of the nonmetal-doped TM-based electrocatalysts and their performance for the HER. It is also shown that by rationally doping nonmetal elements, the electronic structures of TM-based electrocatalysts can be effectively tuned and in turn the Gibbs free energy of the TM for adsorption of H* intermediates (ΔGH*) optimized, consequently enhancing the intrinsic activity of TM-based electrocatalysts. Notably, we highlight that concurrently doping two nonmetal elements can continuously and precisely regulate the electronic structures of the TM, thereby maximizing the activity for HER. Moreover, nonmetal doping also accounts for enhancing the physical properties of the TM (i.e. surface area). Therefore, nonmetal doping is a robust strategy for simultaneous regulation of the chemical and physical features of the TM. 相似文献
13.
Dr. Peiyu Ge Dr. Mohamad Hojeij Dr. Micheál D. Scanlon Prof. Hubert H. Girault 《Chemphyschem》2020,21(24):2630-2633
H2 may be evolved biphasically using a polarised liquid|liquid interface, acting as a “proton pump”, in combination with organic soluble metallocenes as electron donors. Sustainable H2 production requires methodologies to recycle the oxidised donor. Herein, the photo-recycling of decamethylferrocenium cations (DcMFc+) using aqueous core-shell semiconductor CdSe@CdS nanoparticles is presented. Negative polarisation of the liquid|liquid interface is required to extract DcMFc+ to the aqueous phase. This facilitates the efficient capture of electrons by DcMFc+ on the surface of the photo-excited CdSe@CdS nanoparticles, with hydrophobic DcMFc subsequently partitioning back to the organic phase and resetting the system. TiO2 (P25) and CdSe semiconductor nanoparticles failed to recycle DcMFc+ due to their lower conduction band energy levels. During photo-recycling, CdS (on CdSe) may be self-oxidised and photo-corrode, instead of water acting as the hole scavenger. 相似文献
14.
飞行器液压导管受接头和卡箍等约束,在使用的振动环境中,会因弯曲应力而导致破裂,影响到飞行安全.本文对飞行器液压系统通用的不锈钢导管的裂纹萌生寿命进行了试验研究.首先在对8 mm、12 mm 无缺陷导管和含U 型缺口8 mm 导管的疲劳试验和有限元分析的基础上,得到了导管的最大拉应变-裂纹萌生寿命数据.然后采用基于强度极限和弹性模量估算法的Manson-Coffin 公式来预测导管裂纹萌生寿命.最后引入加载类型修正系数、表面质量修正系数、试样尺寸修正系数、应力集中敏感系数和有效应力集中系数,使修正后的公式对三种类型的导管均有较好的裂纹萌生寿命预测精度. 相似文献
15.
Ivan Dragičević Dr. Danijela Barić Dr. Borislav Kovačević Prof. Bernard T. Golding Dr. David M. Smith 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6132-6143
Model studies of prebiotic chemistry have revealed compelling routes for the formation of the building blocks of proteins and RNA, but not DNA. Today, deoxynucleotides required for the construction of DNA are produced by reduction of nucleotides catalysed by ribonucleotide reductases, which are radical enzymes. This study considers potential non‐enzymatic routes via intermediate radicals for the ancient formation of deoxynucleotides. In this context, several mechanisms for ribonucleotide reduction, in a putative H2S/HS. environment, are characterized using computational chemistry. A bio‐inspired mechanistic cycle involving a keto intermediate and HSSH production is found to be potentially viable. An alternative pathway, proceeding through an enol intermediate is found to exhibit similar energetic requirements. Non‐cyclical pathways, in which HSS. is generated in the final step instead of HS., show a markedly increased thermodynamic driving force (ca. 70 kJ mol?1) and thus warrant serious consideration in the context of the prebiotic ribonucleotide reduction. 相似文献
16.
Xueying Jia Prof. Dr. Carsten Streb Prof. Dr. Yu-Fei Song 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(68):15548-15554
Polyoxometalates (POMs) are promising catalysts for the electrochemical hydrogen production from water owing to their high intrinsic catalytic activity and chemical tunability. However, poor electrical conductivity and easy detachment of the POMs from the electrode cause significant challenges under operating condition. Herein, a simple one-step hydrothermal method is reported to synthesize a series of Dexter–Silverton POM/Ni foam composites (denoted as Ni M -POM/Ni; M =Co, Zn, Mn), in which the stable linkage between the POM catalysts and the Ni foam electrodes lead to high activity for the hydrogen evolution reaction (HER). Among them, the highest HER performance can be observed in the NiCo-POM/Ni, featuring an overpotential of 64 mV (at 10 mA cm−2, vs. reversible hydrogen electrode), and a Tafel slope of 75 mV dec−1 in 1.0 m aqueous KOH. Moreover, the NiCo-POM/Ni catalyst showed a high faradaic efficiency ≈97 % for HER. Post-catalytic of NiCo-POM/Ni analyses showed virtually no mechanical or chemical degradation. The findings propose a facile and inexpensive method to design stable and effective POM-based catalysts for HER in alkaline water electrolysis. 相似文献
17.
Yaping Chen Dr. Kun Rui Prof. Jixin Zhu Prof. Shi Xue Dou Dr. Wenping Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):703-713
Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed. 相似文献
18.
Xiaolin Xing Dr. Rongji Liu Kecheng Cao Prof. Ute Kaiser Prof. Carsten Streb 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(47):11098-11104
The rapid development of renewable-energy technologies such as water splitting, rechargeable metal–air batteries, and fuel cells requires highly efficient electrocatalysts capable of the oxygen-reduction reaction (ORR) and the oxygen-evolution reaction (OER). Herein, we report a facile sonication-driven synthesis to deposit the molecular manganese vanadium oxide precursor [Mn4V4O17(OAc)3]3− on multiwalled carbon nanotubes (MWCNTs). Thermal conversion of this composite at 900 °C gives nanostructured manganese vanadium oxides/carbides, which are stably linked to the MWCNTs. The resulting composites show excellent electrochemical reactivity for ORR and OER, and significant reactivity enhancements compared with the precursors and a Pt/C reference are reported. Notably, even under harsh acidic conditions, long-term OER activity at low overpotential is reported. In addition, we report exceptional activity of the composites for the industrially important Cl2 evolution from an aqueous HCl electrolyte. The new composite material shows how molecular deposition routes leading to highly active and stable multifunctional electrocatalysts can be developed. The facile design could in principle be extended to multiple catalyst classes by tuning of the molecular metal oxide precursor employed. 相似文献
19.
Sung Hwan Koo Dong Jun Li Taeyeong Yun Dong Sung Choi Kyung Eun Lee Gil Yong Lee Youngtak Oh Joonwon Lim Suchithra Padmajan Sasikala Ho Jin Lee In Ho Kim Hong Ju Jung Rishabh Jain Sang Ouk Kim 《Particle & Particle Systems Characterization》2019,36(7)
Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS2, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec?1 and a charge transfer resistance (Rct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer. 相似文献
20.