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Currently, there are still many limitations in the research of conductive metal-organic frameworks (MOFs) in the field of electrocatalysis. On the one hand, most MOFs have a solid construction, seriously hindering their mass transfer process. On the other hand, innate bonding is not conducive to the optimization of electronic structures and the excitation of intrinsic active sites. Therefore, external/internal dual-control of MOFs is urgently needed to break the shackles of their activity. Herein, the hollow RuCoCu-MOF/CF nanorods with tunable cavities are directionally constructed by a self-sacrificial template method. Benefiting from the exact morphological control and the unique Ru–O–Co bond bridge, RuCoCu-MOF/CF exhibits superior performances for alkaline hydrogen evolution reaction (HER) and urea oxidation reaction (UOR). Surprisingly, a record-breaking voltage of 1.402 V drives a current density of 10 mA cm−2 for urea-assisted overall water splitting under alkaline conditions, greatly promoting the development of energy-efficient hydrogen production technology. This work firstly constructed the MOF-based self-supporting electrode with ultra-high urea-assisted hydrogen production and urea degradation performances via the dual controls of the cavity size and chemical bond bridge. This points out the direction for the development of unique integrated electrodes for both hydrogen production and decontamination. "External and internal dual-controls" strategy of the cavity size and chemical bridge construction in RuCoCu-MOF nanorod achieves bifunctional catalysis of urea-assisted energy-saving hydrogen production and urea decomposition. Surprisingly, the unique structure and the formation of the Ru–O–Co bond bridge make RuCoCu-MOF/CF only need a voltage of 1.402 V to reach a current density of 10 mA cm−2 in the energy-efficient HER||UOR electrolyzer, this excellent value represents the highest performance of overall water splitting under alkaline conditions. Besides, RuCoCu-MOF/CF also achieves 2.21 times higher HER activity than commercial Pt/C/CF and splendid UOR properties in the alkaline solution. [Display omitted] • The controllable cavity was constructed by the balance of dissolution-coordination and nucleation-growth processes. • The Ru–O–Co bond bridge as the electron channel optimizes the electronic configuration. • RuCoCu-MOF/CF achieves the record-breaking urea-assisted overall water splitting performance (V 10 = 1.402 V). • RuCoCu-MOF/CF achieves the ultra-low overpotential of 11.6 mV at η 10 for HER, which is better than that of Pt/C/CF. • The ultra-low onset potential of 1.32 V is displayed in RuCoCu-MOF for UOR. [ABSTRACT FROM AUTHOR]

The hydrogen energy generated by the electrocatalytic water splitting reaction has been established as a renewable and clean energy carrier with ultra‐high energy density, which can well make up for shortcomings of conventional renewable energy sources, such as geographical limitations, climatic dependence, and energy wastage. Notably, the introduction of electrocatalysts can enhance the efficiency of the water splitting process to generate hydrogen. Particularly, the heterostructure electrocatalysts constructed by coupling multiple components (or phases) have emerged as the most promising option for water splitting due to the well‐known electronic and synergistic effects. The existing reviews on interface engineering for electrocatalyst design mostly focus on the relationship between the heterostructures and specific electrocatalytic reactions. However, a comprehensive overview of the integration of model building, directional synthesis, and electrocatalytic mechanism has been rarely reported. To this end, in this review, the development of heterostructure catalysts is systematically introduced from the perspective of interface classification, interface growth and synthesis, and regulation of electrocatalytic performance based on the interfacial microenvironment (bonding, electronic configuration, lattice strain, etc.), thereby offering useful insights on the design and construction of interfacial models. Besides, combined with the current development and applications of interface engineering strategies, the challenges of future heterostructure catalysts are discussed and relevant solutions are proposed. Overall, this review can serve as a useful theoretical reference for the integration of interfacial model building, directional synthesis, and electrocatalytic mechanism, which can further promote the development of hydrogen production technologies with low energy consumption and high yield. [ABSTRACT FROM AUTHOR]

Currently, the construction of heterostructures to optimize electrocatalytic activities is a hot research topic, since there is still a certain gap between the electrocatalytic properties of these heterostructures and that of Pt/C. With this in mind, we utilized in‐situ vapor‐phase phosphorization‐sulfurization to obtain the CoP3/MoS2−Co0.75Mo3S3.75 (CoP/CoMoS, for short) heterostructure on carbon cloth (CC), which exhibits Pt‐like electrocatalytic performance and excellent stability in acid electrolyte. Activated by CoP3 active phase, the electronic configuration of CoMoS and the adsorption energy of H* (▵GH*) are greatly optimized. Meanwhile, the rapid oxidation of CoMoS phase can be effectively avoided under the protection of CoP3 layer. This work provides a reference for the design of heterostructures and their mechanism of action in electrocatalysis. [ABSTRACT FROM AUTHOR]

Abstract The suitable hydrogen-binding free energy (ΔG H*) of active sites for hydrogen evolution reaction (HER) is the key for enhancing the electrocatalytic performances of transition metal based electrocatalysts. Usually metal/nonmetal elemental doping and unique nanostructure can be used to adjust the M H bonding energy for accelerating both generation and departure of H 2. Herein, a simple in-situ phosphorsulfurization method has been used to synthesized nickel cobalt phosphosulphide (NiCoP|S/CC) nanoneedles grown on the surface of carbon cloth (CC) at low temperature as electrocatalyst for hydrogen evolution reaction (HER) in both acid (0.5 M H 2 SO 4) and alkaline (1.0 M KOH) electrolyte solution. Typically, NiCo 2 O 4 /CC with nanoneedles structure is used as precursor. And NaH 2 PO 2 and H 2 S is used as phosphorus and sulfur source, respectively. Compared with single metal phosphophides, the enhanced electrocatalytic performance of NiCoP|S/CC for HER can be attributed to the formation of new specie phosphosulphide and synergistic effect between phosphosulphide and carbon support CC. This work provide a new method with adjusting ΔG H* of active sites for preparing the excellent electrocatalysts for water splitting. Graphical abstract Image 1 Highlights • NiCo 2 O 4 /CC with nanoneedles was used as precursor for the phosphosulphide. • The phosphosulphide can provide the suitable ΔG H* for hydrogen evolution. • The synergistic effect between phosphosulphide and carbon support contributes to the enhanced activity. [ABSTRACT FROM AUTHOR]

[Display omitted] • a/c-RuCoMo y O x /NF was synthesized by coprecipitation-microwave method. • Microwave time affects the transition from crystalline to amorphous structure. • a/c-interface and electron interaction make a/c-RuCoMo y O x /NF have mighty activity. • The η 10 value of a/c-RuCoMo y O x /NF is 39 and 166 mV for HER and OER. Due to the vast difference in structure and the unique electronic state at the heterointerface, the amorphous/crystalline (a/c) heterostructure exhibits excellent potential in electrocatalysis. However, there are great challenges in constructing the material with ample a/c-heterointerfaces and controllably modulated a/c-heterointerface region through a simple one-step method. Herein, the a/c-RuCoMo y O x /NF (nickel foam) electrocatalyst is synthesized by the coprecipitation-microwave treatment method. Notably, microwave time directly affects the ratio of amorphous region (RuCoMoO x) to crystalline region (CoMoO 4 and CoO). Surprisingly, the a/c-RuCoMo y O x /NF with abundant crystallinity/amorphous heterointerfaces exhibits the ultralow η 10 values of 39 and 166 mV for HER and OER, which are 0.5-fold and 0.63-fold lower than that of Pt/C-NF and RuO 2 -NF benchmarks, respectively. Overall, this work provides a novel idea and convenient method for the construction of amorphous/crystalline heterointerfaces with modulated interface region, and guides the direction for the preparation of superior electrocatalysts by regulating the a/c-heterointerface region. [ABSTRACT FROM AUTHOR]

Developing efficient, stable and ideal urea oxide (UOR) electrocatalyst is key to produce green hydrogen in an economical way. Herein, Ru doped three dimensional (3D) porous Ni 3 N spheres, with tannic acid (TA) and urea as the carbon and nitrogen resources, is synthesized via hydrothermal and low-temperature treated process (Ru–Ni 3 N@NC). The porous nanostructure of Ni 3 N and the nickel foam provide abundant active sites and channel during catalytic process. Moreover, Ru doping and rich defects favor to boost the reaction kinetics by optimizing the adsorption/desorption or dissociation of intermediates and reactants. The above advantages enable Ru–Ni 3 N@NC to have good bifunctional catalytic performance in alkaline media. Only 43 and 270 mV overpotentials are required for hydrogen evolution (HER) and oxygen evolution (OER) reactions to drive a current of 10 mA cm−2. Moreover, it also showed good electrocatalytic performance in neutral and alkaline seawater electrolytes for HER with 134 mV to drive 10 mA cm−2 and 83 mV to drive 100 mA cm−2, respectively. Remarkably, the as-designed Ru–Ni 3 N@NC also owns extraordinary catalytic activity and stability toward UOR. Moreover, using the synthesized Ru–Ni 3 N@NC nanomaterial as the anode and cathode of urea assisted water decomposition, a small potential of 1.41 V was required to reach 10 mA cm−2. It can also be powered by sustainable energy sources such as wind, solar and thermal energies. In order to make better use of the earth's abundant resources, this work provides a new way to develop multi-functional green electrocatalysts. [Display omitted] • The synthesized electrocatalyst exhibits porous specific sphere morphology to exposed abundant active sites. • The prepared electrocatalyst presents excellent electrocatalytic performances toward HER, OER and UOR. • Small overpotential is required to drive overall water-splitting under the urea assistance with remarkable stability. • Sustainable energies are investigated to power the electrolyzer for hydrogen generation. [ABSTRACT FROM AUTHOR]