Atomically Dispersed Dual-Metal Site Catalysts for Enhanced CO2 Reduction: Mechanistic Insight into Active Site Structures.

Carbon-supported nitrogen-coordinated single-metal site catalysts (i.e., M-N-C, M: Fe, Co, or Ni) are active for the electrochemical CO2 reduction reaction (CO2 RR) to CO. Further improving their intrinsic activity and selectivity by tuning their N-M bond structures and coordination is limited. Herein, we expand the coordination environments of M-N-C catalysts by designing dual-metal active sites. The Ni-Fe catalyst exhibited the most efficient CO2RR activity and promising stability compared to other combinations. Advanced structural characterization and theoretical prediction suggest that the most active N-coordinated dual-metal site configurations are 2N-bridged (Fe-Ni)N6 , in which FeN4 and NiN4 moieties are shared with two N atoms. Two metals (i.e., Fe and Ni) in the dual-metal site likely generate a synergy to enable more optimal *COOH adsorption and *CO desorption than single-metal sites (FeN4 or NiN4 ) with improved intrinsic catalytic activity and selectivity.

A facile and simple microwave-assisted synthesis method for mesoporous ultrathin iron sulfide nanosheets as an efficient bifunctional electrocatalyst for overall water splitting.

The engineering of inexpensive, high-efficiency and stable electrodes related to both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is highly desired for full water splitting devices to promote future advances in this energy technology. Therefore, a large surface area, rich in exposed surface atoms, and mesoporosity are very effective parameters in electrochemical reactions. Herein, we have, for the first time, synthesized free-standing mesoporous Fe3S4 nanosheets with a large surface area of 129.65 m2 g-1 through a microwave-assisted synthetic technique. Our present synthesis strategy demonstrates a facile and cost-effective method to overcome the obstacles of fabricating ultrathin two-dimensional graphene-like transition metal sulfide nanosheets. The as-synthesized Fe3S4 nanosheets are applied as both cathodic and anodic electrodes for full water electrolysis. Remarkably, Fe3S4 nanosheets can exhibit a small overpotential (η = 103 mV) to provide the required 10 mA cm-2 current density during the HER process. Meanwhile, a low overpotential of 230 mV is also exhibited for the OER process to allow a 10 mA cm-2 current density. Furthermore, the assembled full water splitting device can achieve potentials of 1.43 and 1.65 V at 10 and 100 mA cm-2 current densities, respectively, in an alkaline electrolyte with excellent cycling stability over 24 h. Our current study may provide an advanced channel for transition metal sulfide catalysts towards commercial water splitting applications.

Thermocatalytic Hydrogen Production Through Decomposition of Methane-A Review.

Consumption of fossil fuels, especially in transport and energy-dependent sectors, has led to large greenhouse gas production. Hydrogen is an exciting energy source that can serve our energy purposes and decrease toxic waste production. Decomposition of methane yields hydrogen devoid of COx components, thereby aiding as an eco-friendly approach towards large-scale hydrogen production. This review article is focused on hydrogen production through thermocatalytic methane decomposition (TMD) for hydrogen production. The thermodynamics of this approach has been highlighted. Various methods of hydrogen production from fossil fuels and renewable resources were discussed. Methods including steam methane reforming, partial oxidation of methane, auto thermal reforming, direct biomass gasification, thermal water splitting, methane pyrolysis, aqueous reforming, and coal gasification have been reported in this article. A detailed overview of the different types of catalysts available, the reasons behind their deactivation, and their possible regeneration methods were discussed. Finally, we presented the challenges and future perspectives for hydrogen production via TMD. This review concluded that among all catalysts, nickel, ruthenium and platinum-based catalysts show the highest activity and catalytic efficiency and gave carbon-free hydrogen products during the TMD process. However, their rapid deactivation at high temperatures still needs the attention of the scientific community.

Pristine Hollow Metal-Organic Frameworks: Design, Synthesis and Application.

Metal-organic frameworks (MOFs), featuring porous crystalline structures with coordinated metal nodes and organic linkers, have recently found increasing interest in diverse applications. By virtue of their versatile and highly tunable compositions and structures, constructing hollow architectures will further endow MOFs with enhanced properties and designability, exceeding the molecular scale. MOFs could be considered as promising building units to fabricate complex hollow nanocomposites with faster mass transport, multiple active components, more exposed active sites, and better compatibility than bulk MOFs. To construct a promising blueprint for hollow pristine MOFs, this review provides a comprehensive overview for structural design strategies and applications of hollow pristine MOFs. We will highlight the merits, challenges and future potential by structuring and applying MOFs in sensing, separation, storage, catalysis, environmental remediation, photochemical and electrochemical energy conversion. This review might pave a new avenue for future development of novel pristine hollow MOFs.

Carbon Fibers Embedded With Iron Selenide (Fe 3 Se 4 ) as Anode for High-Performance Sodium and Potassium Ion Batteries.

The development of sodium and potassium ion batteries (SIBs/KIBs) has seen tremendous growth in recent years due to their promising properties as a potential replacement for lithium-ion batteries (LIBs). Here, we report ultrafine iron selenide (Fe3Se4) nanoparticles embedded into one-dimensional (1D) carbon fibers (Fe3Se4@CFs) as a potential candidate for SIBs/KIBs. The Fe-based metal-organic framework particles (MOFP) are used as a Fe source to obtain highly dispersed Fe3Se4 nanoparticles in the product. The Fe3Se4@CF consisted of ultrafine particles of Fe3Se4 with an average particle size of ~10 nm loaded into CFs with an average diameter of 300 nm. The product exhibited excellent specific activity of ~439 and ~435 mAh/g at the current density of 50 mA/g for SIBs and KIBs, respectively. In addition, the as-prepared anodes (Fe3Se4@CFs) exhibited excellent capacity retention up to several hundred cycles (700 cycles for SIBs and 300 cycles for KIBs). The high activity and excellent stability of the developed electrodes make Fe3Se4@CFs a promising electrode for next-generation batteries.

A Dual Protection System for Heterostructured 3D CNT/CoSe2/C as High Areal Capacity Anode for Sodium Storage.

3D electrode design is normally opted for multiple advantages, however, instability/detachment of active material causes the pulverization and degradation of the structure, and ultimately poor cyclic stability. Here, a dually protected, highly compressible, and freestanding anode is presented for sodium-ion batteries, where 3D carbon nanotube (CNT) sponge is decorated with homogeneously dispersed CoSe2 nanoparticles (NPs) which are protected under carbon overcoat (CNT/CoSe2/C). The 3D CNT sponge delivers enough space for high mass loading while providing high mechanical strength and faster conduction pathway among the NPs. The outer amorphous carbon overcoat controls the formation of solid electrolyte interphase film by avoiding direct contact of CoSe2 with electrolyte, accommodates large volume changes, and ultimately enhances the overall conductivity of cell and assists in transmitting electron to an external circuit. Moreover, the hybrid can be densified up to 11-fold without affecting its microstructure that results in ultrahigh areal mass loading of 17.4 mg cm-2 and an areal capacity of 7.03 mAh cm-2 along with a high gravimetric capacity of 531 mAh g-1 at 100 mA g-1. Thus, compact and smart devices can be realized by this new electrode design for heavy-duty commercial applications.

A Freestanding Single-Wall Carbon Nanotube Film Decorated with N-Doped Carbon-Encapsulated Ni Nanoparticles as a Bifunctional Electrocatalyst for Overall Water Splitting.

Noble-metal free, cost-effective, and highly stable catalysts with efficient activity for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) have attracted tremendous research interest in recent years. Here, a flexible, self-standing hybrid film comprising a N-doped single-wall carbon nanotube (SWCNT) network on which are anchored Ni nanoparticles encapsulated by a monolayer of N-doped carbon (NCNi) is reported. The films are prepared by floating catalyst chemical vapor deposition followed by NH3 treatment. The material obtained at optimum conditions shows excellent bifunctional electrocatalytic activity in alkaline media with low overpotentials of 190 and 270 mV for HER and OER, respectively, to reach a current density of 10 mA cm-2. A current density of 10 mA cm-2 at 1.57 V is achieved when this freestanding and binder-free rod-shaped NCNi/SWCNT assembly is used as cathode and anode in 1 m KOH solution for overall water splitting, presenting one of the best values reported to date.

Ultrafast Sodium/Potassium-Ion Intercalation into Hierarchically Porous Thin Carbon Shells.

The large-scale application of sodium/potassium-ion batteries is severely limited by the low and slow charge storage dynamics of electrode materials. The crystalline carbons exhibit poor insertion capability of large Na+ /K+ ions, which limits the storage capability of Na/K batteries. Herein, porous S and N co-doped thin carbon (S/N@C) with shell-like (shell size ≈20-30 nm, shell wall ≈8-10 nm) morphology for enhanced Na+ /K+ storage is presented. Thanks to the hollow structure and thin shell-wall, S/N@C exhibits an excellent Na+ /K+ storage capability with fast mass transport at higher current densities, leading to limited compromise over charge storage at high charge/discharge rates. The S/N@C delivers a high reversible capacity of 448 mAh g-1 for Na battery, at the current density of 100 mA g-1 and maintains a discharge capacity up to 337 mAh g-1 at 1000 mA g-1 . Owing to shortened diffusion pathways, S/N@C delivers an unprecedented discharge capacity of 204 and 169 mAh g-1 at extremely high current densities of 16 000 and 32 000 mA g-1 , respectively, with excellent reversible capacity for 4500 cycles. Moreover, S/N@C exhibits high K+ storage capability (320 mAh g-1 at current density of 50 mA g-1 ) and excellent cyclic life.

Fe2 N/S/N Codecorated Hierarchical Porous Carbon Nanosheets for Trifunctional Electrocatalysis.

Construction of multifunctional highly active earth-abundant electrocatalysts on a large scale is a great challenge due to poor control over nanostructural features and limited active sites. Here, a simple methodology to tailor metal-organic frameworks (MOFs) to extract highly active multifunctional electrocatalysts on a large scale for oxygen reduction (ORR), oxygen evolution (OER), and hydrogen evolution reaction (HER) is presented. The N, S codoped Fe2 N decorated highly porous and defect-rich carbon nanosheets are grown using MOF xerogels, melamine, and polyvinylpyrollidone. The resulting catalyst exhibits excellent activity for ORR with an onset (0.92 V) and half-wave (0.81 V) potential similar to state-of-the-art Pt/C catalysts. The catalyst also shows outstanding OER and HER activities with a small overpotential of 360 mV in 1 m KOH and -123 mV in 0.5 m H2 SO4 at a current density of 10 mA cm-2 , respectively. Excellent catalytic properties are further supported by theoretical calculations where relevant models are built and various possible activation sites are identified by first-principles calculations. The results suggest that the carbon atoms adjacent to heteroatoms as well as Fe2 -N sites present the active sites for improved catalytic response, which is in agreement with the experimental results.

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co-Doped Graphitic Nanotubes as High-Performance Lithium-Ion Battery Anodes.

Yolk-shell nanostructures have received great attention for boosting the performance of lithium-ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li+ ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co-doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni2 O3 , Mn3 O4 ) through combining pyrolysis with an oxidation method is reported herein. The as-made TMO@BNG exhibits the TMO-dependent lithium-ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium-ion storage capacity of 1554 mA h g-1 at the current density of 96 mA g-1 , good rate ability (410 mA h g-1 at 1.75 A g-1 ), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability.

Hierarchical Cobalt Hydroxide and B/N Co-Doped Graphene Nanohybrids Derived from Metal-Organic Frameworks for High Energy Density Asymmetric Supercapacitors.

To cater for the demands of electrochemical energy storage system, the development of cost effective, durable and highly efficient electrode materials is desired. Here, a novel electrode material based on redox active ß-Co(OH)2 and B, N co-doped graphene nanohybrid is presented for electrochemical supercapacitor by employing a facile metal-organic frameworks (MOFs) route through pyrolysis and hydrothermal treatment. The Co(OH)2 could be firmly stabilized by dual protection of N-doped carbon polyhedron (CP) and B/N co-doped graphene (BCN) nanosheets. Interestingly, the porous carbon and BCN nanosheets greatly improve the charge storage, wettability, and redox activity of electrodes. Thus the hybrid delivers specific capacitance of 1263 F g-1 at a current density of 1A g-1 with 90% capacitance retention over 5000 cycles. Furthermore, the new aqueous asymmetric supercapacitor (ASC) was also designed by using Co(OH)2@CP@BCN nanohybrid and BCN nanosheets as positive and negative electrodes respectively, which leads to high energy density of 20.25 Whkg-1. This device also exhibits excellent rate capability with energy density of 15.55 Whkg-1 at power density of 9331 Wkg-1 coupled long termed stability up to 6000 cycles.

Nanostructured Electrode Materials Derived from Metal-Organic Framework Xerogels for High-Energy-Density Asymmetric Supercapacitor.

This work successfully demonstrates metal-organic framework (MOF) derived strategy to prepare nanoporous carbon (NPC) with or without Fe3O4/Fe nanoparticles by the optimization of calcination temperature as highly active electrode materials for asymmetric supercapacitors (ASC). The nanostructured Fe3O4/Fe/C hybrid shows high specific capacitance of 600 F/g at a current density of 1 A/g and excellent capacitance retention up to 500 F/g at 8 A/g. Furthermore, hierarchically NPC with high surface area also obtained from MOF gels displays excellent electrochemical performance of 272 F/g at 2 mV/s. Considering practical applications, aqueous ASC (aASC) was also assembled, which shows high energy density of 17.496 Wh/kg at the power density of 388.8 W/kg. The high energy density and excellent capacity retention of the developed materials show great promise for the practical utilization of these energy storage devices.