Emerging 2D Copper-Based Materials for Energy Storage and Conversion: A Review and Perspective.

2D materials have shown great potential as electrode materials that determine the performance of a range of electrochemical energy technologies. Among these, 2D copper-based materials, such as Cu-O, Cu-S, Cu-Se, Cu-N, and Cu-P, have attracted tremendous research interest, because of the combination of remarkable properties, such as low cost, excellent chemical stability, facile fabrication, and significant electrochemical properties. Herein, the recent advances in the emerging 2D copper-based materials are summarized. A brief summary of the crystal structures and synthetic methods is started, and innovative strategies for improving electrochemical performances of 2D copper-based materials are described in detail through defect engineering, heterostructure construction, and surface functionalization. Furthermore, their state-of-the-art applications in electrochemical energy storage including supercapacitors (SCs), alkali (Li, Na, and K)-ion batteries, multivalent metal (Mg and Al)-ion batteries, and hybrid Mg/Li-ion batteries are described. In addition, the electrocatalysis applications of 2D copper-based materials in metal-air batteries, water-splitting, and CO2 reduction reaction (CO2 RR) are also discussed. This review also discusses the charge storage mechanisms of 2D copper-based materials by various advanced characterization techniques. The review with a perspective of the current challenges and research outlook of such 2D copper-based materials for high-performance energy storage and conversion applications is concluded.

Exploring 2D Energy Storage Materials: Advances in Structure, Synthesis, Optimization Strategies, and Applications for Monovalent and Multivalent Metal-Ion Hybrid Capacitors.

The design and development of advanced energy storage devices with good energy/power densities and remarkable cycle life has long been a research hotspot. Metal-ion hybrid capacitors (MHCs) are considered as emerging and highly prospective candidates deriving from the integrated merits of metal-ion batteries with high energy density and supercapacitors with excellent power output and cycling stability. The realization of high-performance MHCs needs to conquer the inevitable imbalance in reaction kinetics between anode and cathode with different energy storage mechanisms. Featured by large specific surface area, short ion diffusion distance, ameliorated in-plane charge transport kinetics, and tunable surface and/or interlayer structures, 2D nanomaterials provide a promising platform for manufacturing battery-type electrodes with improved rate capability and capacitor-type electrodes with high capacity. In this article, the fundamental science of 2D nanomaterials and MHCs is first presented in detail, and then the performance optimization strategies from electrodes and electrolytes of MHCs are summarized. Next, the most recent progress in the application of 2D nanomaterials in monovalent and multivalent MHCs is dealt with. Furthermore, the energy storage mechanism of 2D electrode materials is deeply explored by advanced characterization techniques. Finally, the opportunities and challenges of 2D nanomaterials-based MHCs are prospected.

Electrocatalysis CO2 to Tunable Syngas upon Fe Clusters Catalyst Dispersed on Bamboo-like NCTs.

Herein, we report a catalyst of Fe@NBCT with a high performance in electrocatalytic CO2 to syngas with tunable H2/CO ratio. Both in situ synchrotron radiation Fourier transform infrared spectra (SR-FTIR) and density functional theory (DFT) calculation proved that the differing N-doping carbon matrix and Fe nanoclusters (NCs) play dramatic roles in tuning the ratio of syngas during the electrocatalytic carbon dioxide reduction reaction (EC-CO2RR) process.

Design of Binary Cu-Fe Sites Coordinated with Nitrogen Dispersed in the Porous Carbon for Synergistic CO2 Electroreduction.

To relieve the green gas emission and involve the carbon neutral cycle, electrochemical reduction of CO2 attracts more and more attention. Herein, a biatomic site catalyst of Cu-Fe coordinated with the nitrogen, which is doped in the carbon matrix (denoted as Cu-Fe-N6 -C), is designed. The as-obtained Cu-Fe-N6 -C exhibits higher performance than that of Cu-N-C and Fe-N-C, owing to bimetallic sites, proving synergistic functions based on different molecules and their interfaces. Cu-Fe-N6 -C shows high selectivity toward CO, with high Faradaic efficiency (98% at -0.7 V), and maintaining 98% of its initial selectivity after 10 h electrolysis. The experimental results and theoretical calculations reveal that the synergistic catalysis of different metallic sites enlarges the adsorption enthalpy of CO2 , reducing the activation energy result in generating high selectivity, activity, stability, and low impedance.

Cu Nanoclusters Anchored on the Metal-Organic Framework for the Hydrolysis of Ammonia Borane and the Reduction of Quinolines.

Free-access active sites created and the interaction regulated between them and substrates during the heterogeneous catalysis process are crucial, which remain a great challenge. In this work, in suit reduced to afford naked Cu nanoparticles (NPs) have been anchored on the metal-organic framework (MOF), NH2-MOF, to form Cu-NH2-MOF. The strategy can precisely control the Cu NP formation with small size and uniform distribution. The Cu NP properties and MOF advantages have been integrated to create a great catalyst with multiple functions and have resulted in improving the recyclability and superb catalytic activity for the one-pot reduction of heterocycle reactions under mild conditions. The experimental and theoretical calculation results show that the superior performance should be attributed to the framework of NH2-MOF that provides large caves for substrate enrichment and the stabilization of Cu sites by the -NH2 group.

Encapsulating Cobalt into N-Doping Hollow Frameworks for Efficient Cascade Catalysis.

The development of nonprecious catalysts for hydrogenation of organic molecules is of great importance in heterogeneous catalysis. Herein, we report a series of N-doped hollow carbon frameworks encompassing cobalt nanoparticles (denoted as Co@NHF-900) constructed as a new kind of reusable catalyst for this purpose by pyrolysis of ZIF-8@Co-dopamine under Ar atmospheres. Notably, the framework of ZIF-8 is essential for efficient catalyst by providing a carbon framework to support Co-dopamine. The experimental results reveal that the ZIF-8 renders a large hollow place within the catalysts, allowing the enrichment of the substrate and windows of the hollow structure and the ease of mass transfer of products during the reaction. All of the virtues made Co@NHF-900 a good candidate for hydrogenation of quinolines with high activity (TOF value of 119 h-1, which is several times than that of akin catalysts) and chemoselectivity.

Highly Efficient and Chemoselective Hydrogenation of Nitro Compounds into Amines by Nitrogen-Doped Porous Carbon-Supported Co/Ni Bimetallic Nanoparticles.

A novel Co/Ni bimetallic nanoparticle supported by nitrogen-doped porous carbon (NPC), Co5/Ni@NPC-700, exhibits high conversion, chemoselectivity, and recyclability in the hydrogenation of 16 different nitro compounds into desired amines with hydrazine hydrate under mild conditions. The synergistic effects of Co/Ni bimetal nanoparticles and the NPC-supported porous honeycomb structure with more accessible active sites may be responsible for the high catalytic hydrogenation performance.

Fe, Co-codoped layered double hydroxide nanosheet arrays derived from zeolitic imidazolate frameworks for high-performance aqueous hybrid supercapacitors and Zn-Ni batteries.

In the past decade, layered double hydroxides (LDHs) have attracted great attention in the field of energy storage owing to their excellent two-dimensional (2D) hydrotalcite-like structure, highly reversible redox kinetics, and adjustable composition. At the same time, nanomaterials constructed by ultrathin nanosheets have enhanced conductivity, rich electrochemical active sites and fast charge transfer channels, showing better electrochemical properties. Herein, we designed three-dimensional (3D) NiFeCo LDH vertical nanosheet arrays (denoted NiFeCo-LDH NA) assembled by the tight interconnection of 2D nanosheets using a Ni-coordinated zeolitic imidazolate framework (Ni-ZIF-L) as a sacrificial template via facile ion exchange and etching reaction processes under hydrothermal conditions. The appropriate doping ratio of iron and cobalt ions is regulated. Electrochemical tests show that the NiFeCo LDH NA-based electrode shows a high specific capacity of 1495C g-1 at 1 A g-1 and has great cycling stability (89% capacitance retention over 10,000 cycles). The assembled hybrid supercapacitor (NiFeCo LDH NA//AC) achieves a fine energy density of 34.4 W h kg-1 at a power density of 935.5 W kg-1 with good cycling stability of over a 96% retention rate (compared with the initial capacitance) and outstanding coulombic efficiency (nearly 99%) after 15,000 cycles. The constructed aqueous Zn-Ni battery (NiFeCo LDH NA//Zn) exhibits a remarkable specific capacity of 272 mA h g-1 at 3 A g-1 with a high energy density of 464.7 W h kg-1 and retains 81% of the initial specific capacity after 2000 cycles at 20 A g-1. This work not only proves that ternary LDHs can be used as good energy storage materials but also provides a new way to prepare nanomaterials with specific morphology.

Metal-organic frameworks and their derivatives for metal-ion (Li, Na, K and Zn) hybrid capacitors.

Metal-ion hybrid capacitors (MIHCs) hold particular promise for next-generation energy storage technologies, which bridge the gap between the high energy density of conventional batteries and the high power density and long lifespan of supercapacitors (SCs). However, the achieved electrochemical performance of available MIHCs is still far from practical requirements. This is primarily attributed to the mismatch in capacity and reaction kinetics between the cathode and anode. In this regard, metal-organic frameworks (MOFs) and their derivatives offer great opportunities for high-performance MIHCs due to their high specific surface area, high porosity, topological diversity, and designable functional sites. In this review, instead of simply enumerating, we critically summarize the recent progress of MOFs and their derivatives in MIHCs (Li, Na, K, and Zn), while emphasizing the relationship between the structure/composition and electrochemical performance. In addition, existing issues and some representative design strategies are highlighted to inspire breaking through existing limitations. Finally, a brief conclusion and outlook are presented, along with current challenges and future opportunities for MOFs and their derivatives in MIHCs.

Fe Single Atoms and Fe2O3 Clusters Liberated from N-Doped Polyhedral Carbon for Chemoselective Hydrogenation under Mild Conditions.

In the area of catalysis, selective reduction of nitro compounds to amino compounds is a colossal challenge due to the existence of competitive reducible functional groups. Herein, an Fe-based catalyst FeSAs/Fe2O3ACs/N-doped polyhedral carbon (NPC) has been designed and synthesized. As we expected, compared with FeSAs and FeNPs, FeSAs/Fe2O3ACs/NPC shows excellent catalytic performance (turnover frequency up to 1923 h-1, calculated with nitrobenzene), chemoselectivity, and tolerance during the hydrogenation reaction of nitro compounds under room temperature because of the synergistic effects between FeSAs and Fe2O3ACs. The theoretical calculations show that FeSAs prefers to undergo hydrazine decomposition to generate hydrogen and the Fe2O3ACs surface is more active toward the nitrobenzene reduction to aniline.