3D Carbon Materials for Efficient Oxygen and Hydrogen Electrocatalysis

Sustainable energy production at an acceptable cost is key for its widespread application. At present, noble metals and metal oxides are the most widely used for electrocatalysis, but they suffer from low selectivity, poor durability, and scarcity. Because of this, metal‐free carbons have become the subject of great interest as promising alternative electrocatalysts for energy conversion and storage devices, and remarkable progress has been accomplished in the advance of metal‐free carbons as electrocatalysts for renewable energy technologies. Particularly interesting are 3D porous carbon architectures, which exhibit outstanding features for electrocatalysis applications, including broad range of active sites, interconnected porosity, high conductivity, and mechanical stability. This review summarizes the latest advances in 3D porous carbon structures for oxygen and hydrogen electrocatalysis. The structure–performance relationship of these materials is consequently rationalized and perspectives on creating more efficient 3D carbon electrocatalysts are suggested.     

Multifunctional Transition Metal‐Based Phosphides in Energy‐Related Electrocatalysis

The exploitation of cheap and efficient electrocatalysts is the key to make energy‐related electrocatalytic techniques commercially viable. In recent years, transition metal phosphides (TMPs) electrocatalysts have gained a great deal of attention owing to their multifunctional active sites, tunable structure, and composition, as well as unique physicochemical properties. This review summarizes the up‐to‐date progress on TMPs in energy‐related electrocatalysis from diversified synthetic methods, ingenious‐modulated strategies, and novel applications. In order to set forth theory–structure–performance relationships upon TMPs, the corresponding reaction mechanisms, electrocatalytsts' structure/composition designs and desired electrochemical performance are jointly discussed, along with demonstrating their practical electrocatalytic applications in overall water splitting, metal–air batteries, lithium–sulfur batteries, etc. In the end, some underpinning issues and research orientations of TMPs toward efficient energy‐related electrocatalysis are briefly proposed.     

Graphene Quantum Dots‐Based Advanced Electrode Materials: Design,Synthesis and Their Applications in Electrochemical Energy Storage and Electrocatalysis

Graphene quantum dots (GQDs) have aroused great interest in the scientific community in recent years due to their unique physicochemical properties and potential applications in different fields. To date, much research has been conducted on the ingenious design and rational construction of GQDs‐based nanomaterials used as electrode materials and/or electrocatalysts. Despite these efforts, research on the efficient synthesis and application of GQDs‐based nanomaterials is still in the early stages of development and timely updates of recent research progress on new design concepts, synthetic strategies, and significant breakthroughs in GQDs‐based nanomaterials are highly desired. In light of the above, the effect of synthetic methods on the final product of the GQDs, the GQDs synthesis mechanism, and specific perspectives regarding the effect of the unique surface and structural properties of GQDs (e.g., defects, heteroatom doping, surface/edge state, size, conductivity) on the electrochemical energy‐related systems are discussed in‐depth in this review. Additionally, this review also focuses on the design of GQDs‐based composites and their applications in the fields of electrochemical energy storage (e.g., supercapacitors and batteries) and electrocatalysis (e.g., fuel cell, water splitting, CO₂ reduction), along with constructive suggestions for addressing the remaining challenges in the field.     

Enhancement of Thermal Properties of Polyvinylpyrrolidone (PVP)-Coated Silver Nanoparticles by Using Plasmid DNA and their Localized Surface Plasmon Resonance (LSPR) Characteristics

In this paper, the enhancement of thermal properties of polymer-coated silver nanoparticles by the addition of plasmid DNA is described. Nanoparticles of noble metals such as gold and silver possess specific characteristics by virtue of their quantum size effects. Therefore, noble metal nanoparticles are used for chemical sensing and biosensing applications based on their localized surface plasmon resonance absorption that can be measured in the visible region. The polyvinylpyrrolidone (PVP)-coated noble metal nanoparticles, in particular, with high dispersion ability in water, offer several advantages for sensing applications. However, some difficulties are encountered in the use of these PVP-coated noble metal nanoparticles for sensing applications due to their poor thermal properties. To improve the thermal properties of PVP-coated noble metal nanoparticles, we found that the addition of plasmid DNA to PVP-coated silver nanoparticles enhances their thermal properties due to good thermal stability of DNA. The introduction of plasmid DNA into PVP-coated silver nanoparticle dispersion enhanced the thermal properties through the formation of a complex between the nanoparticles and plasmid DNA. Furthermore, other polymers such as proteins and polyethylene glycol did not enhance the thermal properties of PVP-coated silver nanoparticles. Thus, the PVP-coated silver nanoparticle–plasmid DNA complex with enhanced thermal properties has a great potential for use in medical and drug delivery applications.     

Efficiently Enhancing Oxygen Reduction Electrocatalytic Activity of MnO2 Using Facile Hydrogenation

Improving the electrocatalytic oxygen reduction reaction (ORR) activity of transition metal oxides is important for the development of non‐noble metal catalysts that are used in metal‐air batteries and fuel cells. Here, a novel facile strategy of hydrogenation to significantly enhance the ORR performance of MnO₂. The hydrogenated MnO₂ (H‐MnO₂), which is prepared through a simple heat treatment in hydrogen gas, shows characteristics of modified lattice/surface structures and increased electrical conductivity. In 0.1 M KOH aqueous solution, the prepared H‐MnO₂ exhibits high activity toward the oxygen electrocatalysis with more positive onset potential (≈60 mV), ≈14% larger of limiting current, lower yield of peroxide species, and better durability than the pristine oxide. Further conductivity testing and density functional theory (DFT) studies reveal the faster kinetics of ORR after hydrogenation is due to the formation of hydrogen bonds and altered microstructure and improved electronic properties. These results highlight the importance of hydrogenation as a facile yet effective strategy to improve the catalytic activity of transition metal oxides for ORR‐based applications.     

Metal‐Organic Framework‐Derived Non‐Precious Metal Nanocatalysts for Oxygen Reduction Reaction

By virtue of diverse structures and tunable properties, metal‐organic frameworks (MOFs) have presented extensive applications including gas capture, energy storage, and catalysis. Recently, synthesis of MOFs and their derived nanomaterials provide an opportunity to obtain competent oxygen reduction reaction (ORR) electrocatalysts due to their large surface area, controllable composition and pore structure. This review starts with the introduction of MOFs and current challenges of ORR, followed by the discussion of MOF‐based non‐precious metal nanocatalysts (metal‐free and metal/metal oxide‐based carbonaceous materials) and their application in ORR electrocatalysis. Current issues in MOF‐derived ORR catalysts and some corresponding strategies in terms of composition and morphology to enhance their electrocatalytic performance are highlighted. In the last section, a perspective for future development of MOFs and their derivatives as catalysts for ORR is discussed.     

Fundamental Understanding and Material Challenges in Rechargeable Nonaqueous Li–O2 Batteries: Recent Progress and Perspective

Energy storage challenges have triggered growing interest in various battery technologies and electrocatalysis. As a particularly promising variety, the Li–O₂ battery with an extremely high energy density is of great significance, offering tremendous opportunities to improve cell performance via understanding catalytic mechanisms and the exploration of new materials. Furthermore, focus on nonaqueous electrolyte‐based Li–O₂ batteries has markedly intensified since there could be a higher probability of commercialization, compared to that of solid‐state or aqueous electrolytes. The recent advancements of the nonaqueous Li–O₂ battery in terms of fundamental understanding and material challenges, including electrolyte stability, water effect, and noncarbon cathode materials are summarized in this review. Further, the current status of water impact on discharge products, possible mechanisms, and parasitic reactions in nonaqueous electrolytes are reviewed for the first time. The key challenges of noncarbon oxygen electrode materials, such as noble metals and metal oxides‐based cathodes, transition metals, transition metal compounds (carbides, oxides) based cathodes as well as noncarbon supported catalysts are discussed. This review concludes with a perspective on future research directions for nonaqueous Li–O₂ batteries.     

Confined Synthesis of 2D Nanostructured Materials toward Electrocatalysis

2D nanostructured materials have shown great application prospects in energy conversion, owing to their unique structural features and fascinating physicochemical properties. Developing efficient approaches for the synthesis of well‐defined 2D nanostructured materials with controllable composition and morphology is critical. The emerging concept, confined synthesis, has been regarded as a promising strategy to design and synthesize novel 2D nanostructured materials. This review mainly summarizes the recent advances in confined synthesis of 2D nanostructured materials by using layered materials as host matrices (also denoted as “nanoreactors”). By virtue of the space‐ and surface‐confinement effects of these layered hosts, various well‐organized 2D nanostructured materials, including 2D metals, 2D metal compounds, 2D carbon materials, 2D polymers, 2D metal‐organic frameworks (MOFs) and covalent‐organic frameworks (COFs), as well as 2D carbon nitrides are successfully synthesized. The wide employment of these 2D materials in electrocatalytic applications (e.g., electrochemical oxygen/hydrogen evolution reactions, small molecule oxidation, and oxygen reduction reaction) is presented and discussed. In the final section, challenges and prospects in 2D confined synthesis from the viewpoint of designing new materials and exploring practical applications are commented, which would push this fast‐evolving field a step further toward greater success in both fundamental studies and ultimate industrialization.     

Recent Development of Zeolitic Imidazolate Frameworks (ZIFs) Derived Porous Carbon Based Materials as Electrocatalysts

Development of effective, stable, and economic electrocatalysts is critical for further implementation of fuel cells, water electrolysis, and metal–air batteries in clean energy conversion technologies. As a subfamily of metal–organic frameworks (MOFs), zeolitic imidazolate frameworks (ZIFs) possess the characteristics of both MOFs and zeolites, showing highly porous structures, large surface area, and open catalytic active sites. This review presents materials design strategies for constructing improved electrocatalysts based on ZIF precursors/templates, with special emphasis on the varieties of derivatives, controllable building of active sites, the construction of macroscopic structure, and the favored electrocatalytic reactions based on these materials. These ZIF‐derived N‐doped carbon‐based composites or compounds have exhibited remarkable activity and stability for a broad electrocatalysis application, displaying great potential to replace noble‐metal‐based catalysts. The challenges and perspectives regarding ZIF‐derived electrocatalysts are also discussed for better development of ZIF‐derived electrocatalysts.     

Surface‐Guided Formation of Amorphous Mixed‐Metal Oxyhydroxides on Ultrathin MnO2 Nanosheet Arrays for Efficient Electrocatalytic Oxygen Evolution

Earth‐abundant amorphous nanomaterials with rich structural defects are promising alternative catalysts to noble metals for an efficient electrochemical oxygen evolution reaction; however, their inferior electrical conductivity and poor morphological control during synthesis hamper the full realization of their potency in electrocatalysis. Herein, a rapid surface‐guided synthetic approach is proposed to introduce amorphous and mixed‐metal oxyhydroxide overlayers on ultrathin Ni‐doped MnO₂ (Ni? MnO₂) nanosheet arrays via a galvanic replacement mechanism. This method results in a monolithic 3D porous catalyst with a small overpotential of only 232 mV to achieve a current density of 10 mA cm^?2 in 1 m KOH, which is much lower than the corresponding value of 307 mV for the Ni? MnO₂ reference sample. Detailed structural and electrochemical characterization reveal that the unique Ni? MnO₂ ultrathin nanosheet arrays do not only provide a large surface area to guide the formation of active amorphous catalyst layers but also ensure the effective charge transport owing to their high electron conductivity, collectively contributing to the greatly improved catalyst activity. It is envisioned that this highly operable surface‐guide synthetic strategy may open up new avenues for the design and fabrication of novel 3D nanoarchitectures integrated with functional amorphous materials for broadened ranges of applications.     

Identifying Catalytic Active Sites of Trimolybdenum Phosphide (Mo3P) for Electrochemical Hydrogen Evolution

Solid‐state electrocatalysis plays a crucial role in the development of renewable energy to reshape current and future energy needs. However, finding an inexpensive and highly active catalyst to replace precious metals remains a big challenge for this technology. Here, tri‐molybdenum phosphide (Mo₃P) is found as a promising nonprecious metal and earth‐abundant candidate with outstanding catalytic properties that can be used for electrocatalytic processes. The catalytic performance of Mo₃P nanoparticles is tested in the hydrogen evolution reaction (HER). The results indicate an onset potential of as low as 21 mV, H₂ formation rate, and exchange current density of 214.7 µmol s^?1 g^?1_cat (at only 100 mV overpotential) and 279.07 µA cm^?2, respectively, which are among the closest values yet observed to platinum. Combined atomic‐scale characterizations and computational studies confirm that high density of molybdenum (Mo) active sites at the surface with superior intrinsic electronic properties are mainly responsible for the remarkable HER performance. The density functional theory calculation results also confirm that the exceptional performance of Mo₃P is due to neutral Gibbs free energy (ΔG_H*) of the hydrogen (H) adsorption at above 1/2 monolayer (ML) coverage of the (110) surface, exceeding the performance of existing non‐noble metal catalysts for HER.     

Biotemplates in the green synthesis of silver nanoparticles

This article recapitulates the scientific advancement towards the greener synthesis of silver nanoparticles. Applications of noble metals have increased throughout human civilization, and the uses for nano-sized particles are even more remarkable. “Green” nanoparticle synthesis has been achieved using environmentally acceptable solvent systems and eco-friendly reducing and capping agents. Numerous microorganisms and plant extracts have been applied to synthesize inorganic nanostructures either intracellularly or extracellularly. The use of nanoparticles derived from noble metals has spread to many areas including jewelery, medical fields, electronics, water treatment and sport utilities, thus improving the longevity and comfort in human life. The application of nanoparticles as delivery vehicles for bactericidal agents represents a new paradigm in the design of antibacterial therapeutics. Orientation, size and physical properties of nanoparticles influences the performance and reproducibility of a potential device, thus making the synthesis and assembly of shape- and size-controlled nanocrystals an essential component for any practical application. This need has motivated researchers to explore different synthesis protocols.     

Anchoring PdCu Amorphous Nanocluster on Graphene for Electrochemical Reduction of N2 to NH3 under Ambient Conditions in Aqueous Solution

As an alternative approach for N₂ fixation under milder conditions, electrocatalytic nitrogen reduction reaction (NRR) represents a very attractive strategy for sustainable development and N₂ cycle to store and utilize energy from renewable sources. However, the research on NRR electrocatalysts still mainly focuses on noble metals, while, high costs and limited resources greatly restrict their large‐scale applications. Herein, as a proof‐of‐concept experiment, taking PdCu amorphous nanocluster anchored on reduced graphene oxide (rGO) as NRR catalysts, the optimum Pd_0.2Cu_0.8/rGO composite presents a synergistic effect and shows superior electrocatalytic performance toward NRR under ambient conditions (yield: 2.80 µg h^?1 mg_cat.^?1 at ?0.2 V vs reversible hydrogen electrode), which is much higher than that of monometallic, especially noble metal, counterparts. The superior catalytic performance of alloy catalysts with low noble metal loading would strongly spur interest toward more researches on NRR catalysts in the future.     

Molecular recognition by gold, silver and copper nanoparticles

The intrinsic physical properties of the noble metal nanoparticles,which are highly sensitive to the nature of their local molecular environment,make such systems ideal for the detection of molecular recognition events.The current review describes the state of the art concerning molecular recognition of Noble metal nanoparticles.In the first part the preparation of such nanoparticles is discussed along with methods of capping and stabilization.A brief discussion of the three common methods of functionalization:Electrostatic adsorption;Chemisorption;Affinity-based coordination is given.In the second section a discussion of the optical and electrical properties of nanoparticles is given to aid the reader in understanding the use of such properties in molecular recognition.In the main section the various types of capping agents for molecular recognition;nucleic acid coatings,protein coatings and molecules from the family of supramolecular chemistry are described along with their numerous applications.Emphasis for the nucleic acids is on complementary oligonucleotide and aptamer recognition.For the proteins the recognition properties of antibodies form the core of the section.With respect to the supramolecular systems the cyclodextrins,calix[n]arenes,dendrimers,crown ethers and the cucurbitales are treated in depth.Finally a short section deals with the possible toxicity of the nanoparticles,a concern in public health.     

A Triphasic Bifunctional Oxygen Electrocatalyst with Tunable and Synergetic Interfacial Structure for Rechargeable Zn‐Air Batteries

Atomic‐scale design of interfacial structure is an intriguing but challenging approach to developing efficient heterogenous catalysts for bifunctional oxygen electrocatalysis. Herein, an exquisite triphasic interfacial structure featuring the encapsulation of Fe_xNi alloy in a graphitic shell with a partial exposure of the FeO_y thin‐layered surface is manipulated via an electronic modulation strategy. The spontaneous integration of well‐crystallized metal alloy, carbon shell with a tunable active FeO_y layer, not only guarantees smooth charge transfer across the thin oxide layer, but also generates the synergistic effect at the interface, thus dramatically boosting the intrinsic activity of oxygen catalysis. Benefiting from these attributes, the hybrid catalyst outperforms the commercial noble‐metal benchmarks with a higher half‐wave potential of 0.890 V for oxygen reduction reaction and lower overpotential of 308 mV at 10 mA cm^?2 for the oxygen evolution reaction in alkaline media. Beyond that, a high‐performance rechargeable Zn‐air battery is realized with a narrow voltage gap of 0.742 V and excellent cyclability over 500 cycles at 10 mA cm^?2, demonstrating the great potential of the as‐developed triphasic electrocatalyst for practical applications.     

Polymer nanostructures for bioapplications induced by laser treatment

Modification of polymer substrates can essentially change the properties of material and thereby it allows their usage in attractive fields of material research. Laser treatment can be successfully applied for change in physico-chemical surface properties and/or for selective change of surface morphology with pattern construction. Three major applications of laser induced structures were described, cytocompatibility control, application as anti-bacterial substrate and plasmonic-based detection system. The construction of a second generation antibacterials using the synergic effect of either nanopatterning of polymers by application of a laser or noble metals deposition and consequent modification of nanostructures was presented.     

Engineering Multimetallic Aerogels for pH‐Universal HER and ORR Electrocatalysis

The advent of noble metal aerogels (NMAs), that feature the high catalytic activity of noble metals and unique structural attributes of aerogels, has stimulated research on a new class of outstanding electrocatalysts. However, limited by the available compositions, the explored electrocatalytic reactions on NMAs are highly restricted and certain important electrochemical processes have not been investigated. Here, an effective gelation approach is demonstrated by using a strong salting‐out agent (i.e., NH₄F), thereby expanding the composition of NMAs to various multimetallic systems and providing a platform to investigate composition‐dependent electrocatalytic performance of NMAs. Combining structural features of aerogels and optimized chemical compositions, the Au–Pt and Au–Rh aerogel catalysts manifest remarkable pH‐universal (pH = 0–14) performance surpassing commercial Pt/C and many other nanoparticle (NP)‐based catalysts in the electrocatalytic oxygen reduction reaction, hydrogen evolution reaction, and water splitting, displaying enormous potential for the electrochemical hydrogen production, fuel cells, etc.     

Review of Some Interesting Surface Plasmon Resonance-enhanced Properties of Noble Metal Nanoparticles and Their Applications to Biosystems

Noble metal, especially gold (Au) and silver (Ag) nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR). In this review, we discuss the SPR-enhanced optical properties of noble metal nanoparticles, with an emphasis on the recent advances in the utility of these plasmonic properties in molecular-specific imaging and sensing, photo-diagnostics, and selective photothermal therapy. The strongly enhanced SPR scattering from Au nanoparticles makes them useful as bright optical tags for molecular-specific biological imaging and detection using simple dark-field optical microscopy. On the other hand, the SPR absorption of the nanoparticles has allowed their use in the selective laser photothermal therapy of cancer. We also discuss the sensitivity of the nanoparticle SPR frequency to the local medium dielectric constant, which has been successfully exploited for the optical sensing of chemical and biological analytes. Plasmon coupling between metal nanoparticle pairs is also discussed, which forms the basis for nanoparticle assembly-based biodiagnostics and the plasmon ruler for dynamic measurement of nanoscale distances in biological systems.     

Recent Development of Metallic (1T) Phase of Molybdenum Disulfide for Energy Conversion and Storage

The development of a feasible and inexpensive strategy to obtain and utilize sustainable energy is an important issue for the sustainable development of human society. Over the past decade, significant progress has been made in the development of novel functional materials for energy conversion and storage. Owing to their unique physico‐chemical properties, 2D layered materials, such as graphene and transition metal dichalcogenides, have attracted great interest in energy‐related research. 1T‐MoS₂ is a metallic phase of molybdenum disulfide (MoS₂) with extraordinary electronic conductivity, enlarged interlayer spacing, and more electrochemically active sites along the basal plane, which offers intriguing benefits for energy‐related applications compared to its semiconducting counterpart (2H‐MoS₂). This review summarizes the preparation and structure–property relationships of 1T‐MoS₂, as well as the underlying relations between the metallic (1T) and semiconducting (2H) phases of MoS₂. Recent progress in the preparation and stabilization of 1T‐MoS₂ materials and their applications for energy conversion and storage are discussed, including water splitting to form hydrogen via photo/electrocatalysis and electricity storage in lithium‐ion batteries, sodium‐ion batteries, magnesium‐ion batteries, and supercapacitors. Optimization strategies of 1T‐MoS₂ to obtain enhanced practical properties based on theoretical calculations are also presented.