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Recently, the increasing concerns regarding environmental and energy-related issues due to the use of fossil fuels have triggered extensive research on sustainable electrochemical energy storage and conversion (EESC). In this case, covalent triazine frameworks (CTFs) possess a large surface area, tailorable conjugated structures, electron donating–accepting/conducting moieties, and excellent chemical and thermal stabilities. These merits make them leading candidates for EESC. However, their poor electrical conductivity impedes electron and ion conduction, leading to unsatisfactory electrochemical performances, which limit their commercial applications. Thus, to overcome these challenges, CTF-based nanocomposites and their derivatives such as heteroatom-doped porous carbons, which inherit most of the merits of pristine CTFs, lead to excellent performances in the field of EESC. In this review, initially, we briefly highlight the existing strategies for the synthesis of CTFs with application-targeted properties. Next, we review the contemporary progress of CTFs and their derivatives related to electrochemical energy storage (supercapacitors, alkali-ion batteries, lithium–sulfur batteries, etc.) and conversion (oxygen reduction/evolution reaction, hydrogen evolution reaction, carbon dioxide reduction reaction, etc.). Finally, we discuss perspectives on current challenges and recommendations for the further development of CTF-based nanomaterials in burgeoning EESC research. [ABSTRACT FROM AUTHOR]

The carbons containing metals coordinated with nitrogen are emerging as the most promising catalysts toward various heterogeneous catalyses. In this paper, such a carbon catalyst is prepared through a chemical vapor deposition (CVD)‐supported precursor pyrolysis. Compared with the direct pyrolysis of polypyrrole@cobalt salt precursor, the incorporation of dicyanodiamide as the CVD source facilitates the diversification and hierarchization of carbon morphology, the reduction of Co particle size, and the increase of the proportion of interfacial Co−N−C and pyridinic‐N. The catalyst is composed of in‐situ‐grown multiple‐morphology carbons (MMCs) with metallic Co particles embedded, where the MMCs are a combination of nano‐particles, ‐rods, and ‐wires, all comprised by small N‐doped carbon nanoflakes. Owing to the combined modulation on morphology configurations and defect states, the Co/MMCs catalyst demonstrates excellent activities toward hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). A half‐wave potential of 0.84 V and low overpotentials of 86 and 180 mV at 10 mA cm−2 current density for HER and OER are achieved, respectively. Additionally, the catalyst also demonstrates favorable prospects for large‐scale applications in overall water splitting and Zn‐air battery. [ABSTRACT FROM AUTHOR]

• Vertically aligned Co-doped MoS 2 nanosheet array is prepared via CVD sulfurization. • The morphology is controlled by tuning CoCl 2 content in CoCl 2 -MoCl 5 precursor film. • The array exposes active edge sites primarily and facilitates electron transport. • Co-atom doping activates in-plane S atoms presenting at splits of nanosheets. A combination of high surface area, fast-speed charge transportation, excellent intrinsic activity, and low material cost is desired for electrocatalysts' applications, such as hydrogen production, counter electrodes of electrochemical solar cells, etc. In this regard, we originally develop a vertically aligned Co-doped MoS 2 nanosheet array via a facile chemical vapour deposition (CVD) approach that utilizes the reaction between drop-coated CoCl 2 -MoCl 5 precursor film and sulfur vapour released from elemental sulfur powder. Such structure that exposes primarily edge sites of the nanosheets provides reaction with more active centers and guarantees that electrons transport almost along high-electron-mobility basal plane of MoS 2. Simultaneously, the catalytic activity of the in-plane S atoms of MoS 2 , exposing at the splits of MoS 2 nanosheets, can be triggered via Co atom-doping. Such an array that is in-situ grown on graphite foil substrate performs as an efficient electrocatalyst for hydrogen evolution reaction with an overpotential of 185 mV at a current density of 10 mA·cm−2 and an extremely high TOF 0.56 s−1 at 200 mV overpotential, meanwhile, sponsoring as a counter electrode for efficient (8.99%) dye-sensitized solar cells. [ABSTRACT FROM AUTHOR]

• Co-N polymer is pyrolyzed with dicyandiamide to synthesize a Co-N-C catalyst. • Carbon nanosheet/nanotube-interweaved structure favors 3D electrical conduct. • Balanced micro/mesopore distribution facilitates mass diffusion. • Atomic and metal Co separately enable excellent ORR and OER performances. • Promising liquid and flexible rechargeable Zn-air batteries are achieved. Developing active and stable non-precious metal bifunctional electrocatalysts towards the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) still remains a crucial challenge. Herein, we propose a simple strategy of integrating atomically dispersed and nanoscaled Co species embedded in micro-/mesoporous carbon nanosheet/nanotube architecture. Revealed by control and SCN- poisoning experiments, N species and atomically dispersed Co species are the main active centers for ORR; whereas the metal Co nanocrystals are the chief active species for OER. Additionally, the balanced micro/mesopore distribution offers fast mass diffusion, and carbon nanosheet/nanotube architecture supplies favorable 3D electrical conduct. As a result, the as-prepared CoNC (1:4) exhibits a positive half-wave potential of 0.87 V (vs RHE) for ORR, and a low potential of 1.55 V (vs RHE) at 10 mA cm−2 for the OER. Importantly, the flexible Zn-air battery using the catalyst exhibits a peak power density of 117 mW cm−2, a higher round-trip efficiency of 68% cycling at 2 mA/cm−2, and an excellent cycling stability with 3% decrease after 126 cycles test. This work provides a general strategy to design bifunctional catalysts by integrating atomically dispersed and nanoscaled transitional metal species together with N-doped micro-/mesoporous 3D carbon. [ABSTRACT FROM AUTHOR]

Exploration high-efficient bifunctional electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is of great significance for several renewable energy applications. In this paper, a catalyst composed of Co 9 S 8 and porous carbon (Co 9 S 8 –C) is prepared first via the calcination of Co–S–C based precursor coating on carbon-fibre-paper (CFP) substrate under argon atmosphere. Then, the Co 9 S 8 –C is modified via the decomposition gas of dicyandiamide, thus Co 9 S 8 –N-doped carbon (Co 9 S 8 -NC) catalyst is synthesized. As revealed, the morphology and defect features are effectively modulated by the modification, suggesting the reduced particle sizes of Co 9 S 8 component and obviously improved N proportion and various defects. As a result, Co 9 S 8 -NC represents excellent activities electrocatalytic performances toward OER and ORR, which surpass those of its three counterparts including Co 9 S 8 –C, Co 9 S 8 , and NC. A half-wave potential of 0.86 ​V versus RHE for ORR and a low overpotential of 280 ​mV ​at 10 ​mA ​cm-2 current density for OER are achieved, with the Δ E value of 0.64 ​V. Additionally, the catalyst also demonstrates desirable application prospect for Zn-air battery. The post-treatment method reported here might be utilized widespread to promote the synergistic effects between the Co-contained particles and N-doped carbons in composite catalysts. The DCA post-treatment can produce high amounts of N-doped pore edges, and can simultaneously facilitate the intimate electronic contact between moderately eroded Co 9 S 8 and N-doped carbon matrix thus forming abundant high active coupling Co-N x -C centers. The catalyst demonstrates excellent bifunctional performance for catalyzing OER and ORR. Image 1 • Co 9 S 8 -porous N-doped carbon (NC) catalyst was in-situ synthesized on CFP substrate. • Intimate electronic contact between Co 9 S 8 and NC is achieved through a dicyandiamide post-treatment. • N content is much improved with rich new-formed pyridinic N and interfacial Co–N. • The catalyst exhibits remarkable OER/ORR bifunction and good prospect in flexible Zn-air battery. [ABSTRACT FROM AUTHOR]

Development of economical, stable and high-efficient electrocatalysts gives vital incentives to promote the large-scale implementation of clean energy devices. Transition metal sulfides and carbon materials provide broad platforms for design of highly active electrocatalysts thanks to their flexibility, high electrical conductivity, and possessing various catalytically active sites towards different reaction systems. Herein, a ternary-component MoS 2 –Co 9 S 8 -NC nanohybrid is synthesized, in which Co 9 S 8 , MoS 2 , and N-doped carbon (NC) are integrated with each other. Owing to forming abundant varied active centers including Co 9 S 8 –MoS 2 heterojunctions, and Co–N, Mo–N coupling centers locating at the contact interfaces between transition metal sulfides and N-doped carbon, the hybrid demonstrates greatly enhanced performances towards hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Such hybrid represents low overpotentials of 95 mV and 230 mV to achieve 10 mA cm−2 current density for HER and OER in 1.0 M KOH, respectively, and demonstrates favorable prospects for large-scale applications in overall water splitting. Image 1 • MoS 2 –Co 9 S 8 -NC is prepared via a facile precursor-solution-based process. • There are abundant MoS 2 /Co 9 S 8 , Co 9 S 8 /NC and MoS 2 /NC hetero-interfaces. • Abundant interfaces in MoS 2 –Co 9 S 8 -NC facilitate HER and OER performances. • Metal-N bonds are formed at Co 9 S 8 /NC and MoS 2 /NC interfaces with N doping. [ABSTRACT FROM AUTHOR]

[Display omitted] • A series of atomically dispersed Sb-N-C catalysts are prepared via a facile adsorption-pyrolysis strategy. • Atomically dispersed Sb are stabilized by N atoms in terms of Sb-N 5 configuration. • Self-evaporation of Sb during synthesis could create abundant micro/meso-pores. • Sb-N 5 sites enable Sb-N-C catalysts outstanding oxygen reduction reaction activity. • Abundant micro/ meso -pores enable Sb-N-C catalysts enhanced mass transport. Main-group metal based single-atom catalysts are attracting increasing research attention in electrochemical catalysis owing to their partially occupied valence p-orbitals. Herein, we report a series of atomically dispersed Sb-N-C catalysts (including Sb-N-C NP , Sb-N-C NL and Sb-N-C NT) synthesized by a facile adsorption-pyrolysis strategy for oxygen reduction reaction (ORR). Apart from generating atomically dispersed Sb-N 5 sites as active centers, self-evaporation of Sb during pyrolysis process has created abundant micro/meso-pores in Sb-N-C catalysts. Benefitting from these advantageous features, Sb-N-C presents outstanding ORR activity (Sb-N 5 sites) and efficient mass transport (micro/meso-pores). By rotating disk electrode (RDE) test in alkaline media, Sb-N-C exhibits a most positive half-wave potential of 0.90 V vs. RHE and a highest kinetic current density up to 43.8 mA cm−2 at 0.85 V vs. RHE. As gas diffusion electrode (GDE), Sb-N-C NP0.2 demonstrates fast O 2 diffusion and transport that enables smaller mass transport overpotential at high current densities up to 800 mA cm−2. Finally, Zn-air battery that uses the Sb-N-C NP catalyst as air electrode achieves a maximum power density of 180 mW cm−2 and more than 1000 hs of continuous operation. This work further demonstrates the excellent performance of main-group Sb single-atom catalyst toward ORR and applications in practical energy conversion devices. [ABSTRACT FROM AUTHOR]

[Display omitted] • Novel CoSb/NC catalysts are prepared via a novel Sb-modulated strategy. • The feeding amount of Sb salt is tuned to modulate the particle size and pore structure of CoSb/NC catalysts. • CoSb/NC catalysts exhibit enhanced ORR activity and kinetics outperforming the state-of-the-art Pt/C. • CoSb/NC catalysts are electrocatalytically active toward OER. • CoSb/NC catalysts can drive rechargeable Zn-air battery with a high peak power density of 180 mW cm−2. Rational modulation and optimization of structural properties plays a significant role in advancing the electrocatalytic performance of electrocatalysts. In this study, we report a novel Sb-modulated strategy to synthesize novel CoSb/NC catalysts comprised of CoSb alloy supported on nitrogen-doped carbon (denoted as CoSb/NC). Apart from alloying with Co to generate CoSb alloys, we demonstrated that the evaporation of Sb could modulate the particle size and pore structure of CoSb/NC. Such modulation has facilitated the formation of micro/meso-porous structure to accelerate the mass/charge transport and increase the accessibility of active sites, resulting in a highest kinetic current density of 22.6 mA cm−2 at 0.85 V vs. RHE as well as a low Tafel slope of 38 mV dec−1, which even outperforms the state-of-the-art Pt/C. Additionally, CoSb/NC is demonstrated to be electrocatalytic active toward OER with the overpotential to be 430 mV at 10 mA cm−2. Rechargeable Zn-air battery tests reveal that CoSb/NC possesses competitive performance in terms of charge-discharge ability and stability, suggesting its potential application in renewable energy conversion devices. This work provides a novel approach to modulate the structure of nitrogen-doped carbon based materials as efficient oxygen electrocatalysts. [ABSTRACT FROM AUTHOR]

• Co/N-C Zn is prepared via high-temperature gas-transport approach. • The intrinsic structure of Co/ N-C Zn has been greatly modulated by ZnCl 2 treatment. • Co/N-C Zn exhibits enhanced ORR and OER performance. • ORR and OER active sites are determined by control experiments. • Co/N-C Zn can drive liquid and solid-state rechargeable Zn-air battery efficiently. In this study, a facile surface treatment on polypyrrole (PPy) nanofiber with ZnCl 2 solution is employed to fabricate N-doped carbon anchored with metallic Co (denoted as Co/N-C Zn) via gas-transport approach. Structural characterizations reveal that the intrinsic structure of Co/N-C Zn in terms of its morphology, pore structure and defects have been greatly modulated by such a surface treatment, resulting in a higher loading amount of metallic Co, larger surface area and increased pyridinic N and Co-N species as efficient active sites. Benefiting from the structural modulation, Co/N-C Zn exhibits outstanding ORR activity and kinetics with a positive half-wave potential of 0.88 V vs. RHE, a high kinetic current density (J k) value of 36.6 mA cm−2 at 0.85 V vs. RHE, and a small Tafel slope of 55.9 mV dec−1, which even outperforms commercial Pt/C. Moreover, enhanced OER performance is also achieved in Co/N-C Zn , with an overpotential of 280 mV at 10 mA cm−2, surpasses that of commercial RuO 2 (295 mV). Finally, Co/N-C Zn shows promise for substitution of commercial Pt/C and RuO 2 to drive both liquid and solid-state rechargeable Zn-air batteries with high peak power densities of 196 mW cm−2 and 130 mW cm−2. [ABSTRACT FROM AUTHOR]

The particle size and dispersity of metal particles are key factors affecting the activity of electrocatalysts. Herein, employing N-doped carbon fiber as support, we report a facile gas-phase transport strategy for the synthesis of a series of transition metal nanoparticles (denoted as M/N-CF, M = Co, Cu, Mn, Ni, Fe). The current synthesis strategy not only yields metal nanoparticles with ultra-small size (∼5 nm) and good monodispersity, but also introduces a porous nanostructure with large surface area (730 m2 g−1) and rich M-N species. When used for catalyzing oxygen reduction reaction, all the M/N-CF catalysts adopt a highly efficient 4e− ORR pathway, reaching a most positive half-wave potential of 0.87 V vs. RHE for Mn/N-CF, quite approaching that of commercial Pt/C (0.88 V vs. RHE). Among them, Co/N-CF can also catalyze oxygen evolution reaction in an overpotential of 380 mV at 10 mA cm−2, approaching that of commercial RuO 2 (295 mV). Furthermore, as air electrode for rechargeable Zn-air battery, Co/N-CF based device achieves a high power density (163 mW cm−2) and good long-term cycling stability (over 50 h at 10 mA cm−2), suggesting the potential application of M/N-CF catalysts in energy conversion and storage systems. Image 1 • A facile and universal gas-phase transport strategy is presented to synthesize a series of transition metal based oxygen electrocatalysts (M/N-CF). • M/N-CF catalysts possess a porous nanostructure with large surface area and rich M − N species. • All the M/N-CF catalysts can catalyze ORR in a highly efficient 4e− ORR pathway. • Co/N-CF can simultaneously catalyze ORR and OER, achieving a high power density (163 mW cm−2) and good long-term cycling stability as air electrode in Zn-air battery. [ABSTRACT FROM AUTHOR]