Dynamic restructuring of nickel sulfides for electrocatalytic hydrogen evolution reaction.

Transition metal chalcogenides have been identified as low-cost and efficient electrocatalysts to promote the hydrogen evolution reaction in alkaline media. However, the identification of active sites and the underlying catalytic mechanism remain elusive. In this work, we employ operando X-ray absorption spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy to elucidate that NiS undergoes an in-situ phase transition to an intimately mixed phase of Ni3S2 and NiO, generating highly active synergistic dual sites at the Ni3S2/NiO interface. The interfacial Ni is the active site for water dissociation and OH* adsorption while the interfacial S acts as the active site for H* adsorption and H2 evolution. Accordingly, the in-situ formation of Ni3S2/NiO interfaces enables NiS electrocatalysts to achieve an overpotential of only 95 ± 8 mV at a current density of 10 mA cm-2. Our work highlighted that the chemistry of transition metal chalcogenides is highly dynamic, and a careful control of the working conditions may lead to the in-situ formation of catalytic species that boost their catalytic performance.

Activating TiO2 through the Phase Transition-Mediated Hydrogen Spillover to Outperform Pt for Electrocatalytic pH-Universal Hydrogen Evolution.

Endowing conventional materials with specific functions that are hardly available is invariably of significant importance but greatly challenging. TiO2 is proven to be highly active for the photocatalytic hydrogen evolution while intrinsically inert for electrocatalytic hydrogen evolution reaction (HER) due to its poor electrical conductivity and unfavorable hydrogen adsorption/desorption behavior. Herein, the first activation of inert TiO2 for electrocatalytic HER is demonstrated by synergistically modulating the positions of d-band center and triggering hydrogen spillover through the dual doping-induced partial phase transition. The N, F co-doping-induced partial phase transition from anatase to rutile phase in TiO2 (AR-TiO2|(N,F)) exhibits extraordinary HER performance with overpotentials of 74, 80, and 142 mV at a current density of 10 mA cm-2 in 1.0 M KOH, 0.5 M H2SO4, and 1.0 M phosphate-buffered saline electrolytes, respectively, which are substantially better than pure TiO2, and even superior to the benchmark Pt/C catalysts. These findings may open a new avenue for the development of low-cost alternative to noble metal catalysts for electrocatalytic hydrogen production.

Functional nanoporous graphene superlattice.

Two-dimensional (2D) superlattices, formed by stacking sublattices of 2D materials, have emerged as a powerful platform for tailoring and enhancing material properties beyond their intrinsic characteristics. However, conventional synthesis methods are limited to pristine 2D material sublattices, posing a significant practical challenge when it comes to stacking chemically modified sublattices. Here we report a chemical synthesis method that overcomes this challenge by creating a unique 2D graphene superlattice, stacking graphene sublattices with monodisperse, nanometer-sized, square-shaped pores and strategically doped elements at the pore edges. The resulting graphene superlattice exhibits remarkable correlations between quantum phases at both the electron and phonon levels, leading to diverse functionalities, such as electromagnetic shielding, energy harvesting, optoelectronics, and thermoelectrics. Overall, our findings not only provide chemical design principles for synthesizing and understanding functional 2D superlattices but also expand their enhanced functionality and extensive application potential compared to their pristine counterparts.

Atomically Dispersed Co2 MnN8 Triatomic Sites Anchored in N-Doped Carbon Enabling Efficient Oxygen Reduction Reaction.

Atomically dispersed transition metal-nitrogen/carbon (M-N/C) catalysts have emerged as the most promising substitutes to the precious platinum counterparts toward the oxygen reduction reaction (ORR). However, the reported M-N/C catalysts are usually in the form of common M-N4 moieties with only a single metal active site, and they suffer from insufficient activity. Herein, an unusual trinuclear active structure is elaborately developed with a nitrogen-coordinated single Mn atom adjacent to two Co atoms (Co2 MnN8 ) anchored in N-doped carbon as a highly efficient ORR catalyst via adsorption-pyrolysis of a bimetallic zeolitic imidazolate framework precursor. Atomic structural investigations and density functional theory (DFT) calculations reveal that Co2 MnN8 would experience a spontaneous OH binding to form Co2 MnN8 -2OH as the real active site, leading to a single electron-filled state in the d z 2 ${\mathrm{d}}_{{z}^{2}}$ orbital and an optimized binding energy of intermediates. Accordingly, the as-developed Co2 MnN8 /C exhibits an unprecedented ORR activity with a high half-wave potential of 0.912 V and outstanding stability, not only surpassing the Pt/C catalyst but also representing a new record for the Co-based catalyst.

Staggered circular nanoporous graphene converts electromagnetic waves into electricity.

Harvesting largely ignored and wasted electromagnetic (EM) energy released by electronic devices and converting it into direct current (DC) electricity is an attractive strategy not only to reduce EM pollution but also address the ever-increasing energy crisis. Here we report the synthesis of nanoparticle-templated graphene with monodisperse and staggered circular nanopores enabling an EM-heat-DC conversion pathway. We experimentally and theoretically demonstrate that this staggered nanoporous structure alters graphene's electronic and phononic properties by synergistically manipulating its intralayer nanostructures and interlayer interactions. The staggered circular nanoporous graphene exhibits an anomalous combination of properties, which lead to an efficient absorption and conversion of EM waves into heat and in turn an output of DC electricity through the thermoelectric effect. Overall, our results advance the fundamental understanding of the structure-property relationships of ordered nanoporous graphene, providing an effective strategy to reduce EM pollution and generate electric energy.

Inner Co Synergizing Outer Ru Supported on Carbon Nanotubes for Efficient pH-Universal Hydrogen Evolution Catalysis.

Exploring highly active but inexpensive electrocatalysts for the hydrogen evolution reaction (HER) is of critical importance for hydrogen production from electrochemical water splitting. Herein, we report a multicomponent catalyst with exceptional activity and durability for HER, in which cobalt nanoparticles were in-situ confined inside bamboo-like carbon nanotubes (CNTs) while ultralow ruthenium loading (~ 2.6 µg per electrode area ~ cm-2) is uniformly deposited on their exterior walls (Co@CNTsǀRu). The atomic-scale structural investigations and theoretical calculations indicate that the confined inner Co and loaded outer Ru would induce charge redistribution and a synergistic electron coupling, not only optimizing the adsorption energy of H intermediates (ΔGH*) but also facilitating the electron/mass transfer. The as-developed Co@CNTsǀRu composite catalyst requires overpotentials of only 10, 32, and 63 mV to afford a current density of 10 mA cm-2 in alkaline, acidic and neutral media, respectively, representing top-level catalytic activity among all reported HER catalysts. The current work may open a new insight into the rational design of carbon-supported metal catalysts for practical applications.

Integrating trace ruthenium cluster with cobalt boride toward superior overall water splitting in neutral media.

Cobalt boride which is an active bifunctional water splitting catalyst in alkaline media shows poor activity in neutral media. We found that trace ruthenium (Ru) cluster deposition (80 µg·cm-2) on cobalt boride by simple wet chemical reduction method can dramatically improve both its hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity in neutral solution. The electron transfer from Co-B to Ru may result in the easier water dissociation step so as to facilitate the catalytic process. The resulting Ru@Co-B/Ni binder-free electrode could supply 10 mA cm-2 at overpotentials of 56 mV for HER and 280 mV for OER in 0.5 M phosphate buffer electrolyte. This work proposed a fruitful approach to advance the water splitting performance of transition metal boride in neutral media.

Alloying Co Species into Ordered and Interconnected Macroporous Carbon Polyhedra for Efficient Oxygen Reduction Reaction in Rechargeable Zinc-Air Batteries.

Engineering non-precious transition metal (TM)-based electrocatalysts to simultaneously achieve an optimal intrinsic activity, high density of active sites, and rapid mass transfer ability for the oxygen reduction reaction (ORR) remains a significant challenge. To address this challenge, a hybrid composite consisting of Fex Co alloy nanoparticles uniformly implanted into hierarchically ordered macro-/meso-/microporous N-doped carbon polyhedra (HOMNCP) is rationally designed. The combined results of experimental and theoretical investigations indicate that the alloying of Co enables a favorable electronic structure for the formation of the *OH intermediate, while the periodically trimodal-porous structured carbon matrix structure not only provides highly accessible channels for active site utilization but also dramatically facilitates mass transfer in the catalytic process. As expected, the Fe0.5 Co@HOMNCP composite catalyst exhibits extraordinary ORR activity with a half-wave potential of 0.903 V (vs reversible hydrogen electrode), surpassing most Co-based catalysts reported to date. More remarkably, the use of the Fe0.5 Co@HOMNCP catalyst as the air electrode in a zinc-air battery results in superior open-circuit voltage and power density compared to a commercial Pt/C + IrO2 catalyst. The results of this study are expected to inspire the development of advanced TM-based catalysts for energy storage and conversion applications.

Sequential Phase Conversion-Induced Phosphides Heteronanorod Arrays for Superior Hydrogen Evolution Performance to Pt in Wide pH Media.

Developing an efficient and non-precious pH-universal hydrogen evolution reaction electrocatalyst is highly desirable for hydrogen production by electrochemical water splitting but remains a significant challenge. Herein, a hierarchical structure composed of heterostructured Ni2 P-Ni12 P5 nanorod arrays rooted on Ni3 S2 film (Ni2 P-Ni12 P5 @Ni3 S2 ) via a simultaneous corrosion and sulfidation is built followed by a phosphidation treatment toward the metallic nickel foam. The combination of theoretical calculations with in/ex situ characterizations unveils that such a unique sequential phase conversion strategy ensures the strong interfacial coupling between Ni2 P and Ni12 P5 as well as the robust stabilization of 1D heteronanorod arrays by Ni3 S2 film, resulting in the promoted water adsorption/dissociation energy, the optimized hydrogen adsorption energy, and the enhanced electron/proton transfer ability accompanied with an excellent stability. Consequently, Ni2 P-Ni12 P5 @Ni3 S2 /NF requires only 32, 46, and 34 mV overpotentials to drive 10 mA cm-2 in 1.0 m KOH, 0.5 m H2 SO4 , and 1.0 m phosphate-buffered saline electrolytes, respectively, exceeding almost all the previously reported non-noble metal-based electrocatalysts. This work may pave a new avenue for the rational design of non-precious electrocatalysts toward pH-universal hydrogen evolution catalysis.

Binder-Free Air Electrodes for Rechargeable Zinc-Air Batteries: Recent Progress and Future Perspectives.

Designing an efficient air electrode is of great significance for the performance of rechargeable zinc (Zn)-air batteries. However, the most widely used approach to fabricate an air electrode involves polymeric binders, which may increase the interface resistance and block electrocatalytic active sites, thus deteriorating the performance of the battery. Therefore, binder-free air electrodes have attracted more and more research interests in recent years. This article provides a comprehensive overview of the latest advancements in designing and fabricating binder-free air electrodes for electrically rechargeable Zn-air batteries. Beginning with the fundamentals of Zn-air batteries and recently reported bifunctional active catalysts, self-supported air electrodes for liquid-state and flexible solid-state Zn-air batteries are then discussed in detail. Finally, the conclusion and the challenges faced for binder-free air electrodes in Zn-air batteries are also highlighted.

Porous Carbon Architecture Assembled by Cross-Linked Carbon Leaves with Implanted Atomic Cobalt for High-Performance Li-S Batteries.

The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity, polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes. Herein, a hierarchically porous three-dimension (3D) carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been delicately developed as an advanced sulfur host through a SiO2-mediated zeolitic imidazolate framework-L (ZIF-L) strategy. The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithiation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion. Owing to the accelerated kinetics and suppressed shuttle effect, the as-prepared sulfur cathode exhibits a superior electrochemical performance with a high reversible specific capacity of 695 mAh g-1 at 5 C and a low capacity fading rate of 0.053% per cycle over 500 cycles at 1 C. This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.

A flexible electromagnetic wave-electricity harvester.

Developing an ultimate electromagnetic (EM)-absorbing material that can not only dissipate EM energy but also convert the generated heat into electricity is highly desired but remains a significant challenge. Here, we report a hybrid Sn@C composite with a biological cell-like splitting ability to address this challenge. The composite consisting of Sn nanoparticles embedded within porous carbon would split under a cycled annealing treatment, leading to more dispersed nanoparticles with an ultrasmall size. Benefiting from an electron-transmitting but a phonon-blocking structure created by the splitting behavior, an EM wave-electricity device constructed by the optimum Sn@C composite could achieve an efficiency of EM to heat at widely used frequency region and a maximum thermoelectric figure of merit of 0.62 at 473 K, as well as a constant output voltage and power under the condition of microwave radiation. This work provides a promising solution for solving EM interference with self-powered EM devices.

Dual-carbon coupled Co5.47N composites for capacitive lithium-ion storage.

Transition metal nitrides are of great interest as potential anodes for lithium-ion batteries (LIBs) owing to their high theoretical capacity. However, poor cycling stability and rate performance greatly hinder their practical applications. To better alleviate these problems, a unique 3D hierarchical nanocomposite constructed by dual carbon-coated Co5.47N nano-grains wrapped with carbon and reduced graphene oxide (Co5.47N@C@rGO) was synthesized through one-step simultaneous nitridation and carbonization of zeolitic imidazolate frameworks@GO precursor. The 3D hierarchical Co5.47N@C@rGO composite can combine the good conductivity and mechanical strength of rGO and a high theoretical capacity of Co5.47N. When explored as anode material for LIBs, Co5.47N@C@rGO exhibits a high reversible capacity of ~860 mAh g-1 at a current density of 1.0 A g-1 after 500 cycles and excellent high-rate capability (665 and 573 mAh g-1 at current densities of 3.2 and 6.4 A g-1, respectively). The excellent electrochemical performance of Co5.47N@C@rGO can be ascribed to its hierarchically porous structure and the synergistic effect between Co5.47N nano-grains and rGO.

Vacancy Occupation-Driven Polymorphic Transformation in Cobalt Ditelluride for Boosted Oxygen Evolution Reaction.

Transition-metal dichalcogenides (TMDs) hold great potential as an advanced electrocatalyst for oxygen evolution reaction (OER), but to date the activity of transition metal telluride catalysts are demonstrated to be poor for this reaction. In this study, we report the activation of CoTe2 for OER by doping secondary anions into Te vacancies to trigger a structural transition from the hexagonal to the orthorhombic phase. The achieved orthorhombic CoTe2 with partial vacancies occupied by P-doping exhibits an exceptional OER catalytic activity with an overpotential of only 241 mV at 10 mA cm-2 and a robust stability more than 24 h. The combined experimental and theoretical studies suggest that the defective phase transformation is controllable and allows the synergism of vacancy, doping as well as the reconstructed crystallographic structure, ensuring more exposure of catalytic active sites, rapid charge transfer, and energetically favorable intermediates. This vacancy occupation-driven strategy of structural transformation can also be manipulated by S- and Se-doping, which may offer useful guidance for developing tellurides-based electrocatalyst for OER.

In-situ embedding cobalt-doped copper sulfide within ultrathin carbon nanosheets for superior lithium storage performance.

Construction of well-defined hybrid composites consisting of transition metal sulfides and two-dimensional (2D) carbon nanosheets as high-performance anodes for lithium-ion batteries (LIBs) is of great significance but remains challenging. Herein, we have developed a novel strategy to in-situ fabricate a nanohybrid composites consisting of cobalt-doped copper sulfides nanoparticles embedded in 2D carbon nanosheets (2D Co-Cu2S@C) through a one-pot sulfurization of 2D nanosheet-like Co-doped copper-based metal-organic frameworks (MOFs) precursors. When applied as LIBs anodes, the as-prepared 2D Co-Cu2S@C composites could deliver a specific capacity of 780 mAh g-1 at 0.5 A g-1 after 300 cycles and a high-rate capability with 209 mAh g-1 at 5 A g-1, superior to most reported copper sulfide-based anodes. The exceptional performance could be attributed to the synergism of ultrathin structure (~4 nm), appropriate cobalt doping and strong carbon coupling, resulting in the shortened paths for Li+ transportation, enlarged exposing surface for Li+ adsorption, enhanced electric conductivity for charge transfer as well as robust mechanical property against volume expansion.

In Situ Biomimetic Mineralization on ZIF-8 for Smart Drug Delivery.

The exploration of metal-organic frameworks (MOFs) with good biocompatibility and physiological stability as carrier platforms for biomedical applications is of great importance but remains challenging. Herein, we developed an in situ biomimetic mineralization strategy on zeolitic imidazolate framework (ZIF) nanocrystals to construct a drug release system with favorable cytocompatibility, improved stability, and pH responsiveness. With lysozyme (Lys) wrapped on the surface of Zn-based ZIF (ZIF-8), Lys/ZIF-8 could strongly bond metal ions to promote nucleation and growth of bone-like hydroxyapatite (HAp), leading to formation of HAp@Lys/ZIF-8 composites. In vitro investigations indicate that the composites with a hollow Lys/ZIF-8 core and a HAp shell exhibited a high drug-loading efficiency (56.5%), smart pH-responsive drug delivery, cytocompatibility, and stability under physiological conditions. The proposed biomimetic mineralization strategy for designing MOFs-based composites may open a new avenue to construct advanced delivery systems in the biomedical field.

Multifunctional Electrocatalysis on a Porous N-Doped NiCo2O4@C Nanonetwork.

Developing a multifunctional electrocatalyst with eminent activity, strong durability, and cheapness for the hydrogen/oxygen evolution reaction (HER/OER) and oxygen reduction reaction (ORR) is critical to overall water splitting and regenerative fuel cells. Herein, a nitrogen-doped nanonetwork assembled by porous and defective NiCo2O4@C nanowires grown on nickel foam (N-NiCo2O4@C@NF) is crafted via biomimetic mineralization and following carbonization of phase-transited lysozyme (PTL)-coupled NiCo2O4. The as-obtained N-NiCo2O4@C@NF electrocatalysts exhibit an exceptional catalytic activity with ultralow overpotentials for the HER (42 mV) and OER (242 mV) to afford 10 mA cm-2 while maintaining good stability in alkaline media. Meanwhile, the N-NiCo2O4@C electrocatalysts presents a superior catalytic activity for ORR and a favorable four-electron pathway. The unprecedented catalytic performance arises from a highly porous structure and abundant defects and synergistic effects of components. This work may offer a new possibility in the exploration of multifunctional electrocatalysts for various energy-related electrocatalytic reactions.

Phase-Transited Lysozyme-Driven Formation of Self-Supported Co3O4@C Nanomeshes for Overall Water Splitting.

The development of highly efficient catalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of paramount importance in water splitting. Herein, a phase-transited lysozyme (PTL) is employed as the platform to synthesize nitrogen-doped Co3O4@C nanomesh with rich oxygen vacancies supported on the nickel foam (N-Co3O4@C@NF). This PTL-driven N-Co3O4@C@NF integrates the advantages of porous structure, high exposure of surface atoms, strong synergetic effect between the components and unique 3D electrode configuration, imparting exceptional activity in catalyzing both HER and OER. Remarkably, an alkaline electrolyzer assembled by N-Co3O4@C@NF as both cathode and anode delivers a current density of 10 mA cm-2 at an ultralow cell voltage of 1.40 V, which is not only much lower than that of the commercially noble Pt/C and IrO2/C catalyst couple (≈1.61 V) but also a new record for the overall water splitting. The finding may open new possibilities for the design of bifunctional electrocatalysts for application in practical water electrolysis.

Iron-Doping-Induced Phase Transformation in Dual-Carbon-Confined Cobalt Diselenide Enabling Superior Lithium Storage.

Transition metal chalcogenides (TMCs) have been investigated as promising anodes for high-performance lithium-ion batteries, but they usually suffer from poor conductivity and large volume variation, thus leading to unsatisfactory performance. Although nanostructure engineering and hybridization with conductive materials have been proposed to address this concern, a better performance toward practical device applications is still highly desired. Herein, we report an iron-doping-induced structural phase transition from pyrite-type (cubic) to marcasite-type (orthorhombic) phases in porous carbon/rGO-coupled CoSe2. The dual-carbon-confined orthorhombic CoSe2 ( o-Fe xCo1- xSe2@NC@rGO) composites exhibit dramatically enhanced lithium storage performance (920 mAh g-1 after 1000 cycles at 1.0 A g-1) over cubic CoSe2-based composites ( c-CoSe2@NC@rGO). The combined experimental studies and density functional theory calculations reveal that this doping-induced structural phase transformation strategy could create a favorable electronic structure and ensure a rapid charge transfer. These results demonstrate that the phase-transformation engineering may provide another opportunity in the design of high-performance TMC-based electrodes.

Porous hollow composites assembled by NixCo1-xSe2 nanosheets rooted on carbon polyhedra for superior lithium storage capability.

Transition metal chalcogenides (TMCs) have attracted considerable interest owing to their satisfied theoretical capacity, good safety and environmentally benign nature in lithium-ion batteries (LIBs). However, the poor conductivity as well as the severe volume changes during the discharge-charge process cause capacity fading rapidly, which severely impede the practical applications of TMCs. To address this challenge, a hollow hybrid architecture assembled by NixCo1-xSe2 nanosheets and strongly coupled porous carbon have been rational designed. Within this structure, the integration of nanosheets rooted on the surface of porous carbon not only provide three-dimensional conductive network but also offer plentiful pathways and active sites for electrolyte penetration and Li storage, and buffer a large volume expansion/contraction caused by lithium intercalation/deintercalation. As evidenced by electrochemical measurements, the NixCo1-xSe2/C composites used as anodes in LIBs exhibit a superior reversible high capacity of 1667 mA h g-1 at current density of 2.0 A g-1 over 600 cycles and an outstanding rate capability (1580 and 1093 mA h g-1 at 3.2 and 6.4 A g-1, respectively).