2D interspace confined growth of ultrathin MoS2-intercalated graphite hetero-layers for high-rate Li/K storage

Herein,a two-dimensional(2D)interspace-confined synthetic strategy is developed for producing MoS₂intercalated graphite(G-MoS₂)hetero-layers composite through sulfuring the pre-synthesized stage-1 MoCI5-graphite intercalation compound(M0 CI5-GIC).The in situ grown MoS₂nanosheets(3-7 layers)are evenly encapsulated in graphite layers with intimate interface thus forming layer-by-layer MoS₂-intercalated graphite composite.In this structure,the unique merits of MoS₂and graphite components are integrated,such as high capacity contribution of MoS₂and the flexibility of graphite layers.Besides,the tight interfacial interaction between hetero-layers optimizes the potential of conductive graphite layers as matrix for MoS₂.As a result,the G-MoS₂exhibits a high reversible Li+storage of 344 mAh·g^-1even at 10 A·g^-1and a capacity of 539.9 mAh·g^-1after 1,500 cycles at 5 A·g^-1.As for potassium ion battery,G-MoS₂delivers a reversible capacity of 377.0 mAh·g^-1at 0.1 A·g^-1and 141.2 mAh·g^-1even at 2 A·g^-1.Detailed experiments and density functional theory calculation demonstrate the existence of hetero-layers enhances the diffusion rates of Li⁺and K⁺.This graphite interspace-confined synthetic methodology would provide new ideas for preparing function-integrated materials in energy storage and conversion,catalysis or other fields.     

Revealing the effect of anion-tuning in bimetallic chalcogenides on electrocatalytic overall water splitting

Enhancing electrocatalytic water splitting performance by modulating the intrinsic electronic structure is of great importance. Here, porous bimetallic oxide and chalcogenide nanosheets grown on carbon paper denoted as NiCo₂X₄/CP (X = O, S, and Se) are prepared to demonstrate how the anion components affect the electronic structures and thereby disclose the correlation between their intermediates interaction and catalytic activities. The experimental characterization and theoretical calculation demonstrate that Se and S substitution can promote the ratio of Co³⁺/Co²⁺ and thereby modulate the electronic structure accompanied with the upshift of d band centers, which not only enhance the inner conductivity but also regulate the interaction between the catalyst surface and intermediates, especially for the adsorption of absorbed H and hydroperoxy intermediates towards respective hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). As a result, a full alkaline electrolyzer using NiCo₂Se₄/CP and NiCo₂S₄/CP as cathode and anode delivers a low voltage of 1.51 V at 10 mA·cm⁻², which is comparable even superior to most transition metal-based electrolyzers.

     

High power and stable P-doped yolk-shell structured Si@C anode simultaneously enhancing conductivity and Li+ diffusion kinetics

Silicon is a low price and high capacity ancxje material for lithium-ion batteries.The yolk-shell structure can effectively accommodate Si expansion to improve stability.However,the limited rate performance of Si anodes can't meet people's growing demand for high power density.Herein,the phosphorus-doped yolk-shell Si@C materials(P-doped Si@C)were prepared through carbon coating on P-doped Si/SiO_xmatrix to obtain high power and stable devices.Therefore,the as-prepared P-doped Si@C electrodes delivered a rapid increase in Coulombic efficiency from 74.4%to 99.6%after only 6 cycles,high capacity retention of-95%over 800 cycles at 4 A·g^-1,and great rate capability(510 mAh·g^-1at 35 A·g^-1).As a result,P-doped Si@C anodes paired with commercial activated carbon and LiFePO₄cathode to assemble lithium-ion capacitor(high power density of?61,080 W·kg^-1at 20 A·g^-1)and lithium-ion full cell(good rate performance with 68.3 mAh·g^-1at 5 C),respectively.This work can provide an effective way tofurther improve power density and stability for energy storage devices.     

Oxygen vacancy engineering of calcium cobaltate: A nitrogen fixation electrocatalyst at ambient condition in neutral electrolyte

In order to sustainably transform N2 to ammonia(NRR)using electrocatalysts under mild ambient condition,it is urgent to design and develop non-nobel metal nanocatalysts that are inexpensive and suitable for mass-production.Herein,a calcium metalate catalyst CaCoO_xwith oxygen vacancies was synthesized and used as an electrocatalyst for NRR for the first time,whose morphology can be controlled by the calcination temperature and the heating rate.Under the optimal conditions,the CaCoO_xcatalyst achieved the yield of nitrogen conversion to ammonia of 16.25μg·h^-1·mg_cat.^-1at the potential of-0.3 V relative to the reversible hydrogen electrode(RHE)with a Faraday efficiency of 20.51%.The electrocatalyst showed good stability even after 12 times recyclability under environmental conditions and neutral electrolyte.Later,the electrocatalytic nitrogen reduction performance of CaFeO_x,CaNiO_x,CaCuO_xwas investigated.These earth-rich transition metals also exhibited certain NRR electrocatalytic capabilities,which provided a door for further development of inexpensive and easily available transition metal as nitrogen reduction electrocatalysts.     

Functionalized graphene oxide nanosheets with unique three-in-one properties for efficient and tunable antibacterial applications

Developing antibiotics-independent antibacterial agents is of great importance since antibiotic therapy faces great challenges from drug resistance.Graphene oxide(GO)is a promising agent due to its natural antibacterial mechanisms,such as sharp edgemediated cutting effect.However,the antibacterial activity of GO is limited by its negative charge and low photothermal effect.Herein,the amino-functionalized GO nanosheets(AGO)with unique three-in-one properties were synthesized.Three essential properties(positive charge,strong photothermal effect,and natural cutting effect)were integrated into AGO.The positive charge(30 mV)rendered AGO a strong interaction force with model pathogen Streptococcus mutans(330 nN).The natural cutting effect of 100 ng·mL^-1AGO caused 27%loss of bacterial viability after incubation for 30 min.Most importantly,upon the near-infrared irradiation for just 5 min,the three-in-one properties of AGO caused 98%viability loss.In conclusion,the short irradiation period and the tunable antibacterial activity confer the three-in-one AGO a great potential for clinical use.     

Carbon nanotube supported bifunctional electrocatalysts containing iron-nitrogen-carbon active sites for zinc-air batteries

Bifunctional electrocatalysts with high activity toward both oxygen reduction and evolution reaction are highly desirable for rechargeable Zn-air batteries. Herein, a kind of carbon nanotube (CNT) supported single-site Fe-N-C catalyst was fabricated via pyrolyzing in-situ grown Fe-containing zeolitic imidazolate frameworks on CNTs. CNTs not only serve as the physical supports of the Fe-N-C active sites but also provide a conductive network to facilitate the fast electron and ion transfer. The as-synthesized catalysts exhibit a half-wave potential of 0.865 V for oxygen reduction reaction and a low overpotential of 0.442 V at 10 mA·cm⁻² for oxygen evolution, which is 310 mV smaller than that of Fe-N-C without CNTs. The rechargeable Zn-air batteries fabricated with such hybrid catalysts display a high peak power density of 182 mW·cm⁻² and an excellent cycling stability of over 1,000 h at 10 mA·cm⁻², which outperforms commercial Pt-C and most of the reported catalysts. This facile strategy of combining single-site Metal-N-C with CNTs network is effective for preparing highly active bifunctional electrocatalysts.

     

Two-dimensional polymer nanosheets for efficient energy storage and conversion

As a promising graphene analogue, two-dimensional (2D) polymer nanosheets with unique 2D features, diversified topological structures and as well as tunable electronic properties, have received extensive attention in recent years. Here in this review, we summarized the recent research progress in the preparation methods of 2D polymer nanosheets, mainly including interfacial polymerization and solution polymerization. We also discussed the recent research advancements of 2D polymer nanosheets in the fields of energy storage and conversion applications, such as batteries, supercapacitors, electrocatalysis and photocatalysis. Finally, on the basis of their current development, we put forward the existing challenges and some personal perspectives.

     

Two-dimensional d-πconjugated metal-organic framework based on hexahydroxytrinaphthylene

The development of new two-dimensional(2D)d-πconjugated metal-organic frameworks(MOFs)holds great promise for the construction of a new generation of porous and semiconductive materials.This paper describes the synthesis,structural characterization,and electronic properties of a new d-πconjugated 2D MOF based on the use of a new ligand 2,3,8,9,14,15-hexahydroxytrinaphthylene.The reticular self-assembly of this largeπ-conjugated organic building block with Cu(II)ions in a mixed solvent system of 1,3-dimethyl-2-imidazolidinone(DMI)and H2 O with the addition of ammonia water or ethylenediamine leads to a highly crystalline MOF Cu3(HHTN)2,which possesses pore aperture of 2.5 nm.Cu3(HHTN)2 MOF shows moderate electrical conductivity of 9.01×10^-8S·cm^-1at 385 K and temperature-dependent band gap ranging from 0.75 to 1.65 eV.After chemical oxidation by l2,the conductivity of Cu3(HHTN)2 can be increased by 360 times.This access to HHTN based MOF adds an important member to previously reported MOF systems with hexagonal lattice,paving the way towards systematic studies of structure-property relationships of semiconductive MOFs.     

Improved Na storage and Coulombic efficiency in TiP2O7@C microflowers for sodium ion batteries

Ti-based anode materials in sodium ion batteries have attracted extensive interests due to its abundant resources,low toxicity,easy synthesis and long cycle life.However,low Coulombic efficiency and limited specific capacity affect their applications.Here,cubic-phase TiP₂O₇is examined as anode materials,using in-situ/ex-situ characterization techniques.It is concluded that the redox reactions of Ti4⁺/Ti³⁺and Ti³⁺/Ti⁰consecutively occur during the discharge/charge processes,both of which are highly reversible.These reactions make the specific capacity of TiP₂O₇even higher than the case of TiO2 that only contains a simple anion,0^2-.Interestingly,Ti species participate only one of the redox reactions,due to the remarkable difference in local structures related to the sodiation process.The stable discharge/charge products in TiP₂O₇reduce the side reactions and improve the Coulombic efficiency as compared to T i02.These features make it a promising Ti-based anode for sodium ion batteries.Therefore,TiP₂O₇@C microflowers exhibit excellent electrochemical performances,?109 mAh·g^-1after 10,000 cycles at 2 A·g^-1,or 95.2 mAh·g^-1at 10 A·g^-1.The results demonstrate new opportunities for advanced Ti-based anodes in sodium ion batteries.     

Large anisotropic negative thermal expansion in Cu-TDPAT metal-organic framework: A combined in situ X-ray diffraction and DRIFTS study

Cu-TDPAT(H₆TDPAT=2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine),a stable nanoporous metal-organic framework with rht topology,has sparked broad interest as an adsorbent for several chemical separation processes.In this work,in situ synchrotron diffraction experiments followed by sequential LeBail refinements reveal that Cu-TDPAT shows unusually large anisotropic negative thermal expansion(NTE).The PASCal crystallography tool,used to analyze the magnitude of the NTE,reveals an average volumetric thermal expansion coefficientαv=-20.3 MK^-1.This value is significantly higher than the one reported for Cu-BTC(also known as HKUST-1),which contains the same Cu-paddlewheel building unit,αv=-12 MK^-1.In situ synchrotron single crystal X-ray diffraction and in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)were employed to shed light on the NTE mechanism.Using these two methods,we were able to elucidate the three main structural motions that are responsible for the NTE effect.The more pronounced NTE behavior of Cu-TDPAT is attributed to the lower symmetry combined with the more complex ligand structure when compared to Cu-BTC.The knowledge obtained in this work is important for understanding the behavior of the adsorbent under transient variable temperature conditions in fixed adsorption beds.     

Nanovilli electrode boosts hydrogen evolution: A surface with superaerophobicity and superhydrophilicity

Although tremendous efforts have been paid on electrocatalysts toward efficient electrochemical hydrogen generation,breakthrough is still highly needed in the design and synthesis of wonderful non-precious-metal electrocatalyst.Herein,a nanovilli Ni2P electrode,which with superaerophobic and superhydropholic can significantly facilitate the mass and electron transfer was constructed via a facial morphology control strategy.Meanwhile,the substitution of sluggish oxygen evolution with urea oxidation,lowering the two-electrode cell voltage to only 1.48 volts to achieve a current density of 10 mA·cm^-2.Thus,the as-constructed electrode achieves the operation of hydrogen generation by an AA battery.This work sheds new light on the exploration of other high-efficient electrocatalysts for hydrogen generation by using intermittent clean energy.     

Fast and stable K-ion storage enabled by synergistic interlayer and pore-structure engineering

Carbon-based material has been regarded as one of the most promising electrode materials for potassium-ion batteries (PIBs). However, the battery performance based on reported porous carbon electrodes is still unsatisfactory, while the in-depth K-ion storage mechanism remains relatively ambiguous. Herein, we propose a facile “in situ self-template bubbling” method for synthesizing interlayer-tuned hierarchically porous carbon with different metallic ions, which delivers superior K-ion storage performance, especially the high reversible capacity (360.6 mAh·g⁻¹@0.05 A·g⁻¹), excellent rate capability (158.6 mAh·g⁻¹@10.0 A·g⁻¹) and ultralong high-rate cycling stability (82.8% capacity retention after 2,000 cycles at 5.0 A·g⁻¹). Theoretical simulation reveals the correlations between interlayer distance and K-ion diffusion kinetics. Experimentally, deliberately designed consecutive cyclic voltammetry (CV) measurements, ex situ Raman tests, galvanostatic intermittent titration technique (GITT) method decipher the origin of the excellent rate performance by disentangling the synergistic effect of interlayer and pore-structure engineering. Considering the facile preparation strategy, superior electrochemical performance and insightful mechanism investigations, this work may deepen the fundamental understandings of carbon-based PIBs and related energy storage devices like sodium-ion batteries, aluminum-ion batteries, electrochemical capacitors, and dual-ion batteries.

     

Noble-metal-free dye-sensitized selective oxidation of methane to methanol with green light (550 nm)

Developing low-energy input route for conversion of methane (CH₄) to value-added methanol (CH₃OH) at room temperature is important in environment and industry. Bonding in electron donor-acceptor hybrid can potentially promote charge transfer and photocatalytic efficiency of CH₄ conversion. Herein, bonding in electron donor rhodamine B (RhB)-acceptor (TiO₂) hybrid (RhB/TiO₂) significantly promotes the selectivity of photocatalytic oxidation of CH₄ to CH₃OH and utilization of visible light (low-energy photons) at ambient condition. Even under green light irradiation (λ = 550 nm), the noble-metal-free RhB/TiO₂ hybrid synthesized presents enhanced oxidation of CH₄ to CH₃OH with a generation rate of 143 µmol·g⁻¹·h⁻¹ and selectivity of 94%. This work demonstrates the possibility and feasibility of noble-metal-free catalysts for activating CH₄ under visible light at room temperature.

     

A robust bifunctional catalyst for rechargeable Zn-air batteries: Ultrathin NiFe-LDH nanowalls vertically anchored on soybean-derived Fe-N-C matrix

ABSTRACT NiFe layered double hydroxide(NiFe-LDH)nanosheets and metal-nitrogen-carbon materials(M-N-C,M=Ni,Fe,Co,etc.)are supreme catalysts in the oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)process,respectively.Nevertheless,the monotonic performance and insufficient stability severely hamper their practical application in rechargeable batteries.Herein,we simultaneously combine ultrathin NiFe-LDH nanowalls with renewable soybean-derived Fe-N-C matrix to obtain a hybrid materials(NiFe-LDH/FeSoy-CNSs-A),which exhibits robust catalytic activities for OER(E_j=10=1.53 V vs.RHE)and ORR(E_1/2=0.91 V vs.RHE),with a top-notch battery parameters and stability in assembled rechargeable Zn-air batteries.Intensive investigations indicate that the vertically dispersed NiFe-LDH nanosheets,Fe-N-C matrix derived from soybean and the strong synergy between them are responsible for the unprecedented OER and ORR performances.The key role of intrinsic N defects involved in the hybrid materials is firstly specified by ultrasoundassisted extraction of soy protein from soybean.The exquisite design can facilitate the utilization of sustainable biomass-derived catalysts,and the mechanism investigations of N defects and oxygenic groups on the structure-activity relationship can stimulate the progress of other functional hybrid electrocatalysts.     

Two-dimensional oxide derived from high-temperature liquid metals via bubble templating

Two-dimensional (2D) oxide can be continuously produced by bubbling oxygen into liquid metals and the harvesting of these oxide relies on the proper choice of dispersion solvents. The mass-production of ligand-free 2D materials from high melting-point metals will not be possible if the limited stability of the traditional dispersion solvents is not circumvented. Herein, liquid tin was used for the first time in the bubbling protocol and 2D tin oxide was obtained in molten salts. The nanosheets were studied with combined microscopic and spectroscopic techniques, and high-density grain boundaries was identified between the sub-5-nm nano-crystallites in the nanosheets. It gives rise to the high performance in electrocatalytic CO₂ reduction reaction. Density-functional-theory based calculation was applied to achieve a deeper understanding of the relationship between the activity, selectivity, and the grain-boundary features. The molten-salt based protocol could be explored for the synthesis of a library of functional 2D oxides.

     

Dandelion-Like Bi2S3/rGO hierarchical microspheres as high-performance anodes for potassium-ion and half/full sodium-ion batteries

Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) have been considered as attractive alternatives for next-generation battery systems, which have promising application potential due to their earth abundance of potassium and sodium, high capacity and suitable working potential, however, the design and application of bi-functional high-performance anode still remain a great challenge up to date. Bismuth sulfide is suitable as anode owing to its unique laminar structure with relatively large interlayer distance to accommodate larger radius ions, high theoretical capacity and high volumetric capacity etc. In this study, dandelion-like Bi₂S₃/rGO hierarchical microspheres as anode material for PIBs displayed reversible capacity, and 206.91 mAh·g⁻¹ could be remained after 1,200 cycles at a current density of 100 mA·g⁻¹. When applied as anode materials for SIBs, 300 mAh·g⁻¹ could be retained after 300 cycles at 2 A·g⁻¹ and its initial Coulombic efficiency is as high as 97.43%. Even at high current density of 10 A·g⁻¹, 120.3 mAh·g⁻¹ could be preserved after 3,400 cycles. The Na₃V₂(PO₄)₃@rGO//Bi₂S₃/rGO sodium ion full cells were successfully assembled which displays stable performance after 60 cycles at 100 mA·g⁻¹. The above results demonstrate that Bi₂S₃/rGO has application potential as high performance bi-functional anode for PIBs and SIBs.

     

NiCo-LDH nanosheets strongly coupled with GO-CNTs as a hybrid electrocatalyst for oxygen evolution reaction

The rational fabrication of highly efficient electrocatalysts with low cost toward oxygen evolution reaction (OER) is greatly desired but remains a formidable challenge. In this work, we present a facile and straightforward method of incorporating NiCo-layered double hydroxide (NiCo-LDH) into GO-dispersed CNTs (GO-CNTs) with interconnected configuration. X-ray absorption spectroscopy (XAS) reveals the strong electron interaction between NiCo-LDH and the underlying GO-CNTs substrate, which is supposed to facilitate charge transfer and accelerate the kinetics for OER. By tuning the amount of CNTs, the optimized NiCo-LDH/GO-CNTs composite can achieve a low overpotential of 290 mV at 10 mA·cm⁻² current density, a small Tafel slope of 66.8 mV·dec⁻¹ and robust stability, superior to the pure NiCo-LDH and commercial RuO₂ in alkaline media. The preeminent oxygen evolution performance is attributed to the synergistic effect stemming from the merits and the intimate electron interaction between LDH and GO-CNTs. This allows NiCo-LDH/GO-CNTs to be potentially applied in an industrial non-noble metal-based water electrolyzer as the anodic catalysts.

     

Robust enhanced hydrogen production at acidic conditions over molybdenum oxides-stabilized ultrafine palladium electrocatalysts

Electrochemical water splitting is quite seductive for eco-friendly hydrogen fuel energy production,however,the attainment of highly efficient,durable,and cheap catalysts for the hydrogen evolution reaction(HER)remains challenging.In this study,molybdenum oxides stabilized palladium nanoparticle catalysts(MoO_x-Pd)are in situ prepared on commercial carbon cloth(CC)by the facile two-step method of dip-coating and electrochemical reduction.As a self-supported Pd-based catalyst electrode,the MoO_x-Pd/CC presents a competitive Tafel slope of 45.75 mV·dec^-1,an ultralow overpotential of 25 mV,and extremely long cycling durability(one week)in 0.5M H₂S0₄electrolyte,superior to unmodified Pd catalysts and comparable to commercial Pt mesh electrode.On the one hand,the introduction of MoO_xcan inhibit the growth of Pd particles to obtain ultrafine Pd nanoparticles,thus exposing more available active sites.On the other hand,density functional theory(DFT)calculation revealed that MoO_xon the surface of Pd metal can regulate the electronic structure of Pd metal and enhance its intrinsic catalytic activity of HER.This work suggests that transitional metal nanoparticles stabilized by molybdenum oxides are hopeful approaches for obtaining fruitful hydrogen-producing electrocatalysts.     

Unprecedently low thermal conductivity of unique tellurium nanoribbons

Tellurene, probably one of the most promising two-dimensional (2D) system in the thermoelectric materials, displays ultra-low thermal conductivity. However, a linear thickness-dependent thermal conductivity of unique tellurium nanoribbons in this study reveals that unprecedently low thermal conductivity can be achieved via well-defined nanostructures of low-dimensional tellurium instead of pursuing dimension-reduced 2D tellurene. For thinnest tellurium nanoribbon with thickness of 144 nm, the thermal conductivity is only ∼1.88 ± 0.22 W·m⁻¹·K⁻¹ at room temperature. It’s a dramatic decrease (45%), compared with the well-annealed high-purity bulk tellurium. To be more specific, an expected thermal conductivity of tellurium nanoribbons is even lower than that of 2D tellurene, as a result of strong phonon-surface scattering. We have faith in low-dimensional tellurium in which the thermoelectric performance could realize further breakthrough.

     

Corrosion formation and phase transformation of nickel-iron hydroxide nanosheets array for efficient water oxidation

Designing earth-abundant electrocatalysts with high performance towards water oxidation is highly decisive for the sustainable energy technologies. This study develops a facile natural corrosion approach to fabricate nickel-iron hydroxides for water oxidation. The resulted electrode demonstrates an outstanding activity and stability with an overpotential of 275 mV to deliver 10 mA·cm⁻². Experimental and theoretical results suggest the corrosion-induced formation of hydroxides and their transformation to oxyhydroxides would account for this excellent performance. This work not only provides an interesting corrosion approach for the fabrication of excellent water oxidation electrode, but also bridges traditional corrosion engineering and novel materials fabrication, which would offer some insights in the innovative principles for nanomaterials and energy technologies.