Carbonitride MXene Ti_(3)CN(OH)_(x)@MoS_(2)hybrids as efficient electrocatalyst for enhanced hydrogen evolution

Renewable energy powered electrocatalytic water splitting is a promising strategy for hydrogen generation,and the design and development of high-efficiency and earth-abundant electrocatalysts for hydrogen evolution reaction(HER)are highly desirable.Herein,MoS2 nanoflowers decorated two-dimensional carbonitride-based MXene Ti3CN(OH)x hybrids have been constructed by etching and post-hydrothermal methods.The electrochemical performance of the as-obtained Ti_(3)CN(OH)_(x)@MoS_(2)hybrids having a quasi core-shell structure is fascinating:An overpotential of 120 mV and a Tafel slope of 64 mV∙dec^(−1)can be delivered at a current density of 10 mA∙cm^(−2).And after 3,000 cyclic voltammetry cycles,it can be seen that there is no apparent attenuation.Both the experimental results and density functional theory(DFT)calculations indicate that the synergetic effects between Ti_(3)CN(OH)x and MoS_(2)are responsible for the robust electrochemical HER performance.The electrons of-OH group in Ti_(3)CN(OH)x are transferred to MoS_(2),making the adsorption energy of the composite for H almost vanish.The metallic Ti_(3)CN(OH)x is also beneficial to the fast charge transfer kinetics.The construction of MXene-based hybrids with optimal electronic structure and unique morphology tailored to the applications can be further used in other promising energy storage and conversion devices.

Sulfur-doped g-C_(3)N_(4)/g-C_(3)N_(4) isotype step-scheme heterojunction for photocatalytic H_(2) evolution

The rational fabrication of an efficient heterojunction is critical to the enhancement of photocatalytic hydrogen(H_(2)) evolution performance.Herein,a new-fashioned graphitic-carbon nitride(g-C_(3) N_(4)) based isotype step-scheme(S-scheme) heterojunction composed of sulfur-doped and sulfur-free active sites is developed by liquid sulfur-mediation of exfoliated g-C_(3) N_(4).Particularly,the liquid sulfur not only contributes to the full contact between sulfur species and exfoliated g-C_(3) N_(4),but also creates sulfur-doping and abundant pores,since self-gas foaming effect of sulfur vapor.Moreover,the S-doped and S-free active sites located in the structural unit of C_(3) N_(4) jointly construct a typical sulfur-doped g-C_(3) N_(4)/g-C_(3) N_(4) isotype step-scheme heterojunction,which endows highly efficient photocatalytic reaction process.Therefore,the optimal sample possesses remarkable photocatalytic H_(2) evolution activity(5548.1 μmol g^(-1) h^(-1)) and robust durability.Most importantly,the investigation will open up a new path for the exploration of other carbon-based isotype S-scheme heterojunctions.

Improving stability of MXenes

Due to their superior hydrophilicity and conductivity,ultra-high volumetric capacitance,and rich surface-chemistry properties,MXenes exhibit unique and excellent performance in catalysis,energy storage,electromagnetic shielding,and life sciences.Since they are derived from ceramics(MAX phase)through etching,one of the challenges in MXenes preparation is the inevitable exposure of metal atoms on their surface and embedding of anions and cations.Because the as-obtained MXenes are always in a thermodynamically metastable state,they tend to react with trace oxygen or oxygen-containing groups to form metal oxides or degrade,leading to sharply declined activity and impaired performance.Therefore,improving the stability of MXenesbased materials is of practical significance in relevant applications.Unfortunately,there lacks a comprehensive review in the literature on relevant topics.To help promote the wide applications of MXenes,we review from the following aspects:(i)insights into the factors affecting the stability of MXenes-based materials,including oxidation of MXenes flakes,stability of MXenes colloidal solutions,and swelling and degradation of MXenes thin-film,(ii)strategies for enhancing the stability of MXenes-based materials by optimizing MAX phase synthesis and modifying the MXenes preparation,and(iii)techniques for further increasing the stability of freshly prepared MXenes-based materials via controlling the storage conditions,and forming shielding on the surface and/or edge of MXenes flakes.Finally,some outlooks are proposed on the future developments and challenges of highly active and stable MXenes.We aim to provide guidance for the design,preparation,and applications of MXenes-based materials with excellent stability and activity.

Strategic design and fabrication of MXenes-Ti_(3)CNCl_(2)@CoS_(2) core-shell nanostructure for high-efficiency hydrogen evolution

CoS_(2) is considered to be a promising electrocatalyst for hydrogen evolution reaction(HER).However,its further widespread applications are hampered by the unsatisfactory activity due to relatively high chemisorption energy for hydrogen atom.Herein,theoretical predictions of first-principles calculations reveal that the introduction of a Cl-terminated MXenes-Ti_(3)CNCl_(2) can significantly reduce the HER potential of CoS_(2)-based materials and the Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure has Gibbs free energy of hydrogen adsorption(|ΔGH|)close to zero,much lower than that of the pristine CoS_(2) and Ti_(3)CNCl_(2).Inspired by the theoretical predictions,we have successfully fabricated a unique Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure by ingeniously coupling CoS_(2) with a Cl-terminated MXenes-Ti_(3)CNCl_(2).Interface-charge transfer between CoS_(2) and Ti_(3)CNCl_(2) results in a higher degree of electronic localization and a formation of chemical bonding.Thus,the Ti_(3)CNCl_(2)@CoS_(2) core–shell nanostructure achieves a significant enhancement in HER activity compared to pristine CoS_(2) and Ti_(3)CNCl_(2).Theoretical calculations further confirm that the partial density of states of CoS_(2) after hybridization becomes more non-localized,and easier to interact with hydrogen ions,thus boosting HER performance.In this work,the success of oriented experimental fabrication of high-efficiency Ti_(3)CNCl_(2)@CoS_(2) electrocatalysts guided by theoretical predictions provides a powerful lead for the further strategic design and fabrication of efficient HER electrocatalysts.

In-situ Construction of Sulfur-doped g-C_(3)N_(4)/defective g-C_(3)N_(4) Isotype Step-scheme Heterojunction for Boosting Photocatalytic H_(2) Evolution

The rational construction of a high-efficiency stepscheme heterojunctions is an effective strategy to accelerate the photocatalytic H_(2).Unfortunately,the variant energy-level matching between two different semiconductor confers limited the photocatalytic performance.Herein,a newfangled graphitic-carbon nitride(g-C_(3)N_(4))based isotype step-scheme heterojunction,which consists of sulfur-doped and defective active sites in one microstructural unit,is successfully developed by in-situ polymerizing N,N-dimethylformamide(DMF)and urea,accompanied by sulfur(S)powder.Therein,the polymerization between the amino groups of DMF and the amide group of urea endows the formation of rich defects.The propulsive integration of S-dopants contributes to the excellent fluffiness and dispersibility of lamellar g-C_(3)N_(4).Moreover,the developed heterojunction exhibits a significantly enlarged surface area,thus leading to the more exposed catalytically active sites.Most importantly,the simultaneous introduction of S-doping and defects in the units of g-C_(3)N_(4) also results in a significant improvement in the separation,transfer and recombination efficiency of photo-excited electron-hole pairs.Therefore,the resulting isotype step-scheme heterojunction possesses a superior photocatalytic H_(2) evolution activity in comparison with pristine g-C_(3)N_(4).The newly afforded metal-free isotype step-scheme heterojunction in this work will supply a new insight into coupling strategies of heteroatoms doping and defect engineering for various photocatalytic systems.