Recent progress on MOF/MXene nanoarchitectures:A new era in coordination chemistry for energy storage and conversion

The development of urbanization and industrialization leads to rapid depletion of fossil fuels.Therefore,the production of fuel from renewable resources is highly desired.Electrotechnical energy conversion and storage is a benign technique with reliable output and is eco-friendly.Developing an exceptional electrochemical catalyst with tunable properties like a huge specific surface area,porous channels,and abundant active sites is critical points.Recently,Metal-organic frameworks(MOFs)and two-dimensional(2D)transition-metal carbides/nitrides(MXenes)have been extensively investigated in the field of electrochemical energy conversion and storage.However,advances in the research on MOFs are hampered by their limited structural stability and conventionally low electrical conductivity,whereas the practical electrochemical performance of MXenes is impeded by their low porosity,inadequate redox sites,and agglomeration.Consequently,researchers have been designing MOF/MXene nanoarchitectures to overcome the limitations in electrochemical energy conversion and storage.This review explores the recent advances in MOF/MXene nanoarchitectures design strategies,tailoring their properties based on the morphologies(0D,1D,2D,and 3D),and broadening their future opportunities in electrochemical energy storage(batteries,supercapacitors)and catalytic energy conversion(HER,OER,and ORR).The intercalation of MOF in between the MXene layers in the nanoarchitectures functions synergistically to address the issues associated with bare MXene and MOF in the electrochemical energy storage and conversion.This review gives a clear emphasis on the general aspects of MOF/MXene nanoarchitectures,and the future research perspectives,challenges of MOF/MXene design strategies and electrochemical applications are highlighted.

Catalyst activation: Surface doping effects of group Ⅵ transition metal dichalcogenides towards hydrogen evolution reaction in acidic media

Two-dimensional(2D) transition metal dichalcogenides(TMDs) have emerged as promising alternatives to the platinum-based catalysts for hydrogen evolution reaction(HER). The edge site of these2D materials exhibits HER-active properties, whereas the large-area basal plane is inactive.Therefore, recent studies and methodologies have been investigated to improve the performance of TMD-based materials by activating inactive sites through elemental doping strategies. In this review,we focus on the metal and non-metal dopant effects on group VI TMDs such as MoS_(2) MoSe_(2) WS_(2)and WSe_(2) for promoting HER performances in acidic electrolytes. A general introduction to the HER is initially provided to explain the parameters in accessing the catalytic performance of dopedTMDs. Then, synthetic methods for doped-TMDs and their HER performances are introduced in order to understand the effect of various dopants including metallic and non-metallic elements. Finally, the current challenges and future opportunities are summarized to provide insights into developing highly active and stable doped-TMD materials and valuable guidelines for engineering TMD-based nanocatalysts for practical water splitting technologies.

Positively charged carbon electrocatalyst for enhanced power performance of L-ascorbic acid fuel cells

Carbon surface with large oxygen and carbon ratio(O/C) indicated an outstanding electro-catalytic activity toward L-ascorbic acid oxidation, compared to platinum group metals. However, interrelation of surface functional groups and its electro-catalytic activity is still unclear. In this paper, we prepared different levels of oxidized carbons by a simple acid treatment and investigated the correlation between the surface oxygen functional groups of acid-treated carbon and electro-catalytic activity in an electrooxidation of L-ascorbic acid. Positively charged carbon was demonstrated by lone pair electron of oxygen from valence band spectra study. It was revealed that the positively charged carbon, especially involved in carbonyl, showed enhanced the electro-catalytic activity through both better adsorption of negatively charged reactants and lowered LUMO by electronegativity of oxygen.

Selective conversion of N_(2) to NH_(3) on highly dispersed RuO_(2) using amphiphilic ionic liquid-anchored fibrous carbon structure

Ammonia (NH_(3)) plays a key role in the agricultural fertilizer and commodity chemical industries and is useful for exploring hydrogen storage carriers.The electrochemical nitrogen reduction reaction (NRR) is receiving attention as an environmentally sustainable NH_(3) synthesis replacement for the traditional Haber–Bosch process owing to its near ambient reaction conditions (<100℃ and 1 atm).However,its NH_(3) yield and faradaic efficiency are extremely low because of the sluggish kinetics of N≡N bond dissociation and the hindrance from competitive hydrogen evolution.To overcome these challenges,we herein introduce a dual-functionalized ionic liquid (1-(4-hydroxybutyl)-3-methylimidazolium hydroxide[HOBIM]OH) for a highly dispersed ruthenium oxide electrocatalyst to achieve a biased NRR.The observed uniform distribution of RuO_(2) on the carbon fiber and increase in the surface area for N_(2) adsorption by limiting proton access can be attributed to the presence of imidazolium ions.Moreover,extensive N_(2) adsorption contributes to enhanced NRR selectivity with an NH_(3) yield of 3.0×10^(-10)mol cm^(-2)s^(-1)(91.8μg h^(-1)mg^(-1)) and a faradaic efficiency of 2.2%at-0.20 V_(RHE).We expect our observations to provide new insights into the design of effective electrode structures for electrochemical NH;synthesis.

Shape-controlled Pt nanocubes directly grown on carbon supports and their electrocatalytic activity toward methanol oxidation

Synthesis of shape-controlled Pt nanocrystals is substantial and important for enhancing chemical and electrochemical reactions.However,the removal of capping agents,shape-controlling chemicals,on Pt surfaces is essential prior to conducting the catalytic reactions.Here we report a facile one-pot synthesis of Pt nanocubes directly grown on carbon supports(Pt nanocubes/C) with modulating the kinetic reaction factors for shaping the nanocrystals,but without adding any capping agents for preserving the clean Pt surfaces.Well-dispersed Pt nanocubes/C shows enhanced activity and long-term stability toward methanol oxidation reaction compared to the commercial Pt/C catalyst.

Facile synthesis of fully ordered L10-FePt nanoparticles with controlled Pt-shell thicknesses for electrocatalysis

We report a simple one-step approach for the synthesis of -4 nm uniform and fully L10-ordered face-centered tetragonal （fct） FePt nanoparticles （NPs） embedded in -60 nm MCM-41 （fct-FePt NPs@MCM-41）. We controlled the Pt-shell thickness of the fct-FePt NPs by treating the fct-FePt NPs@MCM-41 with acetic acid （HOAc） or hydrochloric acid （HC1） under sonicafion, thereby etching the surface Fe atoms of the NPs. The fct-FePt NPs deposited onto the carbon support （fct-FePt NP/C） were prepared by mixing the fct-FePt NPs@MCM-41 with carbon and subsequently removing the MCM-41 using NaOH. We also developed a facile method to synthesize acid-treated fct-FePt NP/C by using a HF solution for simultaneous surface-Fe etching and MCM-41 removal. We studied the effects of both surface-Fe etching and Pt-shell thickness on the electrocatalytic properties of fct-FePt NPs for the methanol oxidation reaction （MOR）. Compared with the non-treated fct-FePt NP/C catalyst, the HOAc-treated and HCl-treated catalysts exhibit up to 34% larger electrochemically active surface areas （ECASAs）; in addition, the HCl-treated fct-FePt NP （with -1.0 nm Pt shell）/C catalyst exhibits the highest specific activity. The HF-treated fct-FePt NP/C exhibits an ECASA almost 2 times larger than those of the other acid-treated fct-FePt NP/C catalysts and shows the highest mass activity （1,435 mA·mgPt^-1, 2.3 times higher than that of the commercial Pt/C catalyst） and stability among the catalysts tested. Our findings demonstrate that the surface-Fe etching for the generation of the Pt shell on fct-FePt NPs and the Pt-shell thickness can be factors for optimizing the electrocatalysis of the MOR.