Recent Advances and Perspectives of Lewis Acidic Etching Route:An Emerging Preparation Strategy for MXenes

Since the discovery in 2011,MXenes have become the rising star in the field of two-dimensional materials.Benefiting from the metallic-level conductivity,large and adjustable gallery spacing,low ion diffusion barrier,rich surface chemistry,superior mechanical strength,MXenes exhibit great application prospects in energy storage and conversion,sensors,optoelectronics,electromagnetic interference shielding and biomedicine.Nevertheless,two issues seriously deteriorate the further development of MXenes.One is the high experimental risk of common preparation methods such as HF etching,and the other is the difficulty in obtaining MXenes with controllable surface groups.Recently,Lewis acidic etching,as a brand-new preparation strategy for MXenes,has attracted intensive attention due to its high safety and the ability to endow MXenes with uniform terminations.However,a comprehensive review of Lewis acidic etching method has not been reported yet.Herein,we first introduce the Lewis acidic etching from the following four aspects:etching mechanism,terminations regulation,in-situ formed metals and delamination of multi-layered MXenes.Further,the applications of MXenes and MXene-based hybrids obtained by Lewis acidic etching route in energy storage and conversion,sensors and microwave absorption are carefully summarized.Finally,some challenges and opportunities of Lewis acidic etching strategy are also presented.

Effect of acid etching on marginal adaptation of mineral trioxide aggregate to apical dentin:microcomputed tomography and scanning electron microscopy analysis

The present investigation assessed the effect of acid etching on marginal adaptation of white- and gray-colored mineral trioxide aggregate （MTA） to apical dentin using microcomputed tomography （micro-CT） and scanning electron microscopy （SEM）. Sixty-four extracted single-rooted human maxillary teeth were used. Following root-end resection and apical preparation, the teeth were equally divided into four groups according to the following root end filling materials： （i） white-colored MTA （WMTA）, （ii） etched WMTA （EWMTA）, （iii） gray-colored MTA （GMTA） and （iv） etched GMTA （EGMTA）. After 48 h, the interface between root-end filling materials and the dentinal walls was assessed using micro-CT and SEM. Data were statistically analyzed using the KruskaI-Wallis and Dunn tests. Micro-CT analysis revealed gap volumes between the apical cavity dentin walls and EGMTA, GMTA, EWMTA and WMTA of （0.007 1±0.004） mm3, （0.053±0.002） mm3, （0.003 6±0.001） mm3 and （0.005 9±0.002） mm3 respectively. SEM analysis revealed gap sizes for EGMTA, WMTA, EWMTA and GMTA to be （492.3±13.8） μm, （594.5±17.12）μm, （543.1±15.33） μm and （910.7±26.2）μm respectively. A significant difference in gap size between root end preparations filled with GMTA and EGMTA was found （P〈O.05）. No significance difference in gap size between WMTA and EWMTA were found in either SEM or micro-CT analysis. In conclusion, pre-etching of apical dentin can provide a better seal for GMTA but not for WMTA.

Depth profiling of arsenian pyrite in Carlin-type ores through wet chemistry

Enrichment of As and Au at the overgrowth rims of arsenian pyrite is a distinctive feature of Carlin-type gold ores.Revealing distribution of such key elements in high resolution is of fundamental importance yet often proves challenging.In this study,repeated non-oxidative acid etching of ore samples from Shuiyindong gold deposit was applied to enable elemental depth profiling of goldbearing arsenian pyrite grains.ICP-OES and AAS were used to determine the dissolved Fe,As,and Au concentrations in each of the etching solutions,and XPS was carried out to exam the etched mineral surfaces.In contrast to conventional ion beam etching that may cause substantial sample damage,our acid etching method does not seem to significantly alter the composition and chemical state of the samples.The etched depths directly converted from the measured elemental concentrations can reproducibly reach a very high resolution of~1 nm,and can be conveniently controlled through varying the etching time.While the Fe and As depth profiles consistently reflect the surface oxidation property of arsenian pyrite,the Au profile displaying an obvious upward trend reveals the ore fluid evolution at the late stage of mineralization.Based on our experimental results,we demonstrate that our wet chemistry method is capable of effective depth profiling of gold ore and perhaps other geological samples,with advantages surpassing many instrumental techniques including negligible sample damage,nanoscale resolution as well as isotropic etching.

Acid-etching induced metal cation competitive lattice occupancy of perovskite quantum dots for efficient pure-blue QLEDs

Low efficiency and spectral instability caused by the surface defects have been considerable issues for the mixed-halogen blue emitting perovskite quantum dots light-emitting diodes(PeQLEDs).Here,an in situ surface passivation to perovskite quantum dots(PeQDs)is realized by introducing the metal cations competitive lattice occupancy assisted with acid-etching,in which the longchain,insulating and weakly bond surface ligands are removed by addition of octanoic acid(OTAC).Meanwhile,the dissolved A-site cations(Na^(+))compete with the protonated oleyl amine and are subsequently anchored to the surface vacancies.The preadded lead bromide,acting as inorganic ligands,demonstrates strong bonding to the uncoordinated surface ions.The as-synthesized PeQDs show the boosted photoluminescence quantum yield(PLQY)and superior stability with longer lifetime.As a result,the PeQLEDs(470 nm)based on the OTAC-Na PeQDs exhibit an external quantum efficiency of 8.42%in the mixed halogen PeQDs(CsPb(Br_(x)Cl_(1−x))_(3)).Moreover,the device exhibits superior spectra stability with negligible shift.Our competition mechanism in combination with in situ passivation strategy paves a new way for improving the performance of blue PeQLEDs.

Preparation of micro-nanostructure on titanium implants and its bioactivity

Surface modification of medical implants was considered as an effective method to improve the cellular behaviors and the integration of tissue onto materials. The micro-nanostructured surface on the titanium alloy was prepared by laser treatment and multiple acid etching. The surface morphologies of different titanium alloy substrates were characterized by scanning electron microscopy (SEM). The effects of micro-nanostructured surfaces on the cellular responses were investigated in vitro by observing hydroxyapatite formation, cell morphology and cell adhesion. The results indicate that the micro-sized structure promoted the adhesion and proliferation of cultured osteoblasts. Furthermore, the micro-nanostructured surface was more conducive to cell adhension stretching compared with the micro-structured surface. All results suggest that the micro-nanostructured surface improved the biocompatibility and integration of tissue onto titanium alloy implants.

Fabrication of Micro/Nano-textured Titanium Alloy Implant Surface and Its Infl uence on Hydroxyapatite Coatings

We put forward a protocolcombining laser treatment and acid etching to obtain multiscale micro/nano-texture surfaces of titanium alloy implant.Firstly,the operationalparameters of the laser were optimized to obtain an optimum current.Secondly,the laser with the optimum operationalparameters was used to fabricate micro pits.Thirdly,multiple acid etching was used to clean the clinkers of micro pits and generate submicron and nanoscale structures.Finally,the bioactivity of the samples was measured in a simulated body fluid.The results showed that the micropits with a diameter of 150 μm and depth of 50 μm were built successfully with the optimized working current of 13 A.In addition,submicron and nanoscale structures,with 0.5-2 μm microgrooves and 10-20 nm nanopits,were superimposed on micro pits surface by multiple acid etching.There was thick and dense HA coating only observed on the multiscale micro/nano-textured surface compared with polished and micro-textured surface.This indicated that the multiscale micro/nano-texture surface showed better ability toward HA formation,which increased the bioactivity of implants.

Novel process for facile preparation of mesoporous silica-based materials with controllable pore structure from coal fly ash Author links open overlay panel

Extraction of silica from fly ash to produce mesoporous silica materials is one of the most important utilization approaches.Mesoporous silica could not be synthesized on a large-scale by conventional sol-gel method.In this paper,facile preparation of mesoporous silica with controllable pore structure from fly ash by the template-free process via two steps of mineral phase transformation and selective acid etching was proposed.The influence of crystalline structure and acid etching degree on structure of as-synthesized mesoporous silica materials was revealed,as well as mechanism of crystalline structure transformation and pore structure formation.The results show that mullite and quartz could be transformed into acid-soluble kaliophilite when fly ash reacted with K_(2)CO_(3)at temperature of 800-1100℃.The hexagonal kaliophilite would be transformed into orthorhombic KAlSiO_(4)-O1 phase when the temperature is controlled at 1100℃.Mesoporous silica with specific surface area of 475.93 m^(2)/g and 642.57 m^(2)/g could be synthesized from activated fly ash with kaliophilite and KAlSiO_(4)-O1 phase crystalline structure.By controlling the degree of acid etching,mesoporous silica materials with different pore structures can be obtained.This paper provides a cost-effective and large-scale process for the preparation of mesoporous silica materials with controllable pore structure from solid waste fly ash.

Surface tuning of LaCoO_(3) perovskite by acid etching to enhance its catalytic performance

The stoichiometric LaCoO_(3) and nonstoichiometric LaCo_(1.2)O_(3) perovskite catalysts were prepared by citric acid sol-gel method,and then,LaCoO_(3) perovskite was etched with nitric acid.The structure,surface composition and reducibility of the catalyst were studied by X-ray diffraction(XRD),nitrogen desorption,transmission electron microscope(TEM),temperature program reduction of H_(2)(H_(2)-TPR) and X-ray photoelectron spectroscopy(XPS).It was found that nitric acid etching did not change the crystal structure and the overall morphology of the LaCoO_(3) catalyst,but it can cause the exposure of B-site Co metal to the surface of the catalyst.As a result,after acid etching,the reducibility of the LaCoO_(3) catalyst was improved,leading to the improvement in the catalytic activity of the LaCoO_(3) catalyst for CO oxidation and C_(3)H_(8) combustion.Moreover,the catalytic activity of the LaCoO_(3) catalyst after acid etching was higher than that of LaCo_(1.2)O_(3) and CoOx/LaCoO_(3) catalyst.

Microwave-assisted acid-induced formation of linker vacancies within Zr-based metal organic frameworks with enhanced heterogeneous catalysis

Herein,we report a microwave-assisted acid-induced post-treatment method for the formation of linker vacancies within Zr-based metal organic frameworks(Zr-MOFs).The number of linker vacancies can be easily regulated with this method by changing the concentration of the HCl solution and the duration of microwave irradiation.The optimized defective UiO-66 showed higher linker defects with a higher specific surface area and thermal stability.The results of the catalytic cyclization of citronella showed that the Zr-MOFs with more defects exhibited enhanced catalytic performance.This work may provide a new method for the creation of defective MOFs with high activity and stability.

Ultra-lightweight ceramic scaffolds with simultaneous improvement of pore interconnectivity and mechanical strength

The high porosity and interconnectivity of scaffolds are critical for nutrient transmission in bone tis-sue engineering but usually lead to poor mechanical properties.Herein,a novel method that combines acid etching(AE)with selective laser sintering(SLS)and reaction bonding(RB)of Al particles is pro-posed to realize highly improved porosity,interconnectivity,mechanical strength,and in vitro bioactivity in 3D Al_(2)O_(3) scaffolds.By controlling the oxidation and etching behaviors of Al particles,a tunable hol-low spherical feature can be obtained,which brings about the distinction in compressive response and fracture path.The prevention of microcrack propagation on the in situ formed hollow spheres results in unique near elastic buckling rather than traditional brittle fracture,allowing an unparalleled compressive strength of 3.72±0.17 MPa at a high porosity of 87.7%±0.4%and pore interconnectivity of 94.7%±0.4%.Furthermore,scaffolds with an optimized pore structure and superhydrophilic surface show excellent cell proliferation and adhesion properties.Our findings offer a promising strategy for the coexistence of out-standing mechanical and biological properties,with great potential for tissue engineering applications.

Scalable synthesis of nanoporous high entropy alloys for electrocatalytic oxygen evolution

High entropy alloys(HEAs)containing five or more equimolar components have shown promising catalytic performance due to their unique chemical and mechanical properties.However,it is still challenging to prepare scalable and efficient nanoporous HEAs as catalysts.Here,we present a facile strategy to synthesize largescale nanoporous HEAs particles by combing vacuum induction melting,gas atomization,and acidic etching procedure.The application of HEAs to energy conversion is evaluated with electrocatalytic oxygen evolution reaction(OER)on AlCrCuFeNi HEAs.The HEAs exhibit a low OER overpotential of 270 mV to achieve a current density of 10 mA·cm^(-2),a small Tafel slope of 77.5 mV·dec^(-1),and long-term stability for over 35 h in 1 mol·L^(-1) KOH,which is comparable to the state-of-the-art OER electrocatalyst RuO2.The findings in this paper not only provide an industrial approach to produce nanoporous HEAs powder but also inspire the applications of HEAs as catalysts.

A wrinkle to sub-100 nm yolk/shell Fe3O4@SiO2 nanoparticles

Yolk/shell nanoparticles （NPs）, which integrate functional cores （likes Fe3O4） and an inert SiO2 shell, are very important for applications in fields such as biomedicine and catalysis. An acidic medium is an excellent etchant to achieve hollow SiO2 but harmful to most functional cores. Reported here is a method for preparing sub-100 nm yolk/shell Fe3O4@SiO2 NPs by a mild acidic etching strategy. Our results demonstrate that establishment of a dissolution-diffusion equilibrium of silica is essential for achieving yolk/shell Fe3O4@SiO2 NPs. A uniform increase in the silica compactness from the inside to the outside and an appropriate pH value of the etchant are the main factors controlling the thickness and cavity of the SiO2 shell. Under our ＂standard etching code＂, the acid-sensitive Fe3O4 core can be perfectly preserved and the SiO2 shell can be selectively etched away. The mechanism of etching was investigated. regulation of SiO2 etching and acidic