Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

Unveiling the pressure-driven metal–semiconductor–metal transition in the doped TiS_(2)

Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.

A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.

Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications

Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

From VIB‑to VB‑Group Transition Metal Disulfides:Structure Engineering Modulation for Superior Electromagnetic Wave Absorption

The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various fields,such as catalysis,energy storage,sensing,etc.In recent years,a lot of research work on TMDs based functional materials in the fields of electromagnetic wave absorption(EMA)has been carried out.Therefore,it is of great significance to elaborate the influence of TMDs on EMA in time to speed up the application.In this review,recent advances in the development of electromagnetic wave(EMW)absorbers based on TMDs,ranging from the VIB group to the VB group are summarized.Their compositions,microstructures,electronic properties,and synthesis methods are presented in detail.Particularly,the modulation of structure engineering from the aspects of heterostructures,defects,morphologies and phases are systematically summarized,focusing on optimizing impedance matching and increasing dielectric and magnetic losses in the EMA materials with tunable EMW absorption performance.Milestones as well as the challenges are also identified to guide the design of new TMDs based dielectric EMA materials with high performance.

Mass-Based Environmental Factor and Energy Assessment of Microwave-Assisted Synthesized Transition Metal Nanostructures

This paper describes mass-based energy phase-space projection of microwave-assisted synthesis of transition metals (zinc oxide, palladium, silver, platinum, and gold) nanostructures. The projection uses process energy budget (measured in kJ) on the horizontal axes and process density (measured in kJg−1) on the vertical axes. These two axes allow both mass usage efficiency (Environmental-Factor) and energy efficiency to be evaluated for a range of microwave applicator and metal synthesis. The metrics are allied to the: second, sixth and eleventh principle of the twelve principle of Green Chemistry. This analytical approach to microwave synthesis (widely considered as a useful Green Chemistry energy source) allows a quantified dynamic environmental quotient to be given to renewable plant-based biomass associated with the reduction of the metal precursors. Thus allowing a degree of quantification of claimed “eco-friendly” and “sustainable” synthesis with regard to waste production and energy usage.

Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries

Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Quantitative determination of the critical points of Mott metal–insulator transition in strongly correlated systems

Mottness is at the heart of the essential physics in a strongly correlated system as many novel quantum phenomena occur in the metallic phase near the Mott metal–insulator transition. We investigate the Mott transition in a Hubbard model by using the dynamical mean-field theory and introduce the local quantum state fidelity to depict the Mott metal–insulator transition. The local quantum state fidelity provides a convenient approach to determining the critical point of the Mott transition. Additionally, it presents a consistent description of the two distinct forms of the Mott transition points.

Recent Advances of Transition Metal Basic Salts for Electrocatalytic Oxygen Evolution Reaction and Overall Water Electrolysis

Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the most conventional and classical non-noble metal-based electrocatalysts for OER,while TM basic salts[M^(2+)(OH)_(2-x)(A_(m^(-))_(x/m),A=CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)]consisting of OH−and another anion have drawn extensive research interest due to its higher catalytic activity in the past decade.In this review,we summarize the recent advances of TM basic salts and their application in OER and further overall water splitting.We categorize TM basic salt-based OER pre-catalysts into four types(CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)according to the anion,which is a key factor for their outstanding performance towards OER.We highlight experimental and theoretical methods for understanding the structure evolution during OER and the effect of anion on catalytic performance.To develop bifunctional TM basic salts as catalyst for the practical electrolysis application,we also review the present strategies for enhancing its hydrogen evolution reaction activity and thereby improving its overall water splitting performance.Finally,we conclude this review with a summary and perspective about the remaining challenges and future opportunities of TM basic salts as catalysts for water electrolysis.

Current advances of transition metal dichalcogenides in electromagnetic wave absorption:A brief review

Transition metal dichalcogenides(TMDs)show great advantages in electromagnetic wave(EMW)absorption due to their unique structure and electrical properties.Tremendous research works on TMD-based EMW absorbers have been conducted in the last three years,and the comprehensive and systematical summary is still a rarity.Therefore,it is of great significance to elaborate on the interaction among the morphologies,structures,phases,components,and EMW absorption performances of TMD-based absorbers.This review is devoted to analyzing TMD-based absorbers from the following perspectives:the EMW absorption regulation strategies of TMDs and the latest progress of TMD-based hybrids as EMW absorbers.The absorption mechanisms and component-performance dependency of these achievements are also summarized.Finally,a straightforward insight into industrial revolution upgrading in this promising field is proposed.

A review on the synthesis of transition metal nitride nanostructures and their energy related applications

Transition metal nitrides(TMN)have recently grabbed immensely appealing as ideal active materials in energy storage and catalysis fields on account of their remarkable electrical conductivity,excellent chemical stability,wide band gap and tunable morphology.Both pure TMN and TMN-based materials have been extensively studied concerned with their preparation approaches,nanostructures,and favored performance in various applications.However,the processes towards synthesis of TMN are numerous and complex.Choosing appropriate method to obtain target TMN with desired structure is crucial,which further affects its practical application performance.Herein,this review offers a timely and comprehensive summary of the synthetic ways to TMN and their application in energy related domains.The synthesis section is categorized into in-situ and ex-situ based on where the N element in TMN origins from.Then,overviews on the energy related applications including energy storage,electrocatalysis and photocatalysis are discussed.In the end,the problems to be solved and the development trend of the synthesis and application of transition metal nitrides are prospected.

Boosting Lean Electrolyte Lithium-Sulfur Battery Performance with Transition Metals: A Comprehensive Review

Lithium–sulfur(Li–S) batteries have received widespread attention, and lean electrolyte Li–S batteries have attracted additional interest because of their higher energy densities. This review systematically analyzes the effect of the electrolyte-to-sulfur(E/S) ratios on battery energy density and the challenges for sulfur reduction reactions(SRR) under lean electrolyte conditions. Accordingly, we review the use of various polar transition metal sulfur hosts as corresponding solutions to facilitate SRR kinetics at low E/S ratios(< 10 μL mg~(-1)), and the strengths and limitations of different transition metal compounds are presented and discussed from a fundamental perspective. Subsequently, three promising strategies for sulfur hosts that act as anchors and catalysts are proposed to boost lean electrolyte Li–S battery performance. Finally, an outlook is provided to guide future research on high energy density Li–S batteries.

Defect-engineered two-dimensional transition metal dichalcogenides towards electrocatalytic hydrogen evolution reaction

Recently,two-dimensional transition metal dichalcogenides(TMDs)demonstrated their great potential as cost-effective catalysts in hydrogen evolution reaction.Herein,we systematically summarize the existing defect engineering strategies,including intrinsic defects(atomic vacancy and active edges)and extrinsic defects(metal doping,nonmetal doping,and hybrid doping),which have been utilized to obtain advanced TMD-based electrocatalysts.Based on theoretical simulations and experimental results,the electronic structure,intermediate adsorption/desorption energies and possible catalytic mechanisms are thoroughly discussed.Particular emphasis is given to the intrinsic relationship between various types of defects and electrocatalytic properties.Furthermore,current opportunities and challenges for mechanical investigations and applications of defective TMD-based catalysts are presented.The aim herein is to reveal the respective properties of various defective TMD catalysts and provide valuable insights for fabricating high-efficiency TMD-based electrocatalysts.

Activation of Transition Metal(Fe,Co and Ni)-Oxide Nanoclusters by Nitrogen Defects in Carbon Nanotube for Selective CO_(2) Reduction Reaction

The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.

Optical spectroscopy of CrO and electronic states of the Cr group metal monoxides

All of the experimentally known electronic states of the Cr group metal monoxides(Cr O,Mo O,and WO)have been presented in the paper.The optical spectra of the Cr O molecule have been investigated in the gas phase through a combination of the laser-induced fluorescence(LIF)excitation and single-vibronic-level(SVL)emission spectroscopy in the supersonic expansion.The rotational constants of the vibronic electronic states,including X^(5)Π_(-1)(v=0–3),B^(5)Π_(-1)(v=0–10),and B~5Π_1(v=1,5),and the vibrational constants of the spin–orbit components X^(5)Π_(-1,0,1)have been obtained.The molecular constants of the Mo O and WO molecules have been summarized by reviewing the previous spectroscopic studies,and a comprehensive energy level diagram of the Cr group metal monoxides has been constructed.By comparing the electronic configurations,bond lengths,and vibrational frequencies of all the transition metal monoxides in the ground electronic state,the significance of the relativistic effect in the bonding of the 5d transition metal monoxides has been discussed.The related spectroscopic data of the Cr O molecule are available at https://doi.org/10.57760/sciencedb.j00113.00085.

Rubidium-induced phase transitions among metallic,band-insulating,Mott-insulating phases in 1T-TaS_(2)

Realizing phase transitions via non-thermal sample manipulations is important not only for applications,but also for uncovering the underlying physics.Here,we report on the discovery of two distinct metal–insulator transitions in 1T-TaS_(2) via angle-resolved photoemission spectroscopy and in-situ rubidium deposition.At 205 K,the rubidium deposition drives a normal metal–insulator transition via filling electrons into the conduction band.While at 225 K,however,the rubidium deposition drives a bandwidth-controlled Mott transition as characterized by a rapid collapsing of Mott gap and a loss of spectral weight of the lower Hubbard band.Our result,from a doping-controlled perspective,succeeds in distinguishing the metallic,band-insulating,and Mott-insulating phases of 1T-TaS_(2),manifesting a delicate balance among the electronitineracy,interlayer-coupling and Coulomb repulsion.We also establish an effective method to tune the balance between these interactions,which is useful in seeking exotic electronic phases and designing functional phase-changing devices.

Pressure-induced phase transition and electronic structure evolution in layered semimetal HfTe_(2)

Motivated by the recent experimental work,the pressure-induced structural transition of well-known two-dimensional(2D)1T-Hf Te_(2)was investigated up to 50 GPa through the advanced CALYPSO structure search technique combined with the first-principles calculations.Our calculations suggested that the 1T-Hf Te_(2)will first transform to C2/m phase at 3.6 GPa with a volume reduction of 7.6%and then to P62m phase at 9.6 GPa with a volume collapse of 4.6%.The occurrences of 3D C2/m and P62m phases mainly originated from the enhanced Te-Te interlayer coupling and the drastic distortions of Hf-Te polyhedrons in P3m1 phase under compression.Concomitantly,the coordination number of Hf atoms increased from six in P3m1 to eight in C2/m and eventually to nine in P62m at elevated pressure.The metallic and semimetallic nature of C2/m and P62m phases were characterized,and the evidence of the reinforced covalent interactions of Te-Hf and Te-Te orbitals in these two novel high-pressure phases were manifested by the atom-projected electronic DOS and Bader charge.