以高岭土制备β-sialon粉料

在高岭土和碳的混合物中,加入适量氧化铁作催化剂,在N_2气氛下,通过还原-氮化反应,制得β-sialon粉料。用X射线衍射法测定了在反应温度下生成物的相组成及相对含量的变化,并用化学分析方法测定了β-sialon粉料中的氮含量。用TEM观察了粉末合成前后的形貌。在此基础上,讨论了β-sialon形成过程。研究结果表明,β-sialon粉料中氮含量及Z值大小与工艺参数有关。

Single-atom catalysts based on polarization switching of ferroelectric In_(2)Se_(3) for N_(2) reduction

The polarization switching plays a crucial role in controlling the final products in the catalytic pro-cess.The effect of polarization orientation on nitrogen reduction was investigated by anchoring transition metal atoms to form active centers on ferroelectric material In_(2)Se_(3).During the polariza-tion switching process,the difference in surface electrostatic potential leads to a redistribution of electronic states.This affects the interaction strength between the adsorbed small molecules and the catalyst substrate,thereby altering the reaction barrier.In addition,the surface states must be considered to prevent the adsorption of other small molecules(such as *O,*OH,and *H).Further-more,the V@↓-In_(2)Se_(3) possesses excellent catalytic properties,high electrochemical and thermody-namic stability,which facilitates the catalytic process.Machine learning also helps us further ex-plore the underlying mechanisms.The systematic investigation provides novel insights into the design and application of two-dimensional switchable ferroelectric catalysts for various chemical processes.

4d Metal-doped liquid Ga for efficient ammonia electrosynthesis at wide N_(2) concentrations

Electrocatalytic nitrogen reduction reaction under ambient conditions is a promising pathway for ammonia synthesis.Currently nitrogen reduction reactions are carried out in N_(2)-saturated environments and use high-purity nitrogen as feedstock,which is costly.Here,we prepared carbon-coated ultra-low 4d metal Ru-doped liquid metal Ga(Ru_(0.06)/LM@C)for NRR over a wide range of N_(2) concentrations.Comprehensive analyses show that the introduction of the ultra-low 4d element Ru can effectively adjust the electronic structure through orbital interactions,thus enhancing the adsorption of nitrogen-containing intermediates.The liquid catalyst utilized its mobility to provide a higher density of active sites.In addition,the material Ru_(0.06)/Ga@C itself has the ability to promote product desorption.The three act synergistically to optimize the N_(2) mass transfer path,thereby increasing the*NNH coverage and further improving the ammonia yield over a wide range of N_(2) concentrations.The maximum NH_(3) yield of the catalyst can reach 126.0μg h^(-1) mgcat^(-1)(at–0.3 V vs.RHE)with high purity N_(2) as feed gas,and the Faraday efficiency is 60.4%at–0.1 V vs.RHE.Over a wide range of N_(2) concentrations,the NH_(3) yield of the catalyst was greater than 100μg h^(-1) mgcat^(-1) with a Faraday efficiency higher than 47%.The catalytic performance is much higher than that of solid Ga@C and reported p-block metal-based catalysts.

Mild polarization electric field in ultra-thin BN-Fe-graphene sandwich structure for efficient nitrogen reduction

The electrocatalytic N_(2)reduction reaction(NRR)is expected to supersede the traditional Haber-Bosch technology for NH3 production under ambient conditions.The activity and selectivity of electrochemical NRR are restricted to a strong polarized electric field induced by the catalyst,correct electron transfer direction,and electron tunneling distance between bare electrode and active sites.By coupling the chemical vapor deposition method with the poly(methyl methacylate)-transfer method,an ultrathin sandwich catalyst,i.e.,Fe atoms(polarized electric field layer)sandwiched between ultrathin(within electron tunneling distance)BN(catalyst layer)and graphene film(conducting layer),is fabricated for electrocatalytic NRR.The sandwich catalyst not only controls the transfer of electrons to the BN surface in the correct direction under applied voltage but also suppresses hydrogen evolution reaction by constructing a neutral polarization electric field without metal exposure.The sandwich electrocatalyst NRR system achieve NH3 yield of 8.9μg h^(−1)cm^(−2)and Faradaic Efficiency of 21.7%.The N_(2)adsorption,activation,and polarization electric field changes of three sandwich catalysts(BN-Fe-G,BN-Fe-BN,and G-Fe-G)during the electrocatalytic NRR are investigated by experiments and density functional theory simulations.Driven by applied voltage,the neutral polarized electric field induced by BN-Fe-G leads to the high activity of electrocatalytic NRR.

Science Letters:Nitrogen doping of activated carbon loading Fe_2O_3 and activity in carbon-nitric oxide reaction

Nitrogen doping of activated carbon loading Fe2O3 was performed by annealing in ammonia, and the activity of the modified carbon for NO reduction was studied in the presence of oxygen. Results show that Fe2O3 enhances the amount of surface oxygen complexes and facilitates nitrogen incorporation in the carbon, especially in the form of pyridinic nitrogen. The modified carbon shows excellent activity for NO reduction in the low temperature regime （〈500℃） because of the cooperative effect of Fe2O3 and the surface nitrogen species.

Kinetic Model and Simulation of Promoted Selective Non-catalytic Reduction by Sodium Carbonate

Abstract The detailed kinetic model of selective non-catalytic reduction （SNCR） of nitric oxide, including so-dium species reactions, was deyeloped on the basis of recent studies on thermal DeNOx mechanism, NOxOUTmechanism and promotion mechanism of Na2CO3. The model was validated by comparison with several experi-mental findings, thus providing an effective tool for the primary and promoted SNCR process simulation. Experimental and simulated results show part-per-million level of sodium carbonate enhances NO removal efficiency andextend the effective SNCR temperature range in comparison with use of a nitrogen agent alone. The kinetic modeling, sensitivity and rate-of-production analysis suggest that the performance improvement can be explained as ho-mogeneous sodium species reactions producing more reactive OH radicals. The net result of sodium species reac-tions is conversion of H2O and inactive HO2 radicals into reactive OH radicals, i.e. H2O＋HO2=3OH, which enhances the SNCR performance of nitrogen agents by mainly increasing the production rate of NH2 radicals. More-over, N2O and CO are eliminated diversely via the reactions Na＋N20=NaO＋N2, NaO＋CO=Na＋CO2 andNaO2＋CO =NaO＋CO2, in.the pro.moted SNCR process, especially in the NOxOUT process.

Dual-site collaboration boosts electrochemical nitrogen reduction on Ru-S-C single-atom catalyst

Electrocatalytic reduction of nitrogen into ammonia(NH_(3))is a highly attractive but challenging route for NH_(3)production.We propose to realize a synergetic work of multi reaction sites to overcome the limitation of sustainable NH_(3)production.Herein,using ruthenium-sulfur-carbon(Ru-S-C)catalyst as a prototype,we show that the Ru/S dual-site cooperates to catalyse eletrocatalytic nitrogen reduction reaction(eNRR)at ambient conditions.With the combination of theoretical calculations,in situ Raman spectroscopy,and experimental observation,we demonstrate that such Ru/S dual-site cooperation greatly facilitates the activation and first protonation of N_(2)in the rate-determining step of eNRR.As a result,Ru-S-C catalyst exhibits significantly enhanced eNRR performance compared with the routine Ru-N-C catalyst via a single-site catalytic mechanism.We anticipate that our specifically designed dual-site collaborative catalytic mechanism will open up a new way to offers new opportunities for advancing sustainable NH_(3)production.

Orbital symmetry matching:Achieving superior nitrogen reduction reaction over single-atom catalysts anchored on Mxene substrates

The nitrogen reduction reaction(NRR)under ambient conditions is still challenging due to the inertness of N2.Herein,we report a series of superior NRR catalysts identified by examining Ti2NO2 MXenes embedded with 28 different single-atom catalysts using first-principles calculations.The stability of this system was first verified using formation energies,and it is discovered that N2 can be effectively adsorbed due to the synergistic effect between single atom catalysis and the Ti atoms.Examination of the electronic structure demonstrated that this design satisfies orbital symmetry matching where“acceptor-donor”interaction scenario can be realized.A new“enzymatic-distal”reaction mechanism that is a mixture of the enzymatic and distal pathways was also discovered.Among all of the candidates,Ni anchored on MXene system achieves an onset potential as low as–0.13 V,which to the best of our knowledge is the lowest onset potential value reported to date.This work elucidates the significance of orbital symmetry matching and provides theoretical guidance for future studies.

Fe/N-doped mesoporous carbons derived from soybeans: A highly efficient and low-cost non-precious metal catalyst for ORR

Oxygen reduction reaction(ORR)plays a crucial role in many energy storage and conversion devices.Currently,the development of inexpensive and high-performance carbon-based non-precious-metal ORR catalysts in alkaline media still gains a wide attention.In this paper,the mesoporous Fe-N/C catalysts were synthesized through SiO2-mediated templating method using biomass soybeans as the nitrogen and carbon sources.The SiO2 templates create a simultaneous optimization of both the surface functionalities and porous structures of Fe-N/C catalysts.Detailed investigations indicate that the Fe-N/C3 catalyst prepared with the mass ratio of SiO2 to soybean being 3:4 exhibits brilliant electrocatalytic performance,excellent long-term stability and methanol tolerance for the ORR,with the onset potential and the half-wave potential of the ORR being about 0.890 V and 0.783 V(vs RHE),respectively.Meanwhile,the desired 4-electron transfer pathway of the ORR on the catalysts can be observed.It is significantly proposed that the high BET specific surface area and the appropriate pore-size,as well as the high pyridinic-N and total nitrogen loadings may play key roles in enhancing the ORR performance for the Fe-N/C3 catalyst.These results suggest a feasible route based on the economical and sustainable soybean biomass to develop inexpensive and highly efficient non-precious metal electrochemical catalysts for the ORR.

Beyond the thermodynamic volcano picture in the nitrogen reduction reaction over transition-metal oxides:Implications for materials screening

Electrocatalytic production of ammonia from dinitrogen is considered as a sustainable alternative to the energy-demanding and pollutive Haber-Bosch process.A promising class of materials for selective nitrogen reduction(NRR)corresponds to transition-metal oxides given that these electrodes do not show a high activity toward the competing hydrogen evolution reaction.So far,density functional theory calculations have been used to comprehend trends in a class of materials by using the concept of scaling relations and volcano plots.This thermodynamic theory pinpoints that either the formation of the*NNH adsorbate or the formation of ammonia are reconciled with the potential-determining reaction steps.Thus,the development of NRR catalyst has largely focused on the optimization of these two elementary processes.In the present contribution,overpotential and kinetic effects are factored into the volcano plot for the NRR over transition-metal oxides by making use of the recently introduced activity descriptor G_(max)(η).It is illustrated that the thermodynamic volcano picture is too simplistic as the limiting reaction step may alter close to the volcano apex:there,particularly surface reactions may govern the reaction rate.In addition,it is demonstrated how to include the formation of hydrazine as a competing side reaction into the volcano plot,which is of importance for weak binding*NNH catalysts where the formation of hydrazine may compete with the formation of ammonia.Given that the outlined methodology in this manuscript is universal and not restricted to the class of transition-metal oxides,the presented kinetic volcano picture may contribute to the development of NRR catalysts for nitrogen fixation.

Transition metal-nitrogen sites for electrochemical carbon dioxide reduction reaction

Electrochemical CO2 reduction reaction(CO2RR)powered by renewable electricity has emerged as the most promising technique for CO2 conversion,making it possible to realize a carbon‐neutral cycle.Highly efficient,robust,and cost‐effective catalysts are highly demanded for the near‐future practical applications of CO2RR.Previous studies on atomically dispersed metal‐nitrogen(M‐Nx)sites constituted of earth abundant elements with maximum atom‐utilization efficiency have demonstrated their performance towards CO2RR.This review summarizes recent advances on a variety of M‐Nx sites‐containing transition metal‐centered macrocyclic complexes,metal organic frameworks,and M‐Nx‐doped carbon materials for efficient CO2RR,including both experimental and theoretical studies.The roles of metal centers,coordinated ligands,and conductive supports on the intrinsic activity and selectivity,together with the importance of reaction conditions for improved performance are discussed.The mechanisms of CO2RR over these M‐Nx‐containing materials are presented to provide useful guidance for the rational design of efficient catalysts towards CO2RR.

Preparation of high purity vanadium nitride by magnesiothermic reduction of V2O3 followed by nitriding in N2 atmosphere

High purity vanadium nitride(VN)powders were prepared via a two-step process using vanadium trioxide(V2 O3)as the raw material.The V2 O3 was firstly reduced at 873 K in Ar atmosphere via magnesiothermic reduction reaction to get the mixture of V and MgO,and then the products were further nitrided at 1473 K in N2 atmosphere.Finally,the as-prepared samples were acid-leached to obtain pure VN powders.X-ray diffractometry and field-emission scanning electron microscopy were used to analyze the phase transition and morphological evolution of the samples.The results reveal that the overall morphology of the obtained VN powder retains the morphology of the initial V2 O3 powders.After removing MgO by acidic leaching,the porous VN particles can be obtained,with the oxygen content of 0.178 wt.%.Compared with the traditional methods,high purity VN powders with a small amount of oxygen and no carbon can be obtained.

Electrocatalytic ammonia synthesis catalyzed by mesoporous nickel oxide nanosheets loaded with Pt nanoparticles

Owing to its cost‐effectiveness and adjustable eight‐electron distribution in the 3d orbital,nickel oxide(NiO)is considered an effective electrocatalyst for an ambient electrochemical nitrogen reduction reaction(NRR).However,because of the low conductivity of the transition metal oxide electrocatalyst,its application in this field is limited.In this study,we found that the doping of NiO nanosheets with a small amount(3–10 nm)of Pt nanoparticles(Pt/NiO‐NSs)leads to considerable improvements in the Faradaic efficiency(FE)and NH_(3) yield compared with those obtained using pure NiO,breaking the common perception that commercial Pt‐based electrocatalysts demonstrate little potential for NRR due to their high hydrogen evolution tendency.In a 0.1 mol/L Na_(2)SO_(4) solution at−0.2 V vs.RHE,a typical Pt/NiO‐2 sample exhibits an optimum electrochemical NH_(3) yield of 20.59μg h^(–1)mg^(–1)cat.and an FE of 15.56%,which are approximately 5 and 3 times greater,respectively,than those of pure NiO nanosheets at the same applied potential.X‐ray photoelectron spectroscopy analysis revealed that Pt in Pt/NiO‐NSs exist as Pt0,Pt^(2+),and Pt^(4+)and that high‐valence Pt ions are more electropositive,thereby favoring chemisorption and the activation of N2 molecules.Density function theory calculations showed that the d‐band of Pt nanoparticles supported on NiO is significantly tuned compared to that of pure Pt,affording a more favorable electronic structure for NRR.The results of this study show that Pt can be an effective NRR electrochemical catalyst when loaded on an appropriate substrate.Most importantly,it provides a new synthetic avenue for the fabrication of highly active Pt‐based NRR electrocatalysts.

Heterostructuring 2D TiO_(2) nanosheets in situ grown on Ti_(3)C_(2)T_(x) MXene to improve the electrocatalytic nitrogen reduction

In this study,TiO_(2) nanosheets(NSs)grown in situ on extremely conductive Ti_(3)C_(2)T_(x) MXene to form TiO_(2)/Ti_(3)C_(2)T_(x) MXene composites with abundant active sites are proposed to effectively achieve elec‐trocatalytic NH_(3) synthesis.Electron transfer can be promoted by Ti_(3)C_(2)T_(x) MXene with high conduc‐tivity.Meanwhile,the TiO_(2) NSs in‐situ formation can not only avoid Ti_(3)C_(2)T_(x) MXene microstacking but also enhance the surface specific area of Ti_(3)C_(2)T_(x) MXene.The TiO_(2)/Ti_(3)C_(2)T_(x) MXene catalyst reach‐es a high Faradaic efϐiciency(FE)of 44.68%at−0.75 V vs.RHE and a large NH3 yield of 44.17µg h^(-1) mg^(-1)cat.at−0.95 V,with strong electrochemical durability.15N isotopic labeling experiments imply that the N in the produced NH3 originated from the N2 of the electrolyte.DFT calculations were conducted to determine the possible NRR reaction pathways for TiO_(2)/Ti_(3)C_(2)T_(x) MXene composites.MXene catalysts combined with other materials have been rationally designed for efficient ammonia production under ambient conditions。

MXenes for electrocatalysis applications:Modification and hybridization

Two-dimensional carbides,nitrides,and carbonitrides(MXenes)play important roles in promoting the development of sustainable energy because they have abundant reactive sites on their surfaces.An increasing number of MXenes with diverse elements and composites have been predicted and synthesized for electrocatalysis applications since the first report of a Ti-Mo-based MXene for the hydrogen evolution reaction(HER).Herein,we summarize the progress of MXene-based electrocatalysts for the HER,the oxygen evolution reaction,and the oxygen reduction reaction,including regulated pristine MXenes and modified hybrid MXenes,from both theoretical and experimental perspectives.A brief overview on MXene synthesis is presented first,accompanied by a discussion on the relationship between electrocatalytic properties and M,X,T,vacancies,and morphologies.After reviewing strategies in terms of atom substitution,functional modification,defect engineering,and morphology control,we emphasize the construction of heterojunctions between MXenes and other nanostructures,such as metal nanoparticles,oxides,hydroxides,sulfides,and phosphides.We finally discuss prospects for the future development of MXene-based electrocatalysts.

Transition‐metal‐atom‐pairs deposited on g‐CN monolayer for nitrogen reduction reaction:Density functional theory calculations

The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fabricated using transition‐metal(TM)atoms(TM=Sc−Zn)doped into g‐CN monolayers.The electrochemical mechanism of APCs for an NRR has been reported by well‐defined density functional theory calculations.The calculated limiting potentials were−0.47 and−0.78 V for the Fe_(2)@CN and Co_(2)@CN catalysts,respectively.Owing to its high suppression of hydrogen evolution reactions,Co_(2)@CN is a superior electrocatalytic material for a N_(2)fixation.Stable Fe_(2)@CN may be a strongly attractive material for an NRR with a relatively low overpotential after an improvement in the selectivity.The two‐way charge transfer affirmed the donation‐acceptance procedure between N_(2)and Fe_(2)@CN or Co_(2)@CN,which play a crucial role in the activation of inert N≡N bonds.This study provides an in‐depth investigation into atom‐pair catalysts and will open up new avenues for highly efficient g‐CN‐based nanostructures for an NRR.

Synergistic interaction of Nb atoms anchored on g‐C_(3)N_(4) and H^(+) promoting high‐efficiency nitrogen reduction reaction

Nowadays catalytic nitrogen reduction reaction(NRR)by electrochemistry has attracted much attention because of its key role in producing the basic chemical product ammonia with low energy consumption.A stable and environmentally‐friendly single‐or multi‐atom catalyst with good performance in activity and selectivity is highly desired for NRR.From density functional theory calculations,the NRR mechanisms catalyzed by Nb monomer,dimer,trimer and tetramer anchored on graphitic carbon nitride(Nb_(x)@g‐C_(3)N_(4),x=1,2,3,4)have been deeply explored.It has been found that Nb_(3)@g‐C_(3)N_(4) exhibits the best catalytic ability among the four catalysts with the introduction of H+.A more stable intermediate(*NH_(2)+*H)can be found to reduce the huge free energy barrier of forming*NH_(3) from*NH_(2) directly in a multi‐atom system.By analyzing the density of states and projected crystal orbital Hamilton population,a synergistic effect among Nb atoms and the adsorbed H^(+)is responsible for reducing the overpotential of NRR.Furthermore,the competitive hydrogen evolution reaction is suppressed effectively.This work introduces a new insight in the reaction pathway in multi‐atoms for developing high‐efficiency NRR catalysts.

A combinatorial descriptor for volcano relationships of electrochemical nitrogen reduction reaction

Though touted as a potential way to realize clean ammonia synthesis,electrochemical ammonia synthesis is currently limited by its catalytic efficiency.Great effort has been made to find catalysts with improved activity toward electrochemical nitrogen reduction reaction(eNRR).Rational screening of catalysts can be facilitated using the volcano relationship between catalytic activity and adsorption energy of an intermediate,namely,the activity descriptor.In this work,we proposeΔG^(*)_(NH_(2))+ΔG^(*)_(NNH)as a combinatorial descriptor,which shows better predictive power than traditional descriptors using the adsorption free energies of single intermediates.The volcano plots based on the combinatorial descriptor exhibits peak activity fixedly at the descriptor value corresponding to the formation free energy of NH3,regardless of the catalyst types;while the descriptor values correspond to the top activities for eNRR on volcano plots based on single descriptors usually vary with the types of catalysts.

Cu nanoparticles supported on graphitic carbon nitride as an efficient electrocatalyst for oxygen reduction reaction

High active and cost‐effective electrocatalysts for the oxygen reduction reaction(ORR)are essential components of renewable energy technologies,such as fuel cells and metal/air batteries.Herein,we propose that ORR active Cu/graphitic carbon nitride(Cu/g‐CN)electrocatalyst can be prepared via a facile hydrothermal reaction in the present of the ionic liquid(IL)bis(1‐hexadecyl‐3‐methylimidazolium)tetrachlorocuprate[(C16mim)2CuCl4]and protonated g‐CN.The as‐prepared Cu/g‐CN showed an impressive ORR catalytic activity that a99mV positive shift of the onset potential and2times kinetic current density can be clearly observed,comparing with the pure g‐CN.In addition,the Cu/g‐CN revealed better stability and methanol tolerance than commercial Pt/C(HiSPECTM3000,20%).Therefore,the proposed Cu/g‐CN,as the inexpensive and efficient ORR electrocatalyst,would be a potential candidate for application in fuel cells.

Improved nitrogen reduction electroactivity by unique MoS_(2)‐SnS_(2) heterogeneous nanoplates supported on poly(zwitterionic liquids)functionalized polypyrrole/graphene oxide

Unique MoS_(2)‐SnS_(2)heterogeneous nanoplates have successfully in‐situ grown on poly(3‐(1‐vinylimidazolium‐3‐yl)propane‐1‐sulfonate)functionalized polypyrrole/graphene oxide(PVIPS/PPy/GO).PVIPS can attract heptamolybdate ion(Mo7O246−)and Sn^(4+)as the precursors by the ion‐exchange,resulting in the simultaneous growth of 1T’‐MoS2 and the berndtite‐2T‐type hexagonal SnS_(2)by the interfacial induced effect of PVIPS.The obtained MoS_(2)‐SnS_(2)/PVIPS/PPy/GO can serve as electrocatalysts,exhibiting good NRR performance by the synergistic effect.The semi‐conducting SnS_(2)would limit the surface electron accessibility for suppressing HER process of 1T’‐MoS_(2),while metallic 1T’‐MoS_(2)might efficiently improve the NRR electroactivity of SnS_(2)by the creation of Mo‐Sn‐Sn trimer catalytic sites.Otherwise,the irreversible crystal phase transition has taken place during the NRR process.Partial 1T’‐MoS_(2)and SnS_(2)have electrochemically reacted with N_(2),and irreversibly converted into Mo^(2)N and SnxNz due to the formation of Mo−N and Sn−N bonding,meanwhile,partial SnS_(2) has been irreversibly evolved into SnS due to the reduction by the power source in the electrochemical system.It would put forward a new design idea for optimizing the preparation method and electrocatalytic activity of transition metal dichalcogenides.