Efficient and durable seawater electrolysis with a V2O3-protected catalyst.

The ocean, a vast hydrogen reservoir, holds potential for sustainable energy and water development. Developing high-performance electrocatalysts for hydrogen production under harsh seawater conditions is challenging. Here, we propose incorporating a protective V2O3 layer to modulate the microcatalytic environment and create in situ dual-active sites consisting of low-loaded Pt and Ni3N. This catalyst demonstrates an ultralow overpotential of 80 mV at 500 mA cm-2, a mass activity 30.86 times higher than Pt-C and maintains at least 500 hours in seawater. Moreover, the assembled anion exchange membrane water electrolyzers (AEMWE) demonstrate superior activity and durability even under demanding industrial conditions. In situ localized pH analysis elucidates the microcatalytic environmental regulation mechanism of the V2O3 layer. Its role as a Lewis acid layer enables the sequestration of excess OH- ions, mitigate Cl- corrosion, and alkaline earth salt precipitation. Our catalyst protection strategy by using V2O3 presents a promising and cost-effective approach for large-scale sustainable green hydrogen production.

Electrocatalytic Oxygen Reduction Using Metastable Zirconium Suboxide.

Strategies for discovery of high-performance electrocatalysts are important to advance clean energy technologies. Metastable phases such as low temperature or interfacial structures that are difficult to access in bulk may offer such catalytically active surfaces. We report here that the suboxide Zr3O, which is formed at Zr-ZrO2 interfaces but does not appear in the experimental Zr-O phase diagram exhibits outstanding oxygen reduction reaction (ORR) performance surpassing that of benchmark Pt/C and most transition metal-based catalysts. Addition of Fe3C nanoparticles to give a Zr-Zr3O-Fe3C/NC catalyst (NC=nitrogen-doped carbon) gives a half-wave potential (E1/2) of 0.914 V, outperforming Pt/C and showing only a 3 mV decrease after 20,000 electrochemical cycles. A zinc-air battery (ZAB) using this cathode material has a high power density of 241.1 mW cm-2 and remains stable for over 50 days of continuous cycling, demonstrating potential for practical applications. Zr3O demonstrates that interfacial or other phases that are difficult to stabilize may offer new directions for the discovery of high-performance electrocatalysts.

(Ca0.5Mn0.5)2MnTeO6 - An Anomalously Stable High-Pressure Double Perovskite.

High pressure high temperature treatments of the composition CaMnMnTeO6 are found to yield only an A2BB'O6-type double perovskite (Ca0.5Mn0.5)2MnTeO6, rather than a AA'BB'O6 double double perovskite with A- and B- site cation order as found in analogs CaMnMnReO6 and CaMnMnWO6 with similar cation sizes. Double perovskite (Ca0.5Mn0.5)2MnTeO6 adopts a monoclinic structure in space group P21/n with a framework of highly tilted MnO6 and TeO6 octahedra enclosing disordered Ca2+ and Mn2+ cations. Magnetic measurements show that (Ca0.5Mn0.5)2MnTeO6 is a highly frustrated spin glass with a freezing transition at 5 K, and no long-range spin order is apparent by neutron diffraction at 1.6 K.

A New Family of High Oxidation State Antiperovskite Nitrides: La3MN5 (M=Cr, Mn and Mo).

Three new nitrides La3MN5 (M=Cr, Mn, and Mo) have been synthesized using a high pressure azide route. These are the first examples of ternary Cs3CoCl5-type nitrides, and show that this (MN4)NLa3 antiperovskite structure type may be used to stabilise high oxidation-state transition metals in tetrahedral molecular [MN4]n- nitridometallate anions. Magnetic measurements confirm that Cr and Mo are in the M6+ state, but the M=Mn phase has an anomalously small paramagnetic moment and large cell volume. Neutron powder diffraction data are fitted using an anion-excess La3MnN5.30 model (space group I4/mcm, a=6.81587(9) Šand c=11.22664(18) Šat 200 K) in which Mn is close to the +7 state. Excess-anion incorporation into Cs3CoCl5-type materials has not been previously reported, and this or other substitution mechanisms may enable many other high oxidation state transition metal nitrides to be prepared.

Metal nitrides for seawater electrolysis.

Electrocatalytic high-throughput seawater electrolysis for hydrogen production is a promising green energy technology that offers possibilities for environmental and energy sustainability. However, large-scale application is limited by the complex composition of seawater, high concentration of Cl- leading to competing reaction, and severe corrosion of electrode materials. In recent years, extensive research has been conducted to address these challenges. Metal nitrides (MNs) with excellent chemical stability and catalytic properties have emerged as ideal electrocatalyst candidates. This review presents the electrode reactions and basic parameters of the seawater splitting process, and summarizes the types and selection principles of conductive substrates with critical analysis of the design principles for seawater electrocatalysts. The focus is on discussing the properties, synthesis, and design strategies of MN-based electrocatalysts. Finally, we provide an outlook for the future development of MNs in the high-throughput seawater electrolysis field and highlight key issues that require further research and optimization.

Defect rocksalt structures in the La-Na-N system.

Sodium azide (NaN3) is a versatile nitrogen source that can be used for the synthesis of new nitrides under high-pressure and temperature conditions. Reactions between lanthanum nitride (LaN) and sodium azide (NaN3) at 800°C under 8 GPa pressure have led to the discovery of two defect rocksalt phases which are the first reported ternaries in the La-Na-N system. Preliminary structure assignments have been made based on fits to powder X-ray diffraction profiles. One phase is La1-xNa3xN with vacancies at octahedral La sites and interstitial tetrahedral Na cations. This phase has a tetragonally distorted rocksalt structure (space group I4[Formula: see text]mmm, a = 3.8704(2) and c = 5.2098(3) Å for nominal x = 0.10) and the distortion decreases with increasing Na content (space group I4[Formula: see text]mmm, a = 3.8060(2) Å, c = 5.2470(3) Å for nominal x = 0.14), further giving a cubic phase (a = 5.3055(2) Å) for nominal x = 0.25. This coexists with another cubic [Formula: see text] phase (a = 5.1561 (5) Å), tentatively identified as rocksalt 'NaN1/3' stabilized by a small amount of La; NaLayN(1+3y)/3 with y ≈ 1%. These initial investigations reveal that the high-pressure La-Na-N phase diagram may be rich in defect rocksalt-type materials although further work using neutron diffraction will be needed to confirm the structures. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

CaFeFeNbO6 - an iron-based double double perovskite.

Ordering of cations is important for controlling properties of ABO3 perovskites, and CaFeFeNbO6 is the first example of an Fe-based AA'BB'O6 double double perovskite, with Ca2+/Fe2+ ordered on A-site columns, and Fe3+/Nb5+ at the octahedral B-sites. Substantial (37%) antisite disorder of the latter cations leads to spin glassy magnetism below a freezing transition at 12 K. The CaMnFeNbO6 analogue also shows substantial cation disorder and spin glassy behaviour. Comparison of synthesis pressures for ordered materials based on different A-site transition metals, suggests that pressures of at least 14-18 GPa will be required to discover the expected plethora of double double perovskites based on A' cations smaller than Mn2+.

1 : 1 Ca2+ :Cu2+ A-site Order in a Ferrimagnetic Double Double Perovskite.

Cation ordering in ABX3 perovskites is important to structural, physical and chemical properties. Here we report discovery of CaCuFeReO6 with the tetragonal AA'BB'O6 double double perovskite structure that was previously only reported for A'=Mn compositions. CaCuFeReO6 occurs in the same phase field as CaCu3 Fe2 Re2 O12 demonstrating that different A-cation ordered peroskites may be obtained in the same chemical system. CaCuFeReO6 has ferrimagnetic order of Fe, Re and Cu spins below TC =567 K, in contrast to Mn analogues where the Mn spins order separately at much lower temperatures. The magnetoresistance of CaCuFeReO6 displays low-field "butterfly" hysteresis with an unusual change from negative to positive values as field increases. Many more AA'BB'O6 double double perovskites may be accessible for A'=Cu and other divalent transition metals at high pressure, so the presently known phases likely represent only the "tip of the iceberg" for this family.

Magnetism and the Trimeron Bond.

A review of progress in understanding the Verwey transition in magnetite (Fe3O4) over the past decade is presented. This electronic and structural transition at T V ≈ 125 K was reported in 1939 and has since been a contentious issue in magnetism. Long range Fe2+/Fe3+ charge ordering has been confirmed below the transition from crystal structure refinement, and Fe2+ orbital ordering and formation of trimerons through weak bonding of Fe2+ states to two Fe neighbors has been discovered. This model has accounted for many spectroscopic observations such as the 57Fe NMR frequencies. The trimeron lifetime has been measured, and trimeron soft modes have been observed. The origin of the first to second order crossover of Verwey transitions in doped magnetites has been revealed by a nanoparticle study. Electronic and structural fluctuations are found to persist to temperatures far above T V and local structural distortions track the bulk magnetization, disappearing at the 850 K Curie transition. New binary mixed-valent iron oxides discovered at high pressure are found to have electronic transitions and orbital molecule ground states similar to those of magnetite.

Chemical pressure in functional materials.

Chemical pressure, a strange but familiar concept, is a lattice internal force caused by lattice strain with chemical modifications and arouses great interest due to its diversity and efficiency to synthesize new compounds and tune functional materials. Different from physical pressure loaded by an external force that is positive, chemical pressure can be either positive or negative (contract a lattice or expand it), often through flexible and mild chemical synthesis strategies, which are particularly important as a degree of freedom to manipulate material behaviors. In this tutorial review, we summarize the features of chemical pressure as a methodology and demonstrate its role in synthesizing and discovering some typical magnetically, electrically, and thermally responsive functional materials. The measure of chemical pressure using experimental lattice strain and elastic modulus was proposed, which can be used for quantitative descriptions of the correlation between lattice distortion and properties. From a lattice strain point of view, we classify chemical pressure into different categories: (i) chemical substitution, (ii) chemical intercalation/de-intercalation, (iii) size effect, and (iv) interface constraint, etc. Chemical pressure affects chemical bonding and rationalizes the crystal structure by modifying the electronic structure of solids, regulating the lattice symmetry, local structure, phonon structure effects etc., emerging as a general and effective method for synthesizing new compounds and tuning functional materials.

A New Cation-Ordered Structure Type with Multiple Thermal Redistributions in Co2 InSbO6.

Cation ordering in solids is important for controlling physical properties and leads to ilmenite (FeTiO3 ) and LiNbO3 type derivatives of the corundum structure, with ferroelectricity resulting from breaking of inversion symmetry in the latter. However, a hypothetical third ABO3 derivative with R32 symmetry has never been observed. Here we show that Co2 InSbO6 recovered from high pressure has a new, ordered-R32 A2 BCO6 variant of the corundum structure. Co2 InSbO6 is also remarkable for showing two cation redistributions, to (Co0.5 In0.5 )2 CoSbO6 and then Co2 InSbO6 variants of the ordered-LiNbO3 A2 BCO6 structure on heating. The cation distributions change magnetic properties as the final ordered-LiNbO3 product has a sharp ferrimagnetic transition unlike the initial ordered-R32 phase. Future syntheses of metastable corundum derivatives at pressure are likely to reveal other cation-redistribution pathways, and may enable ABO3 materials with the R32 structure to be discovered.

Boosting Oxygen Reduction for High-Efficiency H2 O2 Electrosynthesis on Oxygen-Coordinated CoNC Catalysts.

Atomically dispersed CoNC is a promising material for H2 O2 selective electrosynthesis via a two-electron oxygen reduction reaction. However, the performance of typical CoNC materials with routine CoN4 active center is insufficient and needs to be improved further. This can be done by fine-tuning its atomic coordination configuration. Here, a single-atom electrocatalyst (Co/NC) is reported that comprises a specifically penta-coordinated CoNC configuration (OCoN2 C2 ) with Co center coordinated by two nitrogen atoms, two carbon atoms, and one oxygen atom. Using a combination of theoretical predictions and experiments, it is confirmed that the unique atomic structure slightly increases the charge state of the cobalt center. This optimizes the adsorption energy towards *OOH intermediate, and therefore favors the two-electron ORR relevant for H2 O2 electrosynthesis. In neutral solution, the as-synthesized Co/NC exhibits a selectivity of over 90% over a potential ranging from 0.36 to 0.8 V, with a turnover frequency value of 11.48 s-1 ; thus outperforming the state-of-the-art carbon-based catalysts.

Mesoporous Ti0.5Cr0.5N for trace H2S detection with excellent long-term stability.

Efficient, accurate and reliable detection and monitoring of H2S is of significance in a wide range of areas: industrial production, medical diagnosis, environmental monitoring, and health screening. However the rapid corrosion of commercial platinum-on-carbon (Pt/C) sensing electrodes in the presence of H2S presents a fundamental challenge for fuel cell gas sensors. Herein we report a solution to the issue through the design of a sensing electrode, which is based on Pt supported on mesoporous titanium chromium nitrides (Pt/Ti0.5Cr0.5N). Its desirable characteristics are due to its high electrochemical stability and strong metal-support interactions. The Pt/Ti0.5Cr0.5N-based sensors exhibit a much smaller attenuation (1.3%) in response to H2S than Pt/C-sensor (40%), after 2 months sensing test. Furthermore, the Pt/Ti0.5Cr0.5N-based sensors exhibit negligible cross response to other interfering gases compared with hydrogen sulfide. Results of density functional theory calculation also verify the excellent long-term stability and selectivity of the gas sensor. Our work hence points to a new sensing electrode system that offers a combination of high performance and stability for fuel-cell gas sensors.

Slow oxidation of magnetite nanoparticles elucidates the limits of the Verwey transition.

Magnetite (Fe3O4) is of fundamental importance for the Verwey transition near TV = 125 K, below which a complex lattice distortion and electron orders occur. The Verwey transition is suppressed by chemical doping effects giving rise to well-documented first and second-order regimes, but the origin of the order change is unclear. Here, we show that slow oxidation of monodisperse Fe3O4 nanoparticles leads to an intriguing variation of the Verwey transition: an initial drop of TV to a minimum at 70 K after 75 days and a followed recovery to 95 K after 160 days. A physical model based on both doping and doping-gradient effects accounts quantitatively for this evolution between inhomogeneous to homogeneous doping regimes. This work demonstrates that slow oxidation of nanoparticles can give exquisite control and separation of homogeneous and inhomogeneous doping effects on the Verwey transition and offers opportunities for similar insights into complex electronic and magnetic phase transitions in other materials.

Low-dimensional magnetism in calcium nitridonickelate(II) Ca2NiN2.

Calcium nitridonickelate(II) Ca2NiN2 has been prepared through a high-temperature and high-pressure azide-mediated redox reaction, demonstrating that this method can stabilise nitrides of late transition metals in relatively high oxidation states. Ca2NiN2 crystallizes in the Na2HgO2 structure type and displays low-dimensional antiferromagnetic ordering of Ni2+ spins.

Co3Mo3N-An efficient multifunctional electrocatalyst.

Efficient catalysts are required for both oxidative and reductive reactions of hydrogen and oxygen in sustainable energy conversion devices. However, current precious metal-based electrocatalysts do not perform well across the full range of reactions and reported multifunctional catalysts are all complex hybrids. Here, we show that single-phase porous Co3Mo3N prepared via a facile method is an efficient and reliable electrocatalyst for three essential energy conversion reactions; oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and hydrogen evolution reaction (HER) in alkaline solutions. Co3Mo3N presents outstanding OER, ORR, and HER activity with high durability, comparable with the commercial catalysts RuO2 for OER and Pt/C for ORR and HER. In practical demonstrations, Co3Mo3N gives high specific capacity (850 mA h gZn -1 at 10 mA cm-2) as the cathode in a zinc-air battery, and a low potential (1.63 V at 10 mA cm-2) used in a water-splitting electrolyzer. Availability of Co and Mo d-states appear to result in high ORR and HER performance, while the OER properties result from a cobalt oxide-rich activation surface layer. Our findings will inspire further development of bimetallic nitrides as cost-effective and versatile multifunctional catalysts that will enable scalable usage of electrochemical energy devices.

Preparation of Bulk-Phase Nitride Perovskite LaReN3 and Topotactic Reduction to LaNiO2 -Type LaReN2.

While halide and oxide perovskites are numerous and many display outstanding properties, ABN3 perovskite nitrides are extremely rare due to synthetic challenges arising from the low chemical potential of nitrogen and a tendency to form low-coordination nitridometallate anions. We report the preparation of a perovskite nitride LaReN3 through azide-mediated oxidation at high pressure. High-resolution synchrotron diffraction shows that LaReN3 has a low-symmetry, triclinic, perovskite superstructure resulting from orbital ordering with strong spin-orbit coupling distortions. Topotactic reduction of LaReN3 above 500 °C leads to layered tetragonal LaReN2 via a probable LaReN2.5 intermediate, which is the first reported example of nitride defect perovskites. Magnetisation and conductivity measurements indicate that LaReN3 and LaReN2 are both metallic solids. The two chemical approaches presented are expected to lead to new classes of ABN3 and defect ABN3-x nitride perovskite materials.

Mn3MnNb2O9: high-pressure triple perovskite with 1 : 2 B-site order and modulated spins.

The first triple perovskite with Mn in A- and 1 : 2 B-site order Mn3MnNb2O9, prepared using high pressure phase transformation of the magnetodielectric Mn4Nb2O9, is reported herein. It has a complex magnetic behaviour with a transition from a collinear AFM into an evolving incommensurate spin density wave (SDW) further stabilised into a lock-in structure dictated by the B-site order.

Double Double to Double Perovskite Transformations in Quaternary Manganese Oxides.

Control of cation ordering in ABX3 perovskites is important to structural, physical and chemical properties. Here we show that thermal transformations of AA'BB'O6 double double perovskites, where both A and B sites have 1:1 cation order, to (A0.5 A'0.5 )2 BB'O6 double perovskites with fully disordered A/A' cations can be achieved under pressure in CaMnMnWO6 and SmMnMnTaO6 , enabling both polymorphs of each material to be recovered. This leads to a dramatic switch of magnetic properties from ferrimagnetic order in double double perovskite CaMnMnWO6 to spin glass behaviour in the highly frustrated double perovskite polymorph. Comparison of double double and double perovskite polymorphs of other materials will enable effects of cation order and disorder on other properties such as ferroelectricity and conductivity to be explored.

Alignment facility and software for single-crystal time-of-flight neutron spectroscopy.

An instrument and software algorithm are described for the purpose of characterization of large single crystals at the Alignment Facility of the ISIS spallation neutron source. A method for both characterizing the quality of the sample and aligning it in a particular scattering plane is introduced. A software package written for this instrument is presented, and its utility is demonstrated by way of an example of the structural characterization of large single crystals of Pb(Mg1/3Nb2/3)O3. Extensions and modifications of characterization instruments for future improved beamlines are suggested. It is hoped that this software will be used by the neutron community for pre-characterizing large single crystals for spectroscopy experiments and that in the future such a facility will be included as part of the spectroscopy suite at other spallation neutron sources.