Chemical Diversity for Tailoring Negative Thermal Expansion.

Negative thermal expansion (NTE), referring to the lattice contraction upon heating, has been an attractive topic of solid-state chemistry and functional materials. The response of a lattice to the temperature field is deeply rooted in its structural features and is inseparable from the physical properties. For the past 30 years, great efforts have been made to search for NTE compounds and control NTE performance. The demands of different applications give rise to the prominent development of new NTE systems covering multifarious chemical substances and many preparation routes. Even so, the intelligent design of NTE structures and efficient tailoring for lattice thermal expansion are still challenging. However, the diverse chemical routes to synthesize target compounds with featured structures provide a large number of strategies to achieve the desirable NTE behaviors with related properties. The chemical diversity is reflected in the wide regulating scale, flexible ways of introduction, and abundant structure-function insights. It inspires the rapid growth of new functional NTE compounds and understanding of the physical origins. In this review, we provide a systematic overview of the recent progress of chemical diversity in the tailoring of NTE. The efficient control of lattice and deep structural deciphering are carefully discussed. This comprehensive summary and perspective for chemical diversity are helpful to promote the creation of functional zero-thermal-expansion (ZTE) compounds and the practical utilization of NTE.

Frenkel Defect-modulated Anti-thermal Quenching Luminescence in Lanthanide-doped Sc2 (WO4 )3.

Although large amount of effort has been invested in combating thermal quenching that severely degrades the performance of luminescent materials particularly at high temperatures, not much affirmative progress has been realized. Herein, we demonstrate that the Frenkel defect formed via controlled annealing of Sc2 (WO4 )3 :Ln (Ln=Yb, Er, Eu, Tb, Sm), can work as energy reservoir and back-transfer the stored excitation energy to Ln3+ upon heating. Therefore, except routine anti-thermal quenching, thermally enhanced 415-fold downshifting and 405-fold upconversion luminescence are even obtained in Sc2 (WO4 )3 :Yb/Er, which has set a record of both the Yb3+ -Er3+ energy transfer efficiency (>85 %) and the working temperature at 500 and 1073 K, respectively. Moreover, this design strategy is extendable to other hosts possessing Frenkel defect, and modulation of which directly determines whether enhanced or decreased luminescence can be obtained. This discovery has paved new avenues to reliable generation of high-temperature luminescence.

Two-Dimensional Negative Thermal Expansion in a Facile and Low-Cost Oxalate-Based Metal-Organic Framework.

Two-dimensional negative thermal expansion (NTE) is achieved in a tetragonal oxalate-based metal-organic framework (MOF), CdZrSr(C2O4)4, within a temperature range from 123 to 398 K [space group I4̅m2, αa = -2.4(7) M K-1, αc = 11.3(3) M K-1, and αV = 6.4(1) M K-1]. By combining variable-temperature X-ray diffraction, a high-resolution synchrotron X-ray pair distribution function, and thermogravimetry-differential scanning calorimetry, we shows that NTE within the ab plane derives from the oriented rotation of an oxalate ligand in zigzag chains (-CdO8-ox-ZrO8-ox-)∞. That is simplified to the Zr atom rotating with an unchanged Zr···Cd distance as the radius, which also gives rise to the deformation of a hingelike connection along the c axis and results in its positive thermal expansion. By virtue of the facile and low-cost oxalate ligand, the present NTE MOF may show application prospects in the future.

Resistive pulse sensing device with embedded nanochannel (nanochannel-RPS) for label-free biomolecule and bionanoparticle analysis.

This paper reports an IC-compatible method for fabricating a PDMS-based resistive pulse sensing (RPS) device with embedded nanochannel (nanochannel-RPS) for label-free analysis of biomolecules and bionanoparticles, such as plasmid DNAs and exosomes. Here, a multilayer lithography process was proposed to fabricate the PDMS mold for the microfluidic device, comprising a bridging nanochannel, as the sensing gate. RPS was performed by placing the sensing and excitation electrodes symmetrically upstream and downstream of the sensing gate. In order to reduce the noise level, a reference electrode was designed and placed beside the excitation electrode. To demonstrate the feasibility of the proposed nanochannel-RPS device and sensing system, polystyrene micro- and nanoparticles with diameters of 1µm and 300 nm were tested by the proposed device with signal-to-noise ratios (SNR) ranging from 9.1-30.5 and 2.2-5.9, respectively. Furthermore, a nanochannel with height of 300 nm was applied for 4 kb plasmid DNA detection, implying the potential of the proposed method for label-free quantification of nanoscale biomolecules. Moreover, HeLa cell exosomes, known as a well-studied subtype of extracellular vesicles, were measured and analyzed by their size distribution. The result of the resistive pulse amplitude corresponded well to that of nanoparticle tracking analysis (NTA). The proposed nanochannel-RPS device and the sensing strategy are not only capable of label-free analysis for nanoscale biomolecules and bionanoparticles, but are also cost-effective for large-scale manufacturing.

Accurately Regulating the Electronic Structure of Nix Sey @NC Core-Shell Nanohybrids through Controllable Selenization of a Ni-MOF for pH-Universal Hydrogen Evolution Reaction.

N-doped carbon-encapsulated transition metal selenides (TMSs) have garnered increasing attention as promising electrocatalysts for hydrogen evolution reaction (HER). Accurately regulating the electronic structure of these nanohybrids to reveal the underlying mechanism for enhanced HER performances is still challenging and thus requires deep excavation. Herein, a series of pomegranate-like Nix Sey @NC core-shell nanohybrids (including Ni0.85 Se @ NC, NiSe2 @NC, and NiSe@NC) through controllable selenization of a Ni-MOF precursor is reported. The component of the nanohybrids can be fine-tuned by tailoring the selenization temperature and feed ratio, through which the electronic structure can be synchronously regulated. Among these nanohybrids, the Ni0.85 Se @ NC exhibits the optimum pH-universal HER performance with overpotentials of 131, 135, and 183 mV in 0.5 m H2 SO4 , 1.0 m KOH, and 1.0 m PBS, respectively, at 10 mA cm-2 , which are attributed to the increased partial density of state at the Fermi level and effective van der Waals interactions between Ni0.85 Se and NC matrix explained by density functional theory calculations.

Role of "Dumbbell" Pairs of Fe in Spin Alignments and Negative Thermal Expansion of Lu2Fe17-Based Intermetallic Compounds.

Knowledge of negative thermal expansion (NTE) is an interesting issue in the field of materials science and engineering. It has been proposed that the unique dumbbell pairs of Fe (dumbbells) are highly entangled in the NTE behaviors of R2Fe17 (R = rare earth) compounds but still remain controversial. Here, a facile method is employed to explore the role of dumbbells in spin alignments and NTE by the nonstoichiometric design of Lu2-xFe17 compounds. The powder synchrotron X-ray diffraction, magnetometry, and neutron powder diffraction investigations indicate that a decrease of the Lu content can enhance the dumbbell concentration and motivate an incommensurate magnetic structure simultaneously. However, increasing the dumbbell concentration makes little difference in the amplitude of the ordered magnetic moments of Fe sublattices, which reveals an equivalent NTE behavior for Lu2-xFe17 compounds. This work gives insight into the role that dumbbells played in spin alignments and NTE for Lu2Fe17-based compounds, correcting the previously proposed conjecture and probably conducive to adjusting the related magnetic performances of R2Fe17 compounds in the future.

Manipulating Spin Alignments of (Y,Lu)1.7Fe17 Intermetallic Compounds via Unusual Thermal Pressure.

External pressure has been successfully employed to achieve desirable spin alignments in the field of materials science but is seriously restricted by the difficulty of reaching high pressure with conventional methods. The search for simple and effective ways to apply pressure on the lattice is challenging but intriguing. Here we report a new strategy to manipulate the spin alignments of (Y,Lu)1.7Fe17 intermetallic compounds through unusual thermal pressure. The spin alignments of Fe initially lie parallel inside the basal plane and then turn spirally between adjacent layers with a zone axis along the c direction under higher Lu concentration. The synchrotron and neutron powder diffraction investigations clearly reveal that the direction of spin alignments is highly correlated to large lattice contraction induced by negative thermal expansion (NTE), an unusual thermal pressure, along the c direction. The critical lattice parameter c to form spiral spin alignments is determined unambiguously. This work presents a feasible way to adjust spin alignments through NTE, which might be conducive to the future design of particular spin alignments instead of physical pressure for functional magnetic materials.

Sequential Solid-State Transformations Involving Consecutive Rearrangements of Secondary Building Units in a Metal-Organic Framework.

Solid-state transformations in metal-organic framework (MOF) systems are important phenomena and have led to the creation of new MOF structures. Solid-state transformations from interpenetrated to non-interpenetrated networks involving rearrangement of secondary building units (SBUs) in a single-crystal-to-single-crystal (SCSC) fashion have not been explored to date. Herein, we report the sequential, thermally stimulated solid-state transformations in a barium-organic framework ( UPC-600 ). The two-fold interpenetrated framework of  UPC-600  is converted at 373 K to UPC-601 , a non-interpenetrated framework. This proceeds in a SCSC fashion and involves the rearrangement of two proximate rod-shaped SBUs in different nets to generate a new rod-shaped SBU. At 473 K, a continuous solid-state transformation involving a second rearrangement occurred,  UPC-601  converted to UPC-602  by the rearrangement of the 1D rod-shaped SBU to a 2D layer SBU. This is the first example of such a thermally-driven stepwise transformation involving simultaneous cleavage and regeneration of multiple bonds. This result will enable detailed studies of solid-state transformations, and encourages a deep understanding of the role of solid-state transformations in the synthesis of MOF materials.

Sequential Solid-State Transformations Involving Consecutive Rearrangements of Secondary Building Units in a Metal-Organic Framework (MOF).

Solid-state transformations in metal-organic frameworks (MOFs) are important and have led to the creation of new MOF structures. Solid-state transformations from interpenetrated to non-interpenetrated networks involving rearrangement of secondary building units (SBUs) in a single-crystal-to-single-crystal (SCSC) fashion have not been explored to date. Herein, we report the sequential, thermally stimulated solid-state transformations in a barium-organic framework (UPC-600). The two-fold interpenetrated framework of UPC-600 is converted at 373 K into UPC-601, a non-interpenetrated framework. This proceeds in a SCSC fashion and involves the rearrangement of two proximate rod-shaped SBUs in different nets to generate a new rod-shaped SBU. At 473 K, a continuous solid-state transformation involving a second rearrangement occurred, UPC-601 converted into UPC-602 by the rearrangement of the 1D rod-shaped SBU to a 2D layer SBU. This is the first example of such a thermally driven stepwise transformation involving simultaneous cleavage and regeneration of multiple bonds.

Fabrication of a Hydrogen-Bonded Organic Framework Membrane through Solution Processing for Pressure-Regulated Gas Separation.

Ordered and flexible porous frameworks with solution processability are highly desirable to fabricate continuous and large-scale membranes for the efficient gas separation. Herein, the first microporous hydrogen-bonded organic framework (HOF) membrane has been fabricated by an optimized solution-processing technique. The framework exhibits the superior stability because of the abundant hydrogen bonds and strong π-π interactions. Thanks to the flexible HOF structure, the membrane possesses the unprecedented pressure-responsive H2 /N2 separation performance. Furthermore, the scratched membrane can be healed by the treatment of solvent vapor, achieving the recovery of separation performance.

Neutron Diffraction Study of Unusual Magnetic Behaviors in the Ho2Fe11Al6 Intermetallic Compound.

Knowledge of structure-property relationships is fundamental but significant in the exploitation of magnetic materials. Here we report that the high Al substitution for Fe transformed the crystal structure from a hexagonal Ho2Fe17 compound to a rhombohedral Ho2Fe11Al6 compound. Intriguingly, the latter shows unusual evolution of magnetization around 86 and 220 K compared with the former. Integrated investigations of the detailed structure analysis and magnetic performance on the Ho2Fe11Al6 compound demonstrate that the Ho2Fe11Al6 compound possesses a stable rhombohedral structure (R3̅m) from 5 to 430 K with preferred occupation of Al atoms and ferrimagnetic structure in which the magnetic moments of Ho and Fe lie antiparallel in the basal plane below the Curie temperature. The results of the temperature dependence of moments reveal that the disparate rates of change of the moments for Ho and Fe sublattices give rise to unusual evolution of magnetization around 86 and 220 K and then turn to paramagnetic above 280 K. This work provides clear structure and magnetization information on the Ho2Fe11Al6 compound, which may be beneficial to guiding the future development of magnetic materials.

Structure and Phase Transformation in the Giant Magnetostriction Laves-Phase SmFe2.

As one class of the most important intermetallic compounds, the binary Laves-phase is well-known for its abundant magnetic properties. Samarium-iron alloy system SmFe2 is a prototypical Laves compound that shows strong negative magnetostriction but relatively weak magnetocrystalline anisotropy. SmFe2 has been identified as a cubic Fd3̅m structure at room temperature; however, the cubic symmetry, in principle, does not match the spontaneous magnetization along the [111]cubic direction. Here we studied the crystal structure of SmFe2 by high-resolution synchrotron X-ray powder diffraction, X-ray total scattering, and selected-area electron diffraction methods. SmFe2 is found to adopt a centrosymmetric trigonal R3̅m structure at room temperature, which transforms to an orthorhombic Imma structure at 200 K. This transition is in agreement with the changes of easy magnetization direction from [111]cubic to [110]cubic direction and is further evidenced by the inflection of thermal expansion behavior, the sharp decline of the magnetic susceptibility in the field-cooling-zero field-cooling curve, and the anomaly in the specific heat capacity measurement. The revised structure and phase transformation of SmFe2 could be useful to understand the magnetostriction and related physical properties of other RM2-type pseudocubic Laves-phase intermetallic compounds.

YScSi4N6C:Ce3+-A Broad Cyan-Emitting Phosphor To Weaken the Cyan Cavity in Full-Spectrum White Light-Emitting Diodes.

On the basis of a rough rule of thumb that the difference in ionic radius for the interstitial cationic pair may affect the structure of some nitride and carbonitride compounds, a novel carbonitride phosphor, YScSi4N6C:Ce3+, was successfully designed. The crystal structure (space group P63mc (No. 186), a = b = 5.9109(8) Å, c = 9.67701(9) Å, α = ß = 90°, γ = 120°) was characterized by single-crystal synchrotron X-ray diffraction and further confirmed by powder X-ray diffraction and refined with Rietveld methods. Ce3+-doped YScSi4N6C shows a broad excitation band ranging from 280 to 425 nm and a broad cyan emission band peaking at about 469 nm upon excitation by near-UV light (400 nm). The mechanism of thermal quenching for this phosphor was also investigated. In addition, a white light-emitting diode (w-LED) was prepared by coating a near-UV chip (λem = 405 nm) with YScSi4N6C:Ce3+, ß-sialon:Eu2+ (green), and CaAlSiN3:Eu2+ (red) phosphors. It emitted a well-distributed warm white light with high color rendering index (CRI) of 94.7 and a correlated color temperature (CCT) of 4159 K. The special color rendering index R12 of the obtained white light was as high as 88. All of the results indicate that this novel phosphor can compensate for the cyan cavity and has potential applications in the full-spectrum lighting field.

Spring-like motion caused large anisotropic thermal expansion in nonporous M(eim)2 (M = Zn, Cd).

Two nonporous coordination polymers were found to possess large anisotropic thermal expansion, which was derived from the flexible structures. A "spring-like" thermal motion was proposed to illustrate the mechanism. Compound Cd(eim)2 (eim = 2-ethylimidazole) possesses large linear and reversible thermal expansion properties and the emission intensity shows a linear decrease with temperature, making it a candidate for thermo-responsive materials.

Switching Between Giant Positive and Negative Thermal Expansions of a YFe(CN)6 -based Prussian Blue Analogue Induced by Guest Species.

The control of thermal expansion of solid compounds is intriguing but remains challenging. The effect of guests on the thermal expansion of open-framework structures was investigated. Notably, the presence of guest ions (K+ ) and molecules (H2 O) can substantially switch thermal expansion of YFe(CN)6 from negative (αv =-33.67×10-6  K-1 ) to positive (αv =+42.72×10-6  K-1 )-a range that covers the thermal expansion of most inorganic compounds. The mechanism of such substantial thermal expansion switching is revealed by joint studies with synchrotron X-ray diffraction, X-ray absorption fine structure, neutron powder diffraction, and density functional theory calculations. The presence of guest ions or molecules plays a critical damping effect on transverse vibrations, thus inhibiting negative thermal expansion. An effective method is demonstrated to control the thermal expansion in open-framework materials by adjusting the presence of guests.

Biphenyl tetracarboxylic acid-based metal-organic frameworks: a case of topology-dependent thermal expansion.

The large inherent flexibility and highly modular nature of metal-organic frameworks (MOFs) make them ideal candidates for the study of negative thermal expansion (NTE). Among diverse organic ligands, the biphenyl unit, which can unrestrictedly rotate along its C-C single bond, can largely enhance the structural flexibility. Herein, we explored the thermal expansion behaviors of four indium biphenyl tetracarboxylates (BPTCs). Owing to the different dihedral angles of BPTC ligands and coordination mode of In3+, they show distinct topologies: InOF-1 (nti), InOF-2 (unc), InOF-12 (pts) and InOF-13 (nou). Intriguingly, it is found that the thermal expansion is highly dependent on the specific topology. The MOFs featuring mononuclear nodes show normal positive thermal expansion (PTE), and the magnitudes of coefficients follow the trend of InOF-2 < InOF-12 < InOF-13, inversely related to averaged molecular volumes. In contrast, the InOF-1, composed of a 1D chain of corner-shared InO6 octahedrons, shows pronounced NTE. Detailed high-resolution synchrotron powder X-ray diffraction and lattice dynamic analyses shed light on the fact that NTE in the InOF-1 is a synergy effect of the spring-like distortion of the inorganic 1D helical chain and twisting of the BPTC ligands. The present work shows how the topological arrangement of building blocks governs the thermal expansion behaviors.

Size-induced d band center upshift of copper for efficient nitrate reduction to ammonia.

Electrocatalytic nitrate reduction (NO3RR) technique has emerged as a hotspot in NH3 production, for its practicability, and a series of advanced electrocatalysts with high activity and robust stability needed to be constructed in today's era. In this work, size-tunable Cu nanoparticles on porous nitrogen-doped hexagonal carbon nanorods (Cu@NHC) were reasonably designed and served for catalyzing NO3RR in neutral media. Especially, Cu30%@NHC demonstrated a remarkable electroactivity for NH3 production as it showed a suitable grain size with massive catalytic centers and favorable d band structure with faster *NO3--to-*NO2- catalytic dynamics. As expected, Cu30%@NHC (3628.28 µg h-1 mgcat.-1) had a much higher NH3 yield than those for Cu20%@NHC (1268.42 µg h-1 mgcat.-1) and Cu40%@NHC (725.03 µg h-1 mgcat.-1). And those collected NH3 products indeed derived from NO3RR process revealed by 15N isotope-labeling and systemic control tests. Moreover, Cu30%@NHC was also durable for NO3RR bulk electrolysis with minor loss in activity. This work offered an effective modifying tactics to boost NO3RR catalysis and could guide the design of other advanced electrocatalysts via size-induced surface engineering.

Regulating the thermal expansion of a [FePt(CN)4] layer by axial coordination and dimensional reduction.

Thermal expansion regulation by chemical decoration at a molecular level is of great technological value for materials science. Herein, we show that the spin crossover active compound Fe(pyz)Pt(CN)4 (pyz = pyrazine) shows a rare 2D negative thermal expansion (NTE) in the ab-plane. By introducing axial coordination iodine ions or reducing the framework dimension from 3D to 2D, the NTE behavior can be effectively switched to positive thermal expansion (PTE) or even zero thermal expansion (ZTE). Moreover, it is found that different spin states of Fe2+ also influence the magnitude of NTE. Compared with the low-spin (LS) sate, the high-spin (HS) state tends to enhance the magnitude of NTE. Combined in situ structural and Raman spectral analyses revealed that the NTE mainly originates from the transverse vibration of a bridging cyano group and the tailorable thermal expansion is closely related to the state of the Fe-CN-Pt linkage. The present study shows how the rational regulation of the building unit and framework dimensions can effectively control thermal expansion behaviors. This insight can serve as guidance for designing and synthesizing novel NTE materials.

A new method for estimating ore grade based on sample length weighting.

Estimation of ore grade is very important for the value evaluation of ore deposits, and it directly affects the development of mineral resources. To improve the accuracy of the inverse distance weighting (IDW) method in ore grade estimation and reduce the smoothing effect of the IDW method in grade estimation, the weight calculation method involved in the IDW method was improved. The length parameter of the ore sample was used to calculate the weight of the IDW method. The length of the ore samples was used as a new factor of the weighting calculation. A new method of IDW integrated with sample length weighting (IDWW) was proposed. The grade estimation of Li, Al, and Fe in porcelain clay ore was used as a case study. A comparative protocol for grade estimation via the IDWW method was designed and implemented. The number of samples involved in the estimation, sample combination, sample grade distribution, and other factors affecting the grade estimation were considered in the experimental scheme. The grade estimation results of the IDWW and the IDW methods were used for comparative analysis of grades of the original and combined samples. The estimated results of the IDWW method were also compared with those of the IDW method. The deviation analysis of the estimated grade mainly included the minimum, maximum, mean, and coefficient of variation of the ore grade. The estimation effect of IDWW method was verified. The minimum deviations of the estimated grade of Li, Al, and Fe were between 9.129% and 59.554%. The maximum deviations were between 4.210 and 22.375%. The mean deviations were between - 1.068 and 7.187%. The deviations in the coefficient of variation were between 3.076 and 36.186%. The deviations in the maximum, minimum, mean, and coefficients of variation of the IDWW were consistent with those of the IDW, demonstrating the accuracy and stability of the IDWW method. The more the samples involved in the estimation, the greater the estimation deviations of IDW and IDWW methods. The estimated deviations of Li, Al, and Fe were affected by the shape of the grade distribution, when the same estimation parameters were used. The grade distribution pattern of the samples significantly influenced the grade estimation results. The IDWW method offers significant theoretical advantages and addresses the adverse effects of uneven sample lengths on the estimates. The IDWW method can effectively reduce the smoothing effect and improves the utilization efficiency of the original samples.

Rare-earth squarate frameworks with scu topology.

As a typical planar 4-connected ligand that possesses D4h symmetry, the squarate ligand is expected to construct some interesting topologies. Here, we report that the assembly of the squarate ligand with rare-earth ions can produce a series of (4, 8)-connected frameworks with the "smallest" scu type topology. Among these compounds, the Tb based analogue not only possesses a good proton conductivity, but also exhibits luminescence responses toward MnO4- and Cr2O72-, making it a candidate for multifunctional materials.