Effective remediation of agricultural drainage at three influent strengths by bioaugmented constructed wetlands filled with mixture of iron­carbon and organic solid substrates: Performance and mechanisms.

Agricultural drainage containing a large quantity of nutrients can cause quality deterioration and algal blooming of receiving water bodies, thus needs to be effectively remediated. In this study, iron­carbon (FeC) composite-filled constructed wetlands (Fe-C-CWs) were employed to treat farmland drainage at three pollution levels, and organic solid substrates (walnut shells) and phosphate-accumulating denitrifying bacteria (Pseudomonas sp. DWP1) were supplemented to enhance the treatment performance. The results showed that the Fe-C-CWs exhibited notably superior removal efficiency for total nitrogen (TN, 52.0-58.2 %), total phosphorus (TP, 67.8-70.2 %) and chemical oxygen demand (COD, 56.7-70.4 %) than the control systems filled solely with gravel (28.5-32.5 % for TN, 33.2-40.5 % for TP and 30.2-55.0 % for COD) at all influent strengths, through driving autotrophic denitrification, Fe-based dephosphorization, and organic degradation processes. The addition of organic substrates and functional bacteria markedly enhanced pollutant removal in the Fe-C-CWs. Furthermore, use of FeC and organic substrates and denitrifier inoculation decreased CO2 and CH4 emissions from the CWs, and reduced global warming potential of the CWs at low influent strength. Pollutant removal efficiencies in the CWs were only marginally impacted by the increasing influent loads except for NO3--N, and pollutant removal mass was largely increased with the increase of influent strengths. The microbial community in the FeC composite-filled CWs exhibited distinct distribution patterns compared to the gravel-filled CWs regardless of the influent strengths, with obviously higher proportions of dominant genera Trichococcus, Geobacter and Ferritrophicum. Keystone taxa associated with pollutant removal in the Fe-C-filled CWs were identified to be Pseudomonas, Geobacter, Ferritrophicum, Denitratisoma and Sediminibacterium. The developed augmented Fe-C-filled CWs show great promises for remediating agricultural drainage with varied pollutant loads.

Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites.

Metal-based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X-ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure-activity relationships of low-crystalline cobalt sulfide (L-CoS) catalysts toward overall water splitting. The operando results for L-CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S-Co-Co-S moieties as the true catalytically active species. In comparison, during the acidic HER, L-CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co-S-Co configurations. Further operando characterizations highlight the crucial formation of high-valent Co4+ species in L-CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co-LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Tailoring C─N Containing Compounds into Carbon Nanomaterials with Tunable Morphologies for Electrocatalytic Applications.

Carbon materials with unique sp2 -hybridization are extensively researched for catalytic applications due to their excellent conductivity and tunable physicochemical properties. However, the development of economic approaches to tailoring carbon materials into desired morphologies remains a challenge. Herein, a convenient "bottom-up" strategy by pyrolysis of graphitic carbon nitride (g-C3 N4 ) (or other carbon/nitrogen (C, N)-enriched compounds) together with selected metal salts and molecules is reported for the construction of different carbon-based catalysts with tunable morphologies, including carbon nano-balls, carbon nanotubes, nitrogen/sulfur (S, N) doped-carbon nanosheets, and single-atom catalysts, supported by carbon layers. The catalysts are systematically investigated through various microscopic, spectroscopic, and diffraction methods and they demonstrate promising and broad applications in electrocatalysis such as in the oxygen reduction reaction and water splitting. Mechanistic monitoring of the synthesis process through online thermogravimetric-gas chromatography-mass spectrometry measurements indicates that the release of C─N-related moieties, such as dicyan, plays a key role in the growth of carbon products. This enables to successfully predict other widely available precursor compounds beyond g-C3 N4 such as caffeine, melamine, and urea. This work develops a novel and economic strategy to generate morphologically diverse carbon-based catalysts and provides new, essential insights into the growth mechanism of carbon nanomaterials syntheses.

Built-In Electric Field-Driven Ultrahigh-Rate K-Ion Storage via Heterostructure Engineering of Dual Tellurides Integrated with Ti3C2Tx MXene.

Exploiting high-rate anode materials with fast K+ diffusion is intriguing for the development of advanced potassium-ion batteries (KIBs) but remains unrealized. Here, heterostructure engineering is proposed to construct the dual transition metal tellurides (CoTe2/ZnTe), which are anchored onto two-dimensional (2D) Ti3C2Tx MXene nanosheets. Various theoretical modeling and experimental findings reveal that heterostructure engineering can regulate the electronic structures of CoTe2/ZnTe interfaces, improving K+ diffusion and adsorption. In addition, the different work functions between CoTe2/ZnTe induce a robust built-in electric field at the CoTe2/ZnTe interface, providing a strong driving force to facilitate charge transport. Moreover, the conductive and elastic Ti3C2Tx can effectively promote electrode conductivity and alleviate the volume change of CoTe2/ZnTe heterostructures upon cycling. Owing to these merits, the resulting CoTe2/ZnTe/Ti3C2Tx (CZT) exhibit excellent rate capability (137.0 mAh g-1 at 10 A g-1) and cycling stability (175.3 mAh g-1 after 4000 cycles at 3.0 A g-1, with a high capacity retention of 89.4%). More impressively, the CZT-based full cells demonstrate high energy density (220.2 Wh kg-1) and power density (837.2 W kg-1). This work provides a general and effective strategy by integrating heterostructure engineering and 2D material nanocompositing for designing advanced high-rate anode materials for next-generation KIBs.

Agricultural runoff treatment by constructed wetlands filled with iron-carbon composites in winter: Performance augmentation by organic solids and denitrifying bacteria addition.

Iron-carbon composite-filled constructed wetlands (Fe-C CWs) were employed to treat agricultural runoff in the winter season in this study, and organic substrates and phosphate-accumulating denitrifying bacteria were supplemented to improve the treatment performance. Fe-C CWs performed significantly better in pollutant removal than the control system filled with only gravel by effectively driving autotrophic denitrification, Fe-based dephosphorization and organic degradation. Organic substrate and functional bacteria addition further augmented the performance, and immobilized bacterial cells were more effective than free cells. Fe-C and organic substrates decreased the greenhouse gas emission fluxes of the CWs, and denitrifier inoculation alleviated N2O emission. The microbial community in the Fe-C substrates showed a very distinct distribution pattern compared to that in the gravel, with notably higher proportions of Trichococcus, Thauera and Dechloromonas. Bioaugmented Fe-C-based CWs are highly promising for agricultural runoff treatment, especially at low temperatures.

Oxygen Evolution/Reduction Reaction Catalysts: From In Situ Monitoring and Reaction Mechanisms to Rational Design.

The oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are core steps of various energy conversion and storage systems. However, their sluggish reaction kinetics, i.e., the demanding multielectron transfer processes, still render OER/ORR catalysts less efficient for practical applications. Moreover, the complexity of the catalyst-electrolyte interface makes a comprehensive understanding of the intrinsic OER/ORR mechanisms challenging. Fortunately, recent advances of in situ/operando characterization techniques have facilitated the kinetic monitoring of catalysts under reaction conditions. Here we provide selected highlights of recent in situ/operando mechanistic studies of OER/ORR catalysts with the main emphasis placed on heterogeneous systems (primarily discussing first-row transition metals which operate under basic conditions), followed by a brief outlook on molecular catalysts. Key sections in this review are focused on determination of the true active species, identification of the active sites, and monitoring of the reactive intermediates. For in-depth insights into the above factors, a short overview of the metrics for accurate characterizations of OER/ORR catalysts is provided. A combination of the obtained time-resolved reaction information and reliable activity data will then guide the rational design of new catalysts. Strategies such as optimizing the restructuring process as well as overcoming the adsorption-energy scaling relations will be discussed. Finally, pending current challenges and prospects toward the understanding and development of efficient heterogeneous catalysts and selected homogeneous catalysts are presented.

Optimized NiFe-Based Coordination Polymer Catalysts: Sulfur-Tuning and Operando Monitoring of Water Oxidation.

In-depth insights into the structure-activity relationships and complex reaction mechanisms of oxygen evolution reaction (OER) electrocatalysts are indispensable to efficiently generate clean hydrogen through water electrolysis. We introduce a convenient and effective sulfur heteroatom tuning strategy to optimize the performance of active Ni and Fe centers embedded into coordination polymer (CP) catalysts. Operando monitoring then provided the mechanistic understanding as to how exactly our facile sulfur engineering of Ni/Fe-CPs optimizes the local electronic structure of their active centers to facilitate dioxygen formation. The high OER activity of our optimized S-R-NiFe-CPs outperforms the most recent NiFe-based OER electrocatalysts. Specifically, we start from oxygen-deprived Od-R-NiFe-CPs and transform them into highly active Ni/Fe-CPs with tailored sulfur coordination environments and anionic deficiencies. Our operando X-ray absorption spectroscopy analyses reveal that sulfur introduction into our designed S-R-NiFe-CPs facilitates the formation of crucial highly oxidized Ni4+ and Fe4+ species, which generate oxygen-bridged NiIV-O-FeIV moieties that act as the true OER active intermediates. The advantage of our sulfur-doping strategy for enhanced OER is evident from comparison with sulfur-free Od-R-NiFe-CPs, where the formation of essential high-valent OER intermediates is hindered. Moreover, we propose a dual-site mechanism pathway, which is backed up with a combination of pH-dependent performance data and DFT calculations. Computational results support the benefits of sulfur modulation, where a lower energy barrier enables O-O bond formation atop the S-NiIV-O-FeIV-O moieties. Our convenient anionic tuning strategy facilitates the formation of active oxygen-bridged metal motifs and can thus promote the design of flexible and low-cost OER electrocatalysts.

Community assembly during vegetation succession after metal mining is driven by multiple processes with temporal variation.

The mechanisms governing community assembly is fundamental to ecological restoration and clarification of the assembly processes associated with severe disturbances (characterized by no biological legacy and serious environmental problems) is essential. However, a systematic understanding of community assembly in the context of severe anthropogenic disturbance remains lacking. Here, we explored community assembly processes after metal mining, which is considered to be a highly destructive activity to provide insight into the assembly rules associated with severe anthropogenic disturbance. Using a chronosequence approach, we selected vegetation patches representing different successional stages and collected data on eight plant functional traits from each stage. The traits were classified as establishment and regenerative traits. Based on these traits, null models were constructed to identify the processes driving assembly at various successional stages. Comparison of our observations with the null models indicated that establishment and regenerative traits converged in the primary stage of succession. As succession progressed, establishment traits shifted to neutral assembly, whereas regeneration traits alternately converged and diverged. The observed establishment traits were equal to expected values, whereas regenerative traits diverged significantly after more than 20 years of succession. Furthermore, the available Cr content was linked strongly to species' ecological strategies. In the initial stages of vegetation succession in an abandoned metal mine, the plant community was mainly affected by the available metal content and dispersal limitation. It was probably further affected by strong interspecific interaction after the environmental conditions had improved, and stochastic processes became dominant during the stage with a successional age of more than 20 years.

Dynamics and control of active sites in hierarchically nanostructured cobalt phosphide/chalcogenide-based electrocatalysts for water splitting.

The rational design of efficient electrocatalysts for industrial water splitting is essential to generate sustainable hydrogen fuel. However, a comprehensive understanding of the complex catalytic mechanisms under harsh reaction conditions remains a major challenge. We apply a self-templated strategy to introduce hierarchically nanostructured "all-surface" Fe-doped cobalt phosphide nanoboxes (Co@CoFe-P NBs) as alternative electrocatalysts for industrial-scale applications. Operando Raman spectroscopy and X-ray absorption spectroscopy (XAS) experiments were carried out to track the dynamics of their structural reconstruction and the real catalytically active intermediates during water splitting. Our operando analyses reveal that partial Fe substitution in cobalt phosphides promotes a structural reconstruction into P-Co-O-Fe-P configurations with low-valence metal centers (M0/M+) during the hydrogen evolution reaction (HER). Results from density functional theory (DFT) demonstrate that these in situ reconstructed configurations significantly enhance the HER performance by lowering the energy barrier for water dissociation and by facilitating the adsorption/desorption of HER intermediates (H*). The competitive activity in the oxygen evolution reaction (OER) arises from the transformation of the reconstructed P-Co-O-Fe-P configurations into oxygen-bridged, high-valence CoIV-O-FeIV moieties as true active intermediates. In sharp contrast, the formation of such CoIII/IV-O-FeIII/IV moieties in Co-FeOOH is hindered under the same conditions, which outlines the key advantages of phosphide-based electrocatalysts. Ex situ studies of the as-synthesized reference cobalt sulfides (Co-S), Fe doped cobalt selenides (Co@CoFe-Se), and Fe doped cobalt tellurides (Co@CoFe-Te) further corroborate the observed structural transformations. These insights are vital to systematically exploit the intrinsic catalytic mechanisms of non-oxide, low-cost, and robust overall water splitting electrocatalysts for future energy conversion and storage.

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts.

Single-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm-2. We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O2 atop the Ni-O-Fe sites.

Effects of norfloxacin on decomposition and nutrient release in leaves of the submerged macrophyte Vallisneria natans (Lour.) Hara.

It is well known that antibiotic residuals affect the composition and structure of microbial communities. However, the consequences of these biological changes in terms of ecosystem function remain poorly understood, particularly in aquatic ecosystems. Here, we investigated the impacts of norfloxacin (NOR, 0, 0.5, and 8 mg L-1), a widely used antibiotic, on the microbial community structure on leaf surfaces of the submerged macrophyte Vallisneria natans, and the corresponding variations in litter decomposition, litter nutrient release, and water properties. Results showed that after 40 days of exposure, bacterial richness consistently decreased with increasing NOR concentration, and that richness of fungi was significantly lower in treatments adding NOR than in the control treatment. Moreover, NOR shifted the community toward NOR resistant phyla and genera, especially in the bacteria community. These community shifts resulted in the inhibition of litter decomposition and nutrient release from leaf litter to system water, accompanied by increases in dissolved oxygen concentration and pH of system water. Our results indicate that, by affecting microbial communities, NOR had significant effects on litter decomposition, litter nutrient release, and water properties, highlighting the potential harmful effects of NOR on aquatic ecosystem function.

Reaction kinetics and interplay of two different surface states on hematite photoanodes for water oxidation.

Understanding the function of surface states on photoanodes is crucial for unraveling the underlying reaction mechanisms of water oxidation. For hematite photoanodes, only one type of surface states with higher oxidative energy (S1) has been proposed and verified as reaction intermediate, while the other surface state located at lower potentials (S2) was assigned to inactive or recombination sites. Through employing rate law analyses and systematical (photo)electrochemical characterizations, here we show that S2 is an active reaction intermediate for water oxidation as well. Furthermore, we demonstrate that the reaction kinetics and dynamic interactions of both S1 and S2 depend significantly on operational parameters, such as illumination intensity, nature of the electrolyte, and applied potential. These insights into the individual reaction kinetics and the interplay of both surface states are decisive for designing efficient photoanodes.

Long-term effect of sediment on the performance of a pilot-scale duckweed-based waste stabilization pond.

Duckweed-based waste stabilization ponds (DWPs) have been widely used in wastewater treatment. However, the effects of sediment, an essential component of DWPs, on their performance have rarely been studied. In this study, two pilot-scale DWPs (12 m2) with sediment (DPS) and without sediment (DP) were evaluated over more than 1 year to determine the effects of sediment on duckweed growth, wastewater treatment, and greenhouse gas (GHG) production and emission in DWPs. The results indicated that the annual average duckweed growth rate were comparable, but protein content, carbon (C) and nitrogen (N) recovery rates of duckweed were slightly higher in the DPS than in the DP. Meanwhile, the dissolved oxygen (DO) and oxidation reduction potential (ORP), removal efficiencies of COD, TP, TN, NH4+-N, and turbidity of pond water from the DPS were significantly lower than for DP. More importantly, the DPS had considerably higher CH4 production/emission and global warming potential (GWP) than the DP, even though more than 90% of CH4 released from the sediment was consumed during its passage through the water column and duckweed layer. Sediment increased the recoveries of C and N by 7.94% and 8.82%, respectively. Influencing degree for COD, TP, TN, NH4+-N and turbidity were -27.92%, -20.98%, -22.61%, -24.13% and -14.91%, respectively; for pond water DO and ORP, the values were - 35.68% and -44.59%, respectively; and for CO2, CH4 and N2O emission and "combined GWP", they were 21.66%, 271.67%, -8.47% and 178.02%, respectively. Thus, this study indicates that sediment formed in the DWPs has a multi-faced effect on the performance of a DWP. In particular, sediment has an unfavourable effect on the wastewater treatment and the GHGs mitigation, but a favourable effect on the protein content and the C and N recoveries in duckweed.

Bifunctional Single Atom Electrocatalysts: Coordination-Performance Correlations and Reaction Pathways.

Single atom catalysts (SACs) are ideal model systems in catalysis research. Here we employ SACs to address the fundamental catalytic challenge of generating well-defined active metal centers to elucidate their interactions with coordinating atoms, which define their catalytic performance. We introduce a soft-landing molecular strategy for tailored SACs based on metal phthalocyanines (MPcs, M = Ni, Co, Fe) on graphene oxide (GO) layers to generate well-defined model targets for mechanistic studies. The formation of electronic channels through π-π conjugation with the graphene sheets enhances the MPc-GO performance in both oxygen evolution and reduction reactions (OER and ORR). Density functional theory (DFT) calculations unravel that the outstanding ORR activity of FePc-GO among the series is due to the high affinity of Fe atoms toward O2 species. Operando X-ray absorption spectroscopy and DFT studies demonstrate that the OER performance of the catalysts relates to thermodynamic or kinetic control at low- or high-potential ranges, respectively. We furthermore provide evidence that the participation of ligating N and C atoms around the metal centers provides a wider selection of active OER sites for both NiPc-GO and CoPc-GO. Our strategy promotes the understanding of coordination-activity relationships of high-performance SACs and their optimization for different processes through tailored combinations of metal centers and suitable ligand environments.

Pollutant removal from agricultural drainage water using a novel double-layer ditch with biofilm carriers.

Agricultural drainage ditches can prevent flooding and mitigate agricultural pollution; however, the performance is unsatisfactory in plateau areas like the Dianchi Lake basin. Thus, a novel double-layer ditch system (DDS) with a fibrous packing as biofilm carriers was developed to form the carrier-attached biofilms and enhance the pollutant removal. The results indicated the DDS performed better than a single-layer ditch system, and annual average removal efficiencies of TN, NO3--N, NH4+-N, TP, COD and SS were 18.61%, 17.13%, 7.74%, 11.90%, 11.95% and 23.71%, respectively. High amount and carbon, nitrogen and phosphorus contents of biofilms are favourable to pollutant removal by DDS. Although bacterial diversity of biofilms remained relatively stable throughout the year, the relative abundance of dominant assemblages varied greatly. Denitrifying microorganisms affiliated with Bacteroidetes might contribute to effective NO3--N reduction. This study demonstrates DDS performed well and provides a novel method for application of biofilm carriers in drainage ditches.

Microbial community succession and pollutants removal of a novel carriers enhanced duckweed treatment system for rural wastewater in Dianchi Lake basin.

Carriers strengthened duckweed treatment system (CDW), duckweed treatment system (DW) and water hyacinth treatment system (WH) were developed to treat rural wastewater in Dianchi Lake basin. Results showed that adding microbial carrier did not affect the growth and biomass components of duckweed. The following features were discovered in the CDW system. First, the NO3--N and TN removal efficiencies were the highest among three systems, reaching 80.02% and 56.42%, respectively. Secondly, Illumina sequencing revealed the highest microbial diversity. Thirdly, a distinct succession of microbial community was observed. Rhodobacter, Bacteria vadinCA02, C39 and Flavobacterium dominated in the start-up stage, and contributed to biofilm formation and pollutants degradation. Acinetobacter, Planctomyces and Methylibium significantly increased in the stable stage, and contributed to nitrogen removal. Finally, highly abundant plant growth-promoting bacteria were found. Comprehensive analysis indicated that the functional bacteria community was closely related to the pollutant removals, plant growth and system operating status.

Duckweed systems for eutrophic water purification through converting wastewater nutrients to high-starch biomass: comparative evaluation of three different genera (Spirodela polyrhiza, Lemna minor and Landoltia punctata) in monoculture or polyculture.

The polyculture of different duckweed species is likely to integrate their advantages in removing pollutants and starch accumulation. Here, pilot-scale comparisons of three duckweed species (Spirodela polyrhiza K1, Lemna minor K2 and Landoltia punctata K3) in monoculture and polyculture were investigated. Results showed that the TN (total nitrogen) and TP (total phosphorus) in wastewater decreased from 6.0 and 0.56 mg L-1 to below 0.5 and 0.1 mg L-1, respectively. Namely, the water quality improved to Grade II under the Chinese standard. The highest TN and TP removal efficiencies were found to be 99.1% and 90.8% in the polyculture. Besides, the starch content of S. polyrhiza K1, L. minor K2, L. punctata K3 and the polyculture reached 24.8%, 32.3%, 39.3% and 36.3%, respectively. Accordingly, their average starch accumulation rates were 1.65, 2.15, 3.11 and 2.72 g m-2 d-1, respectively. Our results suggested that L. punctata K3 was a promising energy feedstock due to it having the highest starch production. The advantages of different duckweed species were investigated. In the polyculture, the pollutants were efficiently removed from wastewater, with a high starch accumulation. This study supplies a new insight into the application of duckweed in eutrophic water advanced treatment coupled with starch production.

New microbial resource: microbial diversity, function and dynamics in Chinese liquor starter.

Traditional Chinese liquor (Baijiu) solid state fermentation technology has lasted for several thousand years. The microbial communities that enrich in liquor starter are important for fermentation. However, the microbial communities are still under-characterized. In this study, 454 pyrosequencing technology was applied to comprehensively analyze the microbial diversity, function and dynamics of two most-consumed liquor starters (Jiang- and Nong-flavor) during production. In total, 315 and 83 bacterial genera and 72 and 47 fungal genera were identified in Jiang- and Nong-flavor liquor starter, respectively. The relatively high diversity was observed when the temperature increased to 70 and 62 °C for Jiang- and Nong-flavor liquor starter, respectively. Some thermophilic fungi have already been isolated. Microbial communities that might contribute to ethanol fermentation, saccharification and flavor development were identified and shown to be core communities in correlation-based network analysis. The predictively functional profile of bacterial communities showed significant difference in energy, carbohydrate and amino acid metabolism and the degradation of aromatic compounds between the two kinds of liquor starters. Here we report these liquor starters as a new functionally microbial resource, which can be used for discovering thermophilic and aerobic enzymes and for food and feed preservation.

Influence of Ta substitution for Nb in Zn3Nb2O8 and the impact on the crystal structure and microwave dielectric properties.

Zn3(Nb1-xTax)2O8 (x = 0.02-0.10) ceramics were prepared via a solid-state reaction route and the dependence of their microwave dielectric properties on their structural characteristics were investigated. XRD patterns show that a single Zn3Nb2O8 phase with layered crystal structures was formed in ceramic samples with 0.02 ≤x≤ 0.10. The Raman spectrum was used for the first time to analyze the vibrational phonon modes of the Zn3Nb2O8 samples. Based on P-V-L dielectric theory, the intrinsic factors that influence the microwave dielectric properties were systematically investigated. According to the calculated results, the experimental dielectric constant had a close relationship with the theoretical dielectric constant. The Nb-site lattice energy was found to be a vital factor in explaining the change of the Q×f values. While the Nb-site bond energy increases, the |τf| value decreases which indicates that higher bond energy would result in a more stable system. This work presents a novel method to investigate the intrinsic factors that influence microwave dielectric properties.

Bond ionicity, lattice energy, bond energy and microwave dielectric properties of ZnZr(Nb1-xAx)2O8 (A = Ta, Sb) ceramics.

The dependence of microwave dielectric properties on the structural characteristics of ZnZr(Nb1-xAx)2O8 (A = Ta, Sb) (0 ≤x≤ 0.10) ceramics is investigated. All the compounds were prepared by a conventional solid-state reaction method and analyzed via multiphase structure refinement. The diffraction patterns of ZnZr(Nb1-xAx)2O8 (A = Ta, Sb) show the monoclinic wolframite structure of ZrZrNb2O8 which consists of an oxygen octahedron, with the Nb ion in the center of the oxygen octahedron. For the ZnZr(Nb1-xAx)2O8 (A = Ta, Sb) ceramics, the dielectric constant (εr) decreased with the decrease in Nb-site bond ionicity. The quality factor (Q×f) of ZnZr(Nb1-xSbx)2O8 ceramics was found to be the highest (89 400 GHz), which is explained in terms of the average of the Nb-site lattice energy. With the decrease in the bond energy of the Nb-site, the temperature coefficient of resonant frequency (|τf|) value increased. The substitution of A(5+) (A = Ta, Sb) for Nb(5+) effectively influences the microstructure and microwave dielectric properties of ZrZrNb2O8 ceramics.