Chemical Composition Modulation Realizing Remarkable Improvement of Thermoelectric Performance in CuInTe2-Based Alloy.

CuInTe2 (CIT) is one of the typical ternary chalcogenides known for its characteristic mixed polyanionic/polycationic site defects, making it a subject of continuous interest in the field of thermoelectrics. In this work, we propose a chemical composition modulation strategy for CIT by alloying GeTe and then introducing a copper deficiency (denoted by VCu). This strategy aims to unpin its Fermi level (Fr) and shift Fr into the valence band (VB) while simultaneously enabling coupling between the optical and acoustic phonon, thereby providing an extra phonon scattering path at low frequencies. The simultaneous composition regulations not only enhance the carrier concentration (nH) to 1019-1020 cm-3 but also significantly reduce the lattice thermal conductivity (κL) to ∼0.48 W m-1 K-1, thus effectively realizing electro-acoustic coordination in the present material. As a consequence, the thermoelectric (TE) performance is remarkably improved with the highest TE figure of merit (ZT) of 1.51 at ∼838 K. This value ranks at a higher level among CIT-based materials, which showcases the great significance of chemical composition modulation.

Molecular composition and chemodiversity of dissolved organic matter in wastewater sludge via Fourier transform ion cyclotron resonance mass spectrometry: Effects of extraction methods and electrospray ionization modes.

High-resolution mass spectrometry was extensively applied in molecular composition and transformation pathways of dissolved organic matter (DOM) in wastewater sludge treatments. Sample pretreatment methods and electrospray ionization (ESI) modes significant affect the accuracy of molecular characterization for DOM. This study investigated the effects of pretreatment methods (styrene divinyl benzene polymer (PPL), octadecyl (C18), and electrodialysis (ED)) on molecular characteristics of DOM in two typical wastewater sludges (waste activated sludge (WAS) and anaerobic digestion sludge (ADS)) analyzed by FT-ICR MS in both positive ESI (ESI (+)) and negative ESI (ESI (-)) modes. The results indicated that ED pretreatment exhibited the highest recovery rate of 70% ‒ 95% for sludge-derived DOM. ED and PPL performed well in recovering the different sludge-derived DOM with a high similarity of molecular characteristics (e.g., lipids, proteins/aliphatic, and lignins/CRAM-like), and the C18 method was ineffective in extracting carbohydrates, unsaturated hydrocarbons, and amino sugars. In addition, compared with single ESI (-) analysis mode, the molecular number identified by ESI (+) analysis mode was increased by 200%, especially, more unsaturated hydrocarbons and N-containing compounds were detected. Except for biogenic DOM, plenty of emerging containments (ECs) in sludge-derived DOM were identified; ESI (-) mode was more effectively in recognizing the alkyl benzene sulfonic acids (e.g., anionic surfactants); and ESI (+) mode was more effectively for plasticizers identification, for example, dioctyl terephthalate and dibutyl phthalate. This study illustrated that ED pretreatment coupled with FT-ICR MS in dual ESI modes could give more insights in complexed molecular information for DOM in wastewater sludge, and provides a theoretical basis for subsequent sludge treatments and disposals.

Biostimulants in dissolved organic matters recovered from anaerobic digestion sludge with alkali-hydrothermal treatment: Nontarget identification by ultrahigh-resolution mass spectrometry.

Recovering high-value biomaterials from anaerobic digestion sludge (ADS) has attracted considerable attention. However, the molecular features and biological effects of abundant dissolved organic matters (DOMs) in ADS are still unclear, which limits the efficient recycling and application of these bioproducts. This study investigated the molecular composition and transformation of DOMs recovered from ADS through a mild-temperature alkali-hydrothermal treatment (AHT) with ultrahigh-resolution mass spectrometry and energy spectroscopy, and the fertilizing effects of DOMs were evaluated by rice hydroponics. The results indicated that AHT processes significantly promoted the solubilization and release of DOMs from ADS, where most of DOMs molecules remained unchanged and mainly consisted of N-containing compounds with 1-3 N atoms, featuring aromatic or N-heterocyclic rings. Furthermore, AHT processes at pH of 9-10 induced the hydrolysis of partial protein-like substances in DOMs, which was accompanied by formation of heterocyclic-N compounds. Under AHT at pH of 11-12, protein-like and heterocyclic-N substances were increasingly decomposed into amino-N compounds containing 1 or 5 N atoms, while numerous oxygenated aromatic substances with phytotoxicity were degraded and removed from DOMs. Rice hydroponic test verified that ADS-derived DOMs recovered by AHT process at pH of 12 exhibited the highest bioactivity for rice growth, which was attributed to the abundance of amino compounds and humic substances. This study proposed a novel process for the recovery of high-quality liquid organic fertilizer from ADS through AHT process, which can further enrich the technical options available for the safe utilization of sludge resources.

Band Structure and Phonon Transport Engineering Realizing Remarkable Improvement in Thermoelectric Performance of Cu2SnSe4 Incorporated with In2Te3.

Cu2SnSe4 (CTS) ternary chalcogenides have potential applications in thermoelectrics for they crystallize in a high-symmetry cubic structure and consist of earth-abundant and eco-friendly elements. However, the pristine CTS does not have optimal thermoelectric (TE) performance (ZT = 0.35 at ∼700 K), so further investigation is required in this regard. In this work, we propose an incorporation of In2Te3 with a defect zinc-blende cubic structure into CTS, aiming to regulate the electronic and phonon transport mechanism simultaneously. The first-principles calculation reveals that the element In favors the residing at a vacancy site as an interstitial atom while Te at the Se site, which leads to band convergence and degeneracy, respectively. As a result, the electrical property improves with a 22% increase in the power factor (PF), and at the same time, the lattice thermal conductivity (κL) reduces to 0.31 W K-1 m-1 at 718 K. Synergistic engineering realizes a remarkable improvement in TE performance with the highest figure of merit (ZT) of 0.92 at 718 K. This value is ∼3 times that of the pristine CTS and stands among the highest in the Cu2SnSe4 family so far, which proves that the incorporation of In2Te3 into CTS is a good proposal.

Improved Thermoelectric Performance of p-Type Argyrodite Cu8GeSe6 via the Simultaneous Engineering of the Electronic and Phonon Transports.

Guided by the concept of "phonon-liquid electron-crystal", many n-type argyrodite compounds have been developed as candidates for thermoelectric (TE) materials. In recent years, the p-type Cu8GeSe6 (CGS) compound has attracted some attention in TEs due to the presence of very strong atomic vibrational arharmonicity inside the sublattice, which is caused by the weak bonding between Cu ions and [GeSe6]8-. However, its TE performance is still poor, with a ZT value of only 0.2 at 623 K. Therefore, in this work, we propose to engineer both the electronic and phonon transports in CGS by incorporating the species In2Te3. This strategy tunes the carrier concentration and at the same time increases the phonon scattering on the point defects (InGe, Ininterstitial, and TeSe) and randomly distributed tetrahedra ([InSe4]5- and [GeTeSe3]4-). As a result, the phase transformation at 329 K in CGS is eliminated, and the peak ZT value is enhanced from 0.27 for CGS to ∼0.92 for (Cu8SnSe6)0.9(In2Te3)0.1 at 774 K; this thus proves that the incorporation of In2Te3 in CGS is an effective way of regulating its TE performance.

Improved Thermoelectric Performance of P-type SnTe through Synergistic Engineering of Electronic and Phonon Transports.

SnTe has been regarded as a potential alternative to PbTe in thermoelectrics because of its environmentally friendly features. However, it is a challenge to optimize its thermoelectric (TE) performance as it has an inherent high hole concentration (nH∼2 × 1020 cm-3) and low mobility (µH∼18 cm2 V-1 s-1) at room temperature (RT), arising from a high intrinsic Sn vacancy concentration and large energy separation between its light and heavy valence bands. Therefore, its TE figure of merit is only 0.38 at ∼900 K. Herein, both the electronic and phonon transports of SnTe were engineered by alloying species Ag0.5Bi0.5Se and ZnO in succession, thus increasing the Seebeck coefficient and, at the same time, reducing the thermal conductivity. As a result, the TE performance improves significantly with the peak ZT value of ∼1.2 at ∼870 K for the sample (SnGe0.03Te)0.9(Ag0.5Bi0.5Se)0.1 + 1.0 wt % ZnO. This result proves that synergistic engineering of the electronic and phonon transports in SnTe is a good approach to improve its TE performance.

Molecular composition and biotoxicity effects of dissolved organic matters in sludge-based carbon: Effects of pyrolysis temperature.

Sludge pyrolysis carbonization has shown potential to convert sludge biomass into multifunctional carbon materials. However, ecological risks of dissolved organic matters (DOMs) with obscure molecular characteristics retaining in sludge-based carbons (SBCs) have received little attention. This study investigated the impact of pyrolysis temperatures on the molecular conversion and biotoxicity effects of DOMs in SBCs. The results revealed that DOMs in SBCs300-400 were mainly derived from depolymerization of biopolymers and the polycondensation and cyclization of small intermediate molecules, which mainly consisted of aromatic CHON compounds with 1-3 N atoms, featuring high unsaturation and molecular weights. High-temperature pyrolysis (500-800 °C) promoted the decomposition and ring-opening of aromatic CHON compounds into saturated aliphatic CHO compounds with 2-4 O atoms in SBCs500-800. Noteworthily, SBCs300-400-derived DOMs showed relatively strong biotoxicity on the growth and development of wild-type zebrafish embryos, pakchoi seeds, and Vibrio qinghaiensis Q67, which was significantly related to aromatic amines, phenols, and heterocyclic-N compounds in DOMs of SBCs300-400. SBCs500-800-derived DOMs were mainly straight-chain fatty acids and showed no observable acute biotoxicity. This study highlights the negative impact of DOMs in SBCs on the ecological environment, and provides the theoretical basis for controlling toxic byproducts in sludge pyrolysis process.

Obtaining high-value nitrogen-containing carbon nanosheets with ultrahigh surface area from waste sludge for energy storage and wastewater treatment.

Recovering high value-added resources from waste activated sludge (WAS) is a potential way for the sustainable wastewater treatment. In this study, hydrothermal treatment at 180 °C was used to simultaneously improve sludge dewaterability and recover sludge organic matters (SOMs). The recovered SOMs were subsequently employed as precursors to prepare nitrogen-doped porous carbon nanosheets via a facile stepwise synthesis method. The as-prepared optimal carbon (AP-SOM800) was characterized with an ultrahigh specific surface area (3473 m2/g), appropriate porosity (1.77 cm3/g), and abundant heteroatoms (1.47% N and 7.44% O). AP-SOM800 exhibited a high specific capacitance (409 F/g at 0.25 A/g), low resistance (0.52 Ω), and superior cyclic stability (only 9.09% loss after 10,000 cycles) in 6 M KOH aqueous electrolyte. Furthermore, AP-SOM800 demonstrated an extraordinary adsorption capacity (1528 mg/g for methyl orange (MO) and 1265 mg/g for tetracycline (TC)) that can be maintained (˃ 1200 mg/g) over a wide range of pH conditions. Specifically, 80.97% of MO and 66.67% of TC were rapidly absorbed through AP-SOM800 within 10 min, and 90.27% of MO and 81.24% of TC were eventually removed from wastewater after 60 min. The adsorption processes fit closely with the pseudo-second-order kinetic (R2 > 0.999) and Langmuir models (R2 > 0.914), revealing that the adsorption processes were dominated by a monolayer chemical adsorption reaction. This study suggests that high value-added materials can be obtained from the WAS through improving and extending the traditional sludge treatment processes, which will enrich the technical options available for future sustainable sludge treatment and disposal.

Synergistic Optimization of the Electronic and Phonon Transports of N-Type Argyrodite Ag8Sn1-xGaxSe6 (x = 0-0.6) through Entropy Engineering.

The argyrodite compound, Ag8SnSe6 (ATS), which is one of the promising thermoelectric (TE) candidates, is receiving growing attention in thermoelectrics recently. However, its TE performance is still low and phases are unstable as the temperature varies. In this work, inspired by entropy engineering, we eliminate the ß/γ phase transformation at ∼355 K via alloying Ga, thus extending its high-temperature cubic phase from 320 to 730 K. In the meantime, the power factor (PF) enhances by 10% and lattice thermal conductivity (κL) reduces by 40% at 723 K. As a result, the ZT value is boosted to ∼1.15 for Ag8Sn0.5Ga0.5Se6, which stands high among the ATS systems. This proves that the entropy engineering is an effective approach to extend the high-temperature range for the cubic γ-phase and improve its TE performance simultaneously.

Mechanistic insights into the effects of biopolymer conversion on macroscopic physical properties of waste activated sludge during hydrothermal treatment: Importance of the Maillard reaction.

In this study, the molecular transformation of sludge biopolymers during hydrothermal treatment with the temperature ranging from 25 °C to 200 °C was examined and was seen to significantly affect the macrophysical properties (dewaterability and rheological property) of sludge. The results showed that the sludge dewaterability and flow ability under high shear stress deteriorated by a hydrothermal process at 25 °C to 120 °C, but the deterioration alleviated above the temperature threshold of 120 °C. The consistence of changes in sludge dewaterability and rheological property in HT process was mainly attributed to the variation in gel properties of soluble biopolymer. Two-stage changes in biopolymer transformation were identified, beginning with a solubilization stage from 25 °C to 120 °C in which a biopolymer with a gel-like network structure was released into liquid phase, creating flow resistance under high shear stress such that sludge dewaterability deteriorated. The second stage was identified as a conversion stage (120 °C-200 °C) in which proteins and polysaccharides hydrolyzed and experienced a Maillard reaction, leading to the degradation of the biopolymer network structure. The newly formed recalcitrant Maillard products showed weak flow response to high shear stress, allowing for an improvement in sludge dewaterability. The pathways of a Maillard reaction were identified via gas chromatography-mass spectrometer (GC-MS), 1H nuclear magnetic resonance spectroscopy (1H NMR) and two-dimensional correlation spectral analysis (2D-COS) of Fourier-transform infrared spectrometer (FTIR), etc. Three-dimensional excitation-emission matrix (3D-EEM) proved to be an applicable method for tracking Maillard reaction in sludge hydrothermal process due to the distinctive fluorescence characteristics of Maillard products. This study further clarifies the obscure process of sludge hydrothermal treatment and will help improve the accuracy of subsequent research.

Improved thermoelectric performance of solid solution Cu4Sn7.5S16 through isoelectronic substitution of Se for S.

Cu-Sn-S family of compounds have been considered as very competitive thermoelectric candidates in recent years due to their abundance and eco-friendliness. The first-principles calculation reveals that the density of states (DOS) increases in the vicinity of the Fermi level (Ef) upon an incorporation of Se in the Cu4Sn7.5S16-xSe x (x = 0-2.0) system, which indicates the occurrence of resonant states. Besides, the formation of Cu(Sn)-Se network upon the occupation of Se in S site reduces the Debye temperature from 395 K for Cu4Sn7S16 (x = 0) to 180.8 K for Cu4Sn7.5S16-xSe x (x = 1.0). Although the point defects mainly impact the phonon scattering, an electron-phonon interaction also bears significance in the increase in phonon scattering and the further reducion of lattice thermal conductivity at high temperatures. As a consequence, the resultant TE figure of merit (ZT) reaches 0.5 at 873 K, which is 25% higher compared to 0.4 for Cu4Sn7.5S16.

Unequal bonding in Ag-CuIn3Se5-based solid solutions responsible for reduction in lattice thermal conductivity and improvement in thermoelectric performance.

Owing to their unique crystal and band structures, in thermoelectrics increasing attention has recently been paid to compounds of the ternary I-III-VI chalcopyrite family. In this work, unequal bonding between cation and anion pairs in Cu1-y Ag y In3Se4.9Te0.1 solid solutions, which can be effectively used to disturb phonon transport, has been proposed. The unequal bonding, which is represented by the difference of bond lengths Δd, Δd = d (Cu-Se) - d (In-Se) and anion position displacement from its equilibrium position Δu = u - 0.25, is created by the isoelectronic substitution of Ag for Cu. At y = 0.2 both the Δd and Δu values reach their maxima, resulting in a remarkable reduction in lattice thermal conductivity (κ L) and an improvement in TE performance. However, as the y value increase to 0.3 both Δd and Δu values decrease, causing the κ L value to increase and the ZT value to decrease from 0.5 to 0.24 at 930 K. Accordingly, unequal bonding might be an alternative way to improve the TE performance of ternary chalcopyrites.

Enhanced thermoelectric performance of a chalcopyrite compound CuIn3Se5-xTex (x = 0~0.5) through crystal structure engineering.

In this work the chalcopyrite CuIn3Se5-xTex (x = 0~0.5) with space group through isoelectronic substitution of Te for Se have been prepared, and the crystal structure dilation has been observed with increasing Te content. This substitution allows the anion position displacement ∆u = 0.25-u to be zero at x ≈ 0.15. However, the material at x = 0.1 (∆u = 0.15 × 10-3), which is the critical Te content, presents the best thermoelectric (TE) performance with dimensionless figure of merit ZT = 0.4 at 930 K. As x value increases from 0.1, the quality factor B, which informs about how large a ZT can be expected for any given material, decreases, and the TE performance degrades gradually due to the reduction in nH and enhancement in κL. Combining with the ZTs from several chalcopyrite compounds, it is believable that the best thermoelectric performance can be achieved at a certain ∆u value (∆u ≠ 0) for a specific space group if their crystal structures can be engineered.

Engineering Band Structure via the Site Preference of Pb(2+) in the In(+) Site for Enhanced Thermoelectric Performance of In6Se7.

Although binary In-Se based alloys have in recent years gained interest as thermoelectric (TE) candidates, little attention has been paid to In6Se7-based compounds. Substituting Pb in In6Se7, preference for Pb(2+) in the In(+) site has been observed, allowing Fermi level (Fr) shift toward the conduction band, where the localized state conduction becomes dominant. Consequently, the Hall carrier concentration (nH) has been significantly enhanced with the highest nH value being about 2-3 orders of magnitude higher than that of the Pb-free sample. Meanwhile, the lattice thermal conductivity (κL) tends to be reduced as the nH value increases, owing to an increased phonon scattering on carriers. As a result, a significantly enhanced TE performance has been achieved with the highest TE figure of merit (ZT) of 0.4 at ∼850 K. This ZT value is 27 times that of intrinsic In6Se7 (ZT = 0.015 at 640 K), which proves a successful band structure engineering through site preference of Pb in In6Se7.

Lattice defects and thermoelectric properties: the case of p-type CuInTe2 chalcopyrite on introduction of zinc.

I-III-VI2 chalcopyrites have unique inherent crystal structure defects, and hence are potential candidates for thermoelectric materials. Here, we identified mixed polyanionic/polycationic site defects (ZnIn(-), VCu(-), InCu(2+) and/or ZnCu(+)) upon Zn substitution for either Cu or In or both in CuInTe2, with the ZnIn(-) species originating from the preference of Zn for the cation 4b site. Because of the mutual reactions among these charged defects, Zn substitution in CuInTe2 alters the basic conducting mechanism, and simultaneously changes the lattice structure. The alteration of the lattice structure can be embodied in an increased anion position displacement (u) or a reduced bond length difference (Δd) between d(Cu-Te)4a and d(In-Te)4b with increasing Zn content. Because of this, the lattice distortion is diminished and the lattice thermal conductivity (κL) is enhanced. The material with simultaneous Zn substitution for both Cu and In had a low κL, thereby we attained the highest ZT value of 0.69 at 737 K, which is 1.65 times that of Zn-free CuInTe2.