Sequential Water Sorption/Desorption of a Nonporous Adaptive Organic Ligand Bridged Coordination Polymer for Atmospheric Moisture Harvesting.

Moisture harvesters with favourable attributes such as easy synthetic availability and good processability as alternatives for atmospheric moisture harvesting (AWH) are desirable. This study reports a novel nonporous anionic coordination polymer (CP) of uranyl squarate with methyl viologen (MV2+ ) as charge balancing ions (named U-Squ-CP) which displays intriguing sequential water sorption/desorption behavior as the relative humidity (RH) changes gradually. The evaluation of AWH performance of U-Squ-CP shows that it can absorb water vapor under air atmosphere at a low RH of 20 % typical of the levels found in most dry regions of the world, and have good cycling durability, thus demonstrating the capability as a potential moisture harvester for AWH. To the authors' knowledge, this is the first report on non-porous organic ligand bridged CP materials for AWH. Moreover, a stepwise water-filling mechanism for the water sorption/desorption process is deciphered by comprehensive characterizations combining single-crystal diffraction, which provides a reasonable explanation for the special moisture harvesting behaviour of this non-porous crystalline material.

Colossal negative thermal expansion in a cucurbit[8]uril-enabled uranyl-organic polythreading framework via thermally induced relaxation.

It is an ongoing goal to achieve the effective regulation of the thermal expansion properties of materials. In this work, we propose a method for incorporating host-guest complexation into a framework structure and construct a flexible cucurbit[8]uril uranyl-organic polythreading framework, U3(bcbpy)3(CB8). U3(bcbpy)3(CB8) can undergo huge negative thermal expansion (NTE) and has a large volumetric coefficient of -962.9 × 10-6 K-1 within the temperature range of 260 K to 300 K. Crystallographic snapshots of the polythreading framework at various temperatures reveal that, different from the intrinsic transverse vibrations of the subunits of metal-organic frameworks (MOFs) that experience NTE via a well-known hinging model, the remarkable NTE effect observed here is the result of a newly-proposed thermally induced relaxation process. During this process, an extreme spring-like contraction of the flexible CB8-based pseudorotaxane units, with an onset temperature of ∼260 K, follows a period of cumulative expansion. More interestingly, compared with MOFs that commonly have relatively strong coordination bonds, due to the difference in the structural flexibility and adaptivity of the weakly bonded U3(bcbpy)3(CB8) polythreading framework, U3(bcbpy)3(CB8) shows unique time-dependent structural dynamics related to the relaxation process, the first time this has been reported in NTE materials. This work provides a feasible pathway for exploring new NTE mechanisms by using tailored supramolecular host-guest complexes with high structural flexibility and has promise for the design of new kinds of functional metal-organic materials with controllable thermal responsive behaviour.

Fabrication of an in situ-grown TiO2 nanowire thin film and its enhanced photocatalytic activity.

TiO2 is a promising photocatalyst used in practical environmental remediation. TiO2 photocatalysts are usually implemented in two forms: suspended powder and immobilized thin films. A simple technique for fabricating TiO2 thin film photocatalyst was developed in this work. The fabricated TiO2 thin film photocatalyst featured a homogeneous nanowire layer grown in situ on the parent Ti plate. The optimized fabrication protocol was to soak the ultrasonically cleaned and acid-washed Ti plate in 30% H2O2 solution containing 3.2 mM melamine and 0.29 M HNO3 at 80 °C for 72 h and then anneal at 450 °C for 1 h. TiO2 nanowires with uniform diameters were homogeneously arrayed on the Ti plate surface. The thickness of the TiO2 nanowire array layer was 1.5 µm. The pore properties of the TiO2 thin film were close to those of P25. The band gap of the fabricated photocatalyst was 3.14 eV. The photocatalytic activity of the fabricated photocatalyst toward 10 mg/L RhB and 1 mg/L CBZ demonstrated greater than 60% degradation under 2 h UVC irradiation. The RhB and CBZ degradation efficiencies remained at a good level after 5 consecutive cycles. Mechanical wearing, such as 2 min sonication, will not lead to significant suppression of the photocatalytic activity. Photocatalytic RhB and CBZ degradation using the fabricated photocatalyst favored an acidic > alkaline > neutral environment. The presence of Cl- slightly suppressed the photocatalytic degradation kinetics. However, RhB and CBZ photocatalytic degradation kinetics were promoted in the copresence of SO42- or NO3-.

Modular Assembly of Isostructural Mixed-Ligand Uranyl Coordination Polymers Based on a Patterning Strategy.

Controlling the orderly assembly of molecular building blocks for the formation of the desired architectural, chemical, and physical properties of the resulting solid-state materials remains a long-term goal and deserves to be examined. In this work, we propose a patterning strategy for modular assembly and structural regulation of mixed-ligand uranyl coordination polymers (CPs) through the combination of couples of organic ligands with complementary molecular geometry and well-matched coordination modes. By using a 5-(p-tolyldiazenyl)isophthalic acid ligand (H2ptdi) with different rigid linear bicarboxylic acid linkers to construct a well-defined ladder-like pattern, five novel isostructural uranyl coordination polymers, [(UO)2(ptdi)(bdc)0.5](dma) (1), [(UO)2(ptdi)(bpdc)0.5](dma) (2), [(UO)2(ptdi)(tpdc)0.5](dma) (3), [(UO)2(ptdi)(ndc)0.5](dma) (4), and [(UO)2(ptdi) (pdc)0.5](dma) (5) {H2bdc, 1,4-dicarboxybenzene; H2bpdc, 4,4'-biphenyldicarboxylic acid; H2tpdc, terphenyl-4,4″-dicarboxylic acid; H2ndc, 2,6-naphthalenedicarboxylic acid; H2pdc, 1,6-pyrenedicarboxylic acid; [dma]+, [(CH3)2NH2]+}, were successfully synthesized. Structural analysis reveals that 1-5 have similar ladder-like units but different sizes of one-dimensional nanochannels and interlayer spacing due to the different lengths and widths of the linkers. Because of the changes in interlayer spacing of these isostructural cationic frameworks, differences in the performance of Eu3+ ion exchange with [dma]+ are observed. Moreover, those compounds with high phase purity have been further characterized by thermogravimetric analysis, infrared spectroscopy, and luminescence spectroscopy, element analysis, PXRD and UV spectroscopy. Among them, compound 3 with strong fluorescence can selectively detect Fe3+ over several competing metal cations in aqueous solution. This work not only provides a feasible patterning method for effectively regulating the modular synthesis of functional coordination polymers but also enriches the library of uranyl-based coordination polymers with intriguing structures and functionality.

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity.

The electron-rich squarate ion (C4O42-, SA2-) possesses electronic delocalization over the entire molecule and good redox activity, and the functionalization of metal-organic complexes with the SA2- group is desirable. In this work, a mixed-ligand method is used to construct novel uranyl squarate coordination polymers utilizing 4,4'-bipyridine (bpy), 4,4'-bipyridine-N,N'-dioxide (bpydo), 1,10-phenanthroline (phen), 4,4'-vinylenedipyridine (vidpy), and in situ formed oxalate (OA2-) as ancillary ligands. Seven mixed-ligand uranyl compounds, [(UO2)(OH)(SA)](Hbpy) (1), [(UO2)(H2O)(SA)2](H2bpy) (2), (UO2)(H2O)(SA)(bpydo)·2H2O (3), (UO2)(H2O)(SA)(phen)·H2O (4), (UO2)(OH)(SA)0.5(phen)·H2O (5), [(UO2)(SA)(OA)0.5](Hphen) (6), and [(UO2)(SA)(OA)0.5](Hvidpy) (7), with varying crystal structures were synthesized under hydrothermal conditions. Compound 1, together with bpy molecules filling in the interlayer space as template agents, has a two-dimensional (2D) network structure, while 2 gives a one-dimensional (1D) chain based on mononuclear uranium units. Compound 3 shows a neutral 2D network through the combined linkage of SA2- and bpydo. Both 4 and 5 have a similar chain-like structure due to the capping effect of phen motifs, while phen molecules in 6 act as templating agents after protonation. Similar to 6, compound 7 has a "sandwich-like" structure in which the Hvidpy motifs locate in the voids of layers of 2D uranyl-squarate networks. The redox properties of typical mixed-ligand uranyl-squarate compounds, 1, 4, and 5 with high phase purity, are characterized using cyclic voltammetry. All three of these uranyl coordination compounds show anode peaks (Ea) at 0.777, 0.804, and 0.760 V, respectively, which correspond to the oxidation process of SA2- → SA. Meanwhile, cathodic peaks (Ec) at -0.328, -0.315, and -0.323 V corresponding to the reduction process of U(VI) → U(V) are also observed. The results reveal that all three of these uranyl coordination compounds show good redox activity and, most importantly, the interplay between two different redox-active motifs of SA2- organic linker and uranyl node. This work enriches the library of redox-active uranyl compounds and provides a feasible mixed-ligand method for regulating the synthesis of functional actinide compounds.

Importance of Combined Electrochemical Process Sequence and Electrode Arrangements: A Lab-scale Trial of Real Reverse Osmosis Landfill Leachate Concentrate.

Reverse osmosis (RO) is a widely applied technique for wastewater effluent reuse and landfill leachate treatment. The latter generates a refractory RO leachate concentrate (ROLC), for which cost-effective treatment is required. This study focuses on a two-step electrochemical method consisting of aluminum-based electrocoagulation (EC), and simultaneous electrooxidation-electrocoagulation with a titanium-based lead dioxide (Ti/ß-PbO2) anode and aluminum cathode (EOEC) assembly. The sequence and electrode arrangements of the combined electrochemical process were investigated to determine the organic transformation, Ti/ß-PbO2 anode viability, and energy consumption. Series-based EC-EOEC decreased the total chemical oxygen demand (COD) from 8750 mg L-1 to 380 mg L-1, a 96% removal efficiency, in 3.5 hours at 141 A m-2. Under a low energy consumption of 28.7 kWh kgCOD-1, the ROLC biodegradability (BOD5/COD) significantly increased from 0.015 to 0.530, which was ascribed to aromatic removal (e.g., -C=C) and an increase in -COOH functional groups. Furthermore, the rapid removal of natural organic matter and increase in pH elevation from EC suppressed the dissolution of Pb from the Ti/ß-PbO2 anode during the subsequent EOEC, thereby leaving 0.061 mg L-1 in the ROLC after treatment. The treatment cost was 3.86 USD kgCOD-1, which was approximately 34% lower than that of previously reported electrochemical processes for ROLC treatment. These findings obtained with a real RO concentrate provide a foundation for scaling up this new electrochemical treatment approach.

[Setup and Microbial Community Analysis of ANAMMOX System for Landfill Leachate Treatment Coupling Partial Nitrification-Denitrification Process].

In order to upgrade the current shortcut nitrification and denitrification process for landfill leachate treatment and to stimulate nitrification-denitrification coupled with anaerobic ammonia oxidation (ANAMMOX) at a landfill, an ANAMMOX process was started using an up-flow anaerobic sludge bed (UASB) reactor seeded with nitrification and denitrification sludge. The performances of the reactor were investigated, including the nitrogen loading and nitrogen removal rates. Moreover, Illumina Miseq sequencing was conducted to analyze the microbial community dynamics under long-term operation on a molecular level. The results showed that the ANAMMOX reactor was successfully started in 149 days. The total nitrogen loading rate reached 4000.00 mg·(L·d)-1, and the total nitrogen removal rate reached 3885.76 mg·(L·d)-1 after stable operation. The average ammonium and nitrite removal efficiencies were more than 95%. In 250 days, the Planctomycetes in the reactor experienced rapid growth, and its abundance reached 54.94%. The abundance of Candidatus Kuenenia reached 49.66%. The upgrading process of landfill leachate treatment by coupling ANAMMOX based on short-cut nitrification and denitrification was confirmed to be feasible.

Interactions between tetracycline and extracellular polymeric substances in anammox granular sludge.

The effects of antibiotics on extracellular polymeric substances (EPS) using tetracycline as the model chemical were analyzed in terms of molecular property and structure. Results showed that three components, tryptophan, tryptophan type-proteins and polysaccharides in EPS of granular sludge from anaerobic ammonium oxidation (anammox) reactor can interacted with tetracycline, detected by the static quenching via the endogenous fluorescence quenching and transient fluorescence spectroscopy. Thermodynamic experiment confirmed that their interaction was dominated by the hydrophobic force. Combined with the synchronous fluorescence spectroscopy, it was found that tetracycline facilitated the extension degree of peptide chains in tryptophan type-proteins, leading to the enhancement of hydrodynamic diameter of the macromolecules in EPS when binding with tetracycline. EPS in AnGS demonstrated the resistance ability to tetracycline by converting from gel to sol state in rheological term. With the increase of tetracycline concentration, the stability of elastic structures in EPS declined, influencing the AnGS stability.

Combination of self-organizing map and parallel factor analysis to characterize the evolution of fluorescent dissolved organic matter in a full-scale landfill leachate treatment plant.

The dissolved organic matter (DOM) characterization in a full-scale landfill leachate treatment plant is of great importance for the design and operation of treatment processes. In this study, the long-term removal behaviors of DOM during landfill leachate treatment were explored using excitation emission matrix fluorescence spectroscopy (EEMs) coupled with parallel factor analysis (PARAFAC) and self-organizing map (SOM). Results indicated that the application of combining PARAFAC and SOM on EEMs analysis effectively characterized long-term removal behaviors of DOM during leachate treatment. The DOM in raw leachate was dominated by humic substances, while its composition exhibited significant seasonal differences. A large proportion of protein-like fluorescent dissolved organic matter (FDOM) and bulk DOM were removed within membrane bioreactor (MBR) system. Meanwhile the humic-like FDOM removal capacity in nanofiltration (NF) process was well comparable with those in the MBR system owing to the bio-recalcitrant nature of humic substances. The protein-like FDOM and bulk DOM were removed synchronously in both the process of MBR and NF. Moreover, samples distribution exhibited obvious differences among NF concentrate samples. In general, the performance of MBR-NF treatment for landfill leachate displayed reasonable stability in DOM removal irrespective of seasonal variations. This study enhanced our understanding of EEMs application in characterizing leachate-derived DOM composition and has potential implications for the associated monitoring investigations in engineered systems.

Granulation of sulfur-oxidizing bacteria for autotrophic denitrification.

Sulfur-oxidizing bacteria (SOB) was successfully employed for effective autotrophic denitrification and sludge minimization in a full-scale application of saline sewage treatment in Hong Kong. In this study, a Granular Sludge Autotrophic Denitrification (GSAD) reactor was continuously operated over 600 days for SOB granulation, and to evaluate the long-term stability of SOB granules, microbial communities and denitrification efficacy. Sludge granulation initiated within the first 40 days of start-up with an average particle size of 186.4 µm and sludge volume index (SVI5) of 40 mL/g in 5 min. The sludge granules continued to grow reaching a nearly uniform size of mean diameter 1380 ± 20 µm with SVI5 of 30 mL/g during 600 days of GSAD reactor operation at hydraulic retention time of 5 h and nitrate loading rate of 0.33 kg-N/m3/d. The GSAD reactor with SOB granular sludge achieved 93.7 ± 2.1% nitrogen and complete sulfide removal with low sludge yield of 0.15 g-volatile suspended solids (VSS)/g-N, and much lower nitrous oxide (N2O) emission than the heterotrophic denitrifying process. Microbial community analysis using fluorescence in situ hybridization (FISH) technique revealed that granules were enriched with SOB contributing to autotrophic denitrification. Furthermore, 16S rRNA analysis showed diverse autotrophic denitrification related genera, namely Thiobacillus (32.6%), Sulfurimonas (31.3%), and Arcobacter (0.01%), accounting for 63.9% of total operational taxonomic units at the generic level. No heterotrophic denitrification related genera were detected. The results from this study could provide useful design and operating conditions with respect to SOB sludge granulation and its subsequent application in a full-scale autotrophic denitrification in the Sulfate reduction-Autotrophic denitrification-Nitrification Integrated (SANI) process.

Sulfide-driven autotrophic denitrification significantly reduces N2O emissions.

The Sulfate reduction-Autotrophic denitrification-Nitrification Integrated (SANI) process build on anaerobic carbon conversion through biological sulfate reduction and autotrophic denitrification by using the sulfide byproduct from the previous reaction. This study confirmed extra decreases in N2O emissions from the sulfide-driven autotrophic denitrification by investigating N2O reduction, accumulation, and emission in the presence of different sulfide/nitrate (S/N) mass ratios at pH 7 in a long-term laboratory-scale granular sludge autotrophic denitrification reactor. The N2O reduction rate was linearly proportional to the sulfide concentration, which confirmed that no sulfide inhibition of N2O reductase occurred. At S/N = 5.0 g-S/g-N, this rate resulted by sulfide-driven autotrophic denitrifying granular sludge (average granule size = 701 µm) was 27.7 mg-N/g-VSS/h (i.e., 2 and 4 times greater than those at 2.5 and 0.8 g-S/g-N, respectively). Sulfide actually stimulates rather than inhibits N2O reduction no matter what granule size of sulfide-driven autotrophic denitrifying sludge engaged. The accumulations of N2O, nitrite and free nitrous acid (FNA) with average granule size 701 µm of sulfide-driven autotrophic denitrifying granular sludge engaged at S/N = 5.0 g-S/g-N were 4.7%, 11.4% and 4.2% relative to those at 3.0 g-S/g-N, respectively. The accumulation of FNA can inhibit N2O reduction and increase N2O accumulation during sulfide-driven autotrophic denitrification. In addition, the N2O gas emission level from the reactor significantly increased from 14.1 ± 0.5 ppmv (0.002% of the N load) to 3707.4 ± 36.7 ppmv (0.405% of the N load) as the S/N mass ratio in the influent decreased from 2.1 to 1.4 g-S/g-N over the course of the 120-day continuous monitoring period. Sulfide-driven autotrophic denitrification may significantly reduce greenhouse gas emissions from biological nutrient removal when sulfur conversion processes are applied.

Removal of refractory organics in nanofiltration concentrates of municipal solid waste leachate treatment plants by combined Fenton oxidative-coagulation with photo--Fenton processes.

Removal of the refractory organic matters in leachate brines generated from nanofiltration unit in two full-scale municipal solid waste landfill leachate treatment plants was investigated by Fenton oxidative-coagulation and ultraviolet photo - Fenton processes in this study. Fenton oxidative-coagulation was performed under the condition of an initial pH of 5.0 and low H2O2/Fe(2+) ratios. After precipitate separation, the remaining organic constituents were further oxidized by photo - Fenton process. For both leachate brines with varying pollution strength, more than 90% COD and TOC reductions were achieved at H2O2/Fe(2+) dosages of 35 mM/8 mM and 90 mM/10 mM, respectively. The effluent COD ranged 120-160 mg/L under the optimal operating conditions, and the biodegradability was increased significantly. Fenton oxidative-coagulation was demonstrated to contribute nearly 70% overall removal of organic matters. In the combined processes, the efficiency of hydrogen peroxide varied from 216 to 228%, which may significantly reduce the operating cost of conventional Fenton method. Six phthalic acid esters and thirteen polycyclic aromatic hydrocarbons were found in leachate brines, and, on the average, around 80% phthalic acid esters and 90% polycyclic aromatic hydrocarbons were removed by the combined treatments.