Edge-Rich Pt-O-Ce Sites in CeO2 Supported Patchy Atomic-Layer Pt Enable a Non-CO Pathway for Efficient Methanol Oxidation.

Rational design of efficient methanol oxidation reaction (MOR) catalyst that undergo non-CO pathway is essential to resolve the long-standing poisoning issue. However, it remains a huge challenge due to the rather difficulty in maximizing the non-CO pathway by the selective coupling between the key *CHO and *OH intermediates. Here, we report a high-performance electrocatalyst of patchy atomic-layer Pt epitaxial growth on CeO2 nanocube (Pt ALs/CeO2) with maximum electron-metal support interactions for enhancing the coupling selectively. The small-size monolayer material achieves an optimal geometrical distance between edge Pt-O-Ce sites and *OH absorbed on CeO2, which well restrains the dehydrogenation of *CHO, resulting in the non-CO pathway. Meanwhile, the *CHO/*CO intermediate generated at inner Pt-O-Ce sites can migrate to edge, inducing the subsequent coupling reaction, thus avoiding poisoning while promoting reaction efficiency. Consequently, Pt ALs/CeO2 exhibits exceptionally catalytic stability with negligible degradation even under 1000 s pure CO poisoning operation and high mass activity (14.87 A/mgPt), enabling it one of the best-performing alkali-stable MOR catalysts.

Sodium alginate based adsorbent: Facile fabrication, extraordinary removal efficacy of anionic dyes and adsorption mechanism.

Eco-friendly and renewable sodium alginate, as a potential alternative to fossil resources, has attracted considerable attention in wastewater treatment field. Herein, we develop a SA/PEI/PEG (sodium alginate/polyethyleneimine/polyethylene glycol diglycidyl ether) adsorbent in which SA was functionalized by PEI/PEG via a facile but effective strategy of one-pot gelation of aqueous SA/PEI/PEG solution. Systematic investigations were accomplished to explore the effects of adsorbent factors on the adsorption performances of the adsorbent towards the anionic dyes CR (congo red), AB-10B (amido black-10B), and AB-25 (acid blue-25). Strikingly, the SA/PEI/PEG exhibited exceptional adsorption performance to CR (2782 mg g-1, 90.6 %), AB-10B (1369 mg g-1, 90.9 %) and AB-25 (4221 mg g-1, 92.6 %) at 30 °C, pH = 3, 200 r min-1 and oscillated 24 h, and demonstrating exceptional reusability after six cycles of adsorption-desorption cycles. Furthermore, the three kinetic, four isothermic and one thermodynamic models were used to investigate the adsorption behaviors of the adsorbent towards these dyes. The possible adsorption mechanism is suggested: Hydrogen bond interactions and electrostatic attractions between SA/PEI/PEG and the dyes primarily contribute to exceptional adsorption capacity. The SA/PEI/PEG adsorbent endowed with easy fabrication, extraordinary adsorption capacity and excellent reusability promises potential application prospects in wastewater purification industry.

Recyclable chitosan adsorbent: Facile functionalization strategy, excellent removal capacity of dyes and adsorption mechanism.

The development of chitosan-based adsorbents with facile preparation, high adsorption performance and reusability for the removal of contaminant dyes remains a persistent challenge. To overcome this challenge, herein, we have developed a novel and extremely facile one-step strategy by which a new high-performance chitosan/polyethyleneimine/polyethylene glycol diglycidyl ether adsorbent (named as CC/PEI/PGDE) has been successfully fabricated via direct functionalization of CC by PEI at ambient temperature followed by subsequent freeze-drying. The Box-Behnken Design was employed to optimize the concentrations of adsorbent components. Attractively, this adsorbent exhibit outstanding adsorption performances to congo red (RED), acid blue-25 (BLUE) and amino black-10B (BLACK) with 2901 mg g-1 (90.9 %), 3434 mg g-1 (90.9 %), and 1438 mg g-1 (90.1 %) of adsorption capacities (removal efficiencies), respectively, and maintains nearly the same adsorption behaviors to original adsorbent even after 6 cycles of adsorption-desorption processes. Meanwhile, three kinetic models, three isothermal models, and the Vant Hoff model are employed to further investigate the adsorption behaviors of RED, BLUE, and BLACK dyes by CC/PEI/PGDE. The results from SEM, EDS, BET, FT-IR, pHZPC and XPS confirm that hydrogen bond interactions and electrostatic attractions play crucial roles in facilitating dyes adsorption by CC/PEI/PGDE. It is expected that this work can bring forward a new perspective for the facile design of high-performance adsorbent for removing anionic dyes from wastewater.

Boosting Electrocatalytic Ammonia Synthesis via Synergistic Effect of Iron-Based Single Atoms and Clusters.

Electrocatalytic reduction of nitrate to ammonia (NO3RR) is gaining attention for low carbon emissions and environmental protection. However, low ammonia production rate and poor selectivity have remained major challenges in this multi-proton coupling process. Herein, we report a facile strategy toward a novel Fe-based hybrid structure composed of Fe single atoms and Fe3C atomic clusters that demonstrates outstanding performance for synergistic electrocatalytic NO3RR. By operando synchrotron Fourier transform infrared spectroscopy and theoretical computation, we clarify that Fe single atoms serve as the active site for NO3RR, while Fe3C clusters facilitate H2O dissociation to provide protons (*H) for continued hydrogenation reactions. As a result, the Fe-based electrocatalyst exhibits ammonia Faradaic efficiency of nearly 100%, with a corresponding production rate of 24768 µg h-1 cm-2 at -0.4 V vs RHE, exceeding most reported metal-based catalysts. This research provides valuable guidance toward multi-step reactions.

Recoverable cellulose composite adsorbents for anionic/cationic dyes removal.

GO/HEC/PGDE/Fe3O4 materials were successfully fabricated using environmentally-friendly hydroxyethyl cellulose (HEC), poly(ethylene glycol) diglycidyl ether (PGDE), graphene oxide (GO) and magnetic Fe3O4. Systematic investigations were completed to explore the influences of GO content in GO/HEC/PGDE/Fe3O4 and adsorption conditions on the adsorptions of cationic dyes (methylene blue (MB), crystal violet (CV)) and anionic dye acid blue 25 (AB-25). The increase of GO content can remarkably improve the adsorption capacity of GO/HEC/PGDE/Fe3O4 for the dyes. The three kinetic, four isothermic and three thermodynamic models were investigated to reveal the adsorption behaviors of the dyes. The formation of HEC/PGDE/Fe3O4 and adsorption mechanisms of the dyes by GO/HEC/PGDE/Fe3O4 were suggested. The GO/HEC/PGDE/Fe3O4 endowed with easy-fabrication, eco-friendly feature, efficient adsorption capacity of anionic/cationic dyes, convenient separation and reusability has potential applications in wastewater purification industry.

Eco-Friendly High-Performance Poly(methyl methacrylate) Film Reinforced with Methylcellulose.

Poly(methyl methacrylate) (PMMA) is a thermoplastic polyester with excellent properties such as lightweight, low price, biocompatibility, and so on. However, its extensive utilization is restricted by the deficiencies of brittleness and poor mechanical properties. In this study, high-performance PMMA films enhanced by methylcellulose (MC) were fabricated by a simple procedure at ambient temperatures. The effects of PMMA/MC mass ratio and thermal compression treatment on mechanical properties (tensile strength and elongation) were systematically investigated. The PMMA/MC films showed remarkably enhanced mechanical properties compared with neat PMMA. The tensile strengths of the PMMA/MC (3:97) and PMMA/MC (1:1) films are higher than that of the PMMA/MC (9:1) film by about 471 and 83%, respectively. The mechanical properties were also improved after thermal compression treatment. Importantly, the PMMA/MC films could be recovered and reused. In addition, the morphologies, crystalline state, and chemical structures of the films were investigated by scanning electron microscopy, X-ray diffraction, and 13C NMR spectroscopy. The films are expected to be used as sustainable and potential alternatives to petroleum-based polymer film products because of their simple preparation procedure, high-performance mechanical properties, excellent recycling, eco-friendly features, and scale manufacture.

Cellulose dissolution in diallylimidazolium methoxyacetate + N-methylpyrrolidinone mixture.

The utilization of cellulose in industrial applicat is of great significance to sustainable development of human society and reducing dependence on dwindling fossil resources. Nevertheless, this utilization of cellulose has actually been limited due to its insolubilization. Here, novel solvents consisting of diallylimidazolium methoxy acetate ([A2im][CH3OCH2COO]) and N-methylpyrrolidinone (NMP) were developed. The solubility of cellulose in [A2im][CH3OCH2COO]/NMP was determined, and the influence of [A2im][CH3OCH2COO]/NMP molar ratio on cellulose dissolution was systematically investigated. Meanwhile, we also presented the affecting factors of the cellulose material fabrication including preparation approach, [A2im][CH3OCH2COO] and cellulose solution concentration. Attractively, the [A2im][CH3OCH2COO]/NMP solvents display much powerful dissolution capacity for cellulose even at 25 °C (25.4 g 100 g-1). This is mainly ascribed to the combined factors: The hydrogen bond interactions of the H2, H4 and H6 in [A2im]+ and carboxyl O atom in [CH3OCH2COO]- with the hydroxyl H atom and O atom in cellulose; the dissociation of NMP towards [A2im][CH3OCH2COO]; the stabilization of NMP towards the dissolved cellulose chains. In addition, the thermostability and chemical structure of the regenerated cellulose from the solvents was also estimated.

Development of Diallylimidazolium Methoxyacetate/DMSO (DMF/DMA) Solvents for Improving Cellulose Dissolution and Fabricating Porous Material.

Cellulose is the most abundant natural biopolymer, with unique properties such as biodegradability, biocompability, nontoxicity, and so on. However, its extensive application has actually been hindered, because of its insolubility in water and most solvents. Herein, highly efficient cellulose solvents were developed by coupling diallylimidazolium methoxyacetate ([A2im][CH3OCH2COO]) with polar aprotic solvents dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA). Attractively, these solvents showed extraordinarily powerful dissolution performance for cellulose (e.g., 26.1 g·100g-1) in [A2im][CH3OCH2COO]/DMSO(RDMSO = 1.01 solvent even at 25 °C), which is much more advantageous over previously reported solvents. To our knowledge, such powerful cellulose solvents have not been reported before. The cellulose dissolution mechanism is proposed to be of three combined factors: (1) The hydrogen bond interactions of the H2, H4 and H6 in [A2im]+ and the carboxyl O atom in [CH3OCH2COO]-, along with the hydroxyl H atom and O atom in cellulose, are main driving force for cellulose dissolution; (2) the dissociation of [A2im][CH3OCH2COO] by DMF increases the anion and cation concentrations and thus promotes cellulose dissolution; (3) at the same time, DMF also stabilizes the dissolved cellulose chains. Meanwhile, the porous cellulose material with a varying morphologic structure could be facially fabricated by modulating the cellulose solution concentration. Additionally, the dissolution of cellulose in the solvents is only a physical process, and the regenerated cellulose from the solvents retains sufficient thermostability and a chemical structure similar to the original cellulose. Thus, this work will provide great possibility for developing cellulose-based products at ambient temperatures or under no extra heating/freezing conditions.

Dissolution performance of cellulose in [A2im][MOA]/MIM solvents.

Cellulose solvents ([A2im][MOA]/MIM) were developed by combining diallylimidazolium methoxyacetate ([A2im][MOA]) with N-methylimidazole (MIM). The cellulose solubilities in the ([A2im][MOA]/MIM) solvents were determined at 25 °C, and the effect of the MIM/[A2im][MOA] molar ratio on cellulose solubility was systematically investigated. Attractively, the solvents show cellulose solubility as high as 25.2 g 100 g-1 even at 25 °C. It is proposed that the H2, H4 and H6 in [A2im]+ and the carboxyl O atom in [MOA]- primarily contribute to the dissolution of cellulose; MIM mainly acts to dissociate [A2im][MOA] into [A2im]+ and [MOA]-, and stabilize the dissolved cellulose chains. Moreover, the porous cellulose materials with varying morphological structures could be tailored by simply tuning the cellulose solution concentration, and the formation mechanism of the cellulose material was discussed.

Biodegradable lignocellulosic porous materials: Fabrication, characterization and its application in water processing.

Biodegradable porous materials based on natural lignocellulosic biomass have multiple advantages of low cost, lightweight, non-toxicity, and the potential in place of non-biodegradable petrochemical products. However, the fabrication process for the porous materials was complicated by the slow and costly prefreeze or supercritical drying methods. Herein, a facile and green/clean strategy was presented to fabricate corncob and willow wood porous materials in ambient conditions. The effect of biomass solution concentration and preparation condition on porous material morphology structure was investigated systematically by scanning electron microscope (SEM). Further, X-ray diffraction (XRD), Fourier transform infrared (FTIR), Brunauer-Emmet-Teller (BET) and thermogravimetric analysis (TGA) were used to estimate the structure and thermostability of the porous materials. Furthermore, the adsorptive properties of the biomass porous materials towards dye methylene blue and oil were evaluated. The biomass porous materials with a fluffy and porous structure were readily obtained via this procedure and showed effective adsorption capacity for dye methylene blue and oil.

Pretreatment of corn straw using the alkaline solution of ionic liquids.

In the present work, the pretreatment of corn stalk with the solution of 1-ethyl-3-methylimidazolium acetate ([Emim]Ac) ionic liquid containing NaOH was explored for its lignin removal. The effects of reaction temperature, reaction time, and solid-liquid ratio on the lignin removal efficiency were determined by the response surface methodology (RSM). The pretreatment conditions were optimized by the Box-Behnken design and the comparative study of the composition and structure of corn straw before and after the pretreatment to be: reaction temperature 98.5 °C, reaction time 1.31 h, and solid-liquid ratio 1:8.7. Under the optimized conditions, the cellulose and hemicellulose contents of the corn straw were increased to 85.69% and 9.1%, respectively, and the lignin content was reduced to 2.27% with the lignin removal efficiency up to 87.4%.

Graphene Oxide Reinforced Alginate/PVA Double Network Hydrogels for Efficient Dye Removal.

Dually crosslinked graphene oxide reinforced alginate/polyvinyl alcohol (PVA) double network (DN) hydrogels were prepared via a facile freeze/thaw method followed by soaking in a Ca2+ solution. The morphology and structure of the hydrogels were systematically examined by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The effects of pH, dosage of hydrogel, adsorption time, and temperature on the adsorptive property of DN hydrogels towards methylene blue (MB) were also studied. Results indicated that the hydrogels exhibited typical 3D porous structures and had an efficient adsorption effect towards MB due to strong interactions between DN hydrogels and MB molecules. The adsorption isotherm was found to coincide with the Langmuir model with a monolayer adsorption. The highest adsorption capacity of DN hydrogels for MB was examined as 480.76 mg·g-1.

Recyclable Choline Nicotinate and Ferulate Aqueous Solutions as Efficient Lignin Solvents.

Four novel choline carboxylate aqueous solution systems were developed by mixing H2O with choline nicotinate [Ch][Na], choline ferulate [Ch][Fa], choline vanillate [Ch][Va] and choline syringate [Ch][Sa]. The solubility of lignin in the four solvents was determined at 25 °C. The influence of the molar ratio of H2O to [Ch][Na] ([Ch][Fa], [Ch][Va] and [Ch][Sa]) and the anionic structure on lignin solubility were systematically investigated. It was found that, the anionic structure and H2O content significantly affected lignin dissolution. Interestingly, H2O/[Ch][Na] and H2O/[Ch][Fa] solvents show efficient capacity for lignin dissolution even at room temperatures. The dissolution of lignin in H2O/[Ch][Na] and H2O/[Ch][Fa] solvents is mainly ascribed to the interaction of lignin with the alkyl chain in the anion and cation dissociated from [Ch][Na]([Ch][Fa]) by H2O. In addition, the recycling of the lignin solvent was examined, and the structure and thermostability of the lignin regenerated from the solvent were also estimated.

Sustainable and Low Viscous 1-Allyl-3-methylimidazolium Acetate + PEG Solvent for Cellulose Processing.

Developing sustainable, low viscous and efficient solvents are always advantageous to the processing/fabricating of cellulose materials in practical applications. To this end, in this work novel solvents were developed; ([Amim][CH3COO]/PEG) by dissolving polyethylene glycol 200 (PEG-200) in 1-allyl-3-methylimidazolium acetate ([Amim][CH3COO]). The solubilities of cellulose in [Amim][CH3COO]/PEG solvents were determined as a function of temperature, and the possible dissolution mechanism of cellulose in [Amim][CH3COO]/PEG solvent was investigated. The novel solvent exhibits outstanding advantages for good dissolution capacity of cellulose, such as low viscosity, negligible vapor pressure, and recycling capability. The [CH3COO]- anion and the [Amim]⁺ cation of [Amim][CH3COO] in [Amim][CH3COO]/PEG-10 are the driving force for cellulose dissolution verified by the 13C NMR spectra. In addition, the regenerated cellulose films from [Amim][CH3COO]/PEG solvent were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and thermogravimetric analysis (TGA) to estimate their morphologies and structures.

A facile synthesis of gold micro/nanostructures at the interface of 1,3-dibutylimidazolium bis(trifluoromethylsulfonyl)imide and water.

The development of a simple, template-free, and one-step strategy to synthesize nanostructured Au architectures with fascinating morphology is highly desirable and technically important due to their valuable applications in varied fields. In this work, the "green" strategy of "tunable ionic liquids-water (ILs-H2O) interfacial synthesis" developed previously by us is utilized for feasible synthesis of gold needle mushroom-like micro/nanostructures at the 1,3-dibutylimidazolium bis(trifluoromethylsulfonyl)imide ([C4bim][Tf2N]) - water interface and ambient conditions. The as-obtained gold needle mushrooms (AuNMs) have been characterized and analyzed systemically by scanning electron microscopy, X-ray powder diffraction, energy-dispersive X-ray spectroscopy, and transmission electron microscopy. It is shown that the as-prepared AuNMs can be used as substrates to perform surface enhanced Raman scattering (SERS) investigation with striking SERS sensitivity. By employing ILs with different alkyl chain lengths of the imidazolium cations and/or different nature of anions, Au nanomaterials with diverse morphologies can be easily prepared at different ILs-H2O interfaces. Based on the analysis of the control experiments, the growth and formation of AuNMs at the [C4bim][Tf2N]-H2O interface have been discussed.

Understanding the dissolution of cellulose in 1-butyl-3-methylimidazolium acetate+DMAc solvent.

Cellulose solvent ([C4mim][CH3COO]/DMAc) could be obtained by adding N,N-dimethylacetamide (DMAc) in 1-butyl-3-methylimidazolium acetate ([C4mim][CH3COO]). The solubilities of cellulose in [C4mim][CH3COO]/DMAc solvents were determined at 25°C. The effects of molar ratio of DMAc to [C4mim][CH3COO] on cellulose solubility and the possible dissolution mechanism of cellulose in [C4mim][CH3COO]/DMAc solvent have been studied. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). It was found that, cellulose was more readily dissolved in [C4mim][CH3COO]/DMAc solvent than in a neat [C4mim][CH3COO], which mainly attributed to the increased "free" [CH3COO](-) anions and [C4mim](+) cations which result from the dissociation of [C4mim][CH3COO] by DMAc. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent displayed good thermostability and similar molecular structure to the original cellulose.

Facile cellulose dissolution without heating in [C4mim][CH 3COO]/DMF solvent.

Novel cellulose solvents, [C4mim][CH3COO]/DMF, were designed by adding an aprotic polar solvent N,N-dimethylformamide (DMF) in 1-butyl-3-methylimidazolium acetate ([C4mim][CH3COO]). The solubilities of cellulose in [C4mim][CH3COO]/DMF solvents were determined at 25°C. The effects of molar ratio of DMF to [C4mim][CH3COO] on cellulose solubility and the possible dissolution mechanism of cellulose in [C4mim][CH3COO]/DMF solvent have been studied. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMF solvent were characterized by scanning electron micrograph (SEM) Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD), and the degree of polymerization (DP) of regenerated cellulose was determined. The findings reveal that the facile dissolution of cellulose in such solvents is mainly attributed to the increased "free" [CH3COO](-) anions and [C4mim](+) cations which result from the dissociation of [C4mim][CH3COO] by DMF. Moreover, the macromolecular chain of the cellulose is hardly broken during the dissolution and precipitation processes.

Dissolution of cellulose in 1-allyl-3-methylimizodalium carboxylates at room temperature: a structure-property relationship study.

The development of highly efficient cellulose solvents is imperative to the effective utilization of cellulose. In this work, ionic liquids (ILs) with the same 1-allyl-3-methylimidazolium cation ([Amim](+)) but different carboxylate anions, such as formate ([HCOO](-)), acetate ([CH3COO](-)), propionate ([CH3CH2COO](-)), butyrate ([CH3CH2CH2COO](-)), glycollate ([HOCH2COO](-)), lactate ([CH3CHOHCOO](-)) and benzoate ([C6H5COO](-)) were synthesized, and their thermal properties and viscosities were determined. Then these ILs were used to investigate the effect of anion structure on solubility of cellulose in the ILs. It was shown that the viscosity and cellulose solubility depended strongly on the anion structure of the ILs. For example, at 30 °C solubility of cellulose in [Amim][CH3CH2COO] was as high as 19.0%, whereas cellulose was not soluble in [Amim][HOCH2COO], [Amim][CH3CHOHCOO] and [Amim][C6H5COO]. In addition, solvatochromic UV/vis probe and (13)C NMR measurements were performed to demonstrate dissolution mechanism of cellulose in the ILs. The results suggested that although cations of the ILs have un-negligible contribution to the highly efficient dissolution of cellulose, hydrogen bonding interactions of anions of the ILs with cellulose is predominant.

Cellulose dissolution at ambient temperature: role of preferential solvation of cations of ionic liquids by a cosolvent.

Highly effective cellulose solvents for the dissolution of cellulose at ambient temperature have been designed by adding any aprotic polar solvent to 1-butyl-3-methylimidazolium acetate ([C(4) mim][CH(3)COO]). The effects of molar ratio of the aprotic polar solvents to [C(4) mim][CH(3)COO], anionic structure of the ionic liquids (ILs) and nature of the co-solvents on cellulose solubility have been studied in detail. The enhanced dissolution of cellulose is suggested to be mainly resulted from the preferential solvation of cations of the ILs by the aprotic polar solvents, and this has been supported by our conductivity measurements.