Separation of Mono-/Divalent Ions via Controlled Dynamic Adsorption/Desorption at Polythiophene Coated Carbon Surface with Flow-Electrode Capacitive Deionization.

Capacitive deionization for selective separation of ions is rarely reported since it relies on the electrostatic attraction of oppositely charged ions with no capability to distinguish ions of different valent states. Using molecular dynamic simulation, a screening process identified a hybrid material known as AC/PTh, which consists of activated carbon with a thin layer of polythiophene (PTh) coating. By utilizing AC/PTh as electrode material implementing the short-circuit cycle (SCC) mode in flow-electrode capacitive deionization (FCDI), selective separation of mono-/divalent ions can be realized via precise control of dynamic adsorption and desorption of mono-/divalent ions at a particular surface. Specifically, AC/PTh shows strong interaction with divalent ions but weak interaction with monovalent ions, the distribution of divalent ions can be enriched in the electric double layer after a couple of adsorption-desorption cycles. At Cu2+/Na+ molar ratio of 1:40, selectivity toward divalent ions can reach up to 110.3 in FCDI SCC mode at 1.0 V. This work presents a promising strategy for separating ions of different valence states in a continuously operated FCDI device.

Solar Driven Gas Phase Advanced Oxidation Processes for Methane Removal - Challenges and Perspectives.

Methane (CH4 ) is a potent greenhouse gas and the second highest contributor to global warming. CH4 emissions are still growing at an alarmingly high pace. To limit global warming to 1.5 °C, one of the most effective strategies is to reduce rapidly the CH4 emissions by developing large-scale methane removal methods. The purpose of this perspective paper is threefold. (1) To highlight the technology gap dealing with low concentration CH4 (at many emission sources and in the atmosphere). (2) To analyze the challenges and prospects of solar-driven gas phase advanced oxidation processes for CH4 removal. And (3) to propose some ideas, which may help to develop solar-driven gas phase advanced oxidation processes and make them deployable at a climate significant scale.

Regulating Surface Wettability and Charge Density of Porous Carbon Particles by In Situ Growth of Polyaniline for Constructing an Efficient Electrical Percolation Network in Flow-Electrode Capacitive Deionization.

Both electrical conductivity and surface wettability are required for the selection of active carbon materials in flow-electrode capacitive deionization, while a trade-off exists between these two properties. In this work, a hybrid material with a thin layer of polyaniline (PANI) coating on activated carbon (AC/PANI) was successfully developed to retain excellent electrical conductivity and acquire good surface wettability. By adjusting the dosage of initiator, AC/PANI composites with different loading fractions of PANI were obtained. The electrochemical testing demonstrated that the AC/PANI composites have higher specific capacitance and lower ion diffusion resistance compared to pure AC, resulting in better desalinization performance. Specifically, with a feed concentration of 1600 mg/L, excellent adsorption capacity and high charge efficiency can be simultaneously achieved at 13.51 mg/g and 92.21%, respectively. Benefiting from the formation of a continuous electrical percolation network and reduced solid/liquid interfacial transport resistance, a 39% enhancement of average salt adsorption rate (from 0.54 to 0.75 µmol/min/cm2) was obtained.

Lignin from Hardwood and Softwood Biomass as a Lubricating Additive to Ethylene Glycol.

Ethylene glycol (EG)-based lubricant was prepared with dissolved organosolv lignin from birch wood (BL) and softwood (SL) biomass. The effects of different lignin types on the rheological, thermal, and tribological properties of the lignin/EG lubricants were comprehensively investigated by various characterization techniques. Dissolving organosolv lignin in EG results in outstanding lubricating properties. Specifically, the wear volume of the disc by EG-44BL is only 8.9% of that lubricated by pure EG. The enhanced anti-wear property of the EG/lignin system could be attributed to the formation of a robust lubrication film and the strong adhesion of the lubricant on the contacting metal surface due to the presence of a dense hydrogen bonding (H-bonding) network. The lubricating performance of EG-BL outperforms EG-SL, which could be attributed to the denser H-bonding sites in BL and its broader molecular weight distribution. The disc wear loss of EG-44BL is only 45.7% of that lubricated by EG-44SL. Overall, H-bonding is the major contributor to the different tribological properties of BL and SL in EG-based lubricants.

Pore size dependent molecular adsorption of cationic dye in biomass derived hierarchically porous carbon.

Hierarchically porous carbon adsorbents were successfully fabricated from different biomass resources (softwood, hardwood, bamboo and cotton) by a facile two-step process, i.e. carbonization in nitrogen and thermal oxidation in air. Without involving any toxic/corrosive chemicals, large surface area of up to 890 m2/g was achieved, which is comparable to commercial activated carbon. The porous carbons with various surface area and pore size were used as adsorbents to investigate the pore size dependent adsorption phenomenon. Based on the density functional theory, effective (E-SSA) and ineffective surface area (InE-SSA) was calculated considering the geometry of used probing adsorbate. It was demonstrated that the adsorption capacity strongly depends on E-SSA instead of total surface area. Moreover, a regression model was developed to quantify the adsorption capacities contributed from E-SSA and InE-SSA, respectively. The applicability of this model has been verified by satisfactory prediction results on porous carbons prepared in this work as well as commercial activated carbon. Revealing the pore size dependent adsorption behavior in these biomass derived porous carbon adsorbents will help to design more effective materials (either from biomass or other carbon resources) targeting to specific adsorption applications.

Molecular Transformation, Diffusion, and Assembling into Three-Dimensional Freestanding Tube Arrays via a Triphasic Reaction.

Converting nitrobenzene to freestanding polyaniline tube arrays has been successfully carried out in a "water-oil-water" triphasic reaction system, where catalytic reduction of nitrobenzene to aniline and aniline polymerization reactions were synergistically integrated. With optimized control over molecular diffusion and reaction at separate solid/liquid and liquid/liquid interfaces, polyaniline nanostructures could be synthesized with different morphologies. The paired molecular diffusion and reaction rate is revealed as the dominating factor that determines the feasibility of the reaction system to produce a patterned array structure. Slow molecular diffusion leads to a better ordered three-dimensional (3D) assembling structure. This work demonstrates a new approach to control 3D assembling structures with integrated control on diffusion and reaction across multiple liquid/liquid interfaces.

Facing the solid waste of cotton straw and plastic mulch film mixture in China: Centralized or decentralized pyrolysis facility?

The widespread use of plastic mulch film (PMF) has led to significant environmental pollution, with PMF residues dispersed and mixed with straw and soil, posing challenges for recycling. Here, we proposed the mobile pyrolysis facility for the cotton straw and mulch film mixture (CMM) to mitigate the collection, storage, and transportation costs, while the application of co-pyrolysis technology for CMM conversion could improve the added value of products. Additionally, centralized combustion power generation and centralized pyrolysis systems were also established to evaluate and compare their sustainability from economic and environmental perspectives. Results showed that mobile pyrolysis has better economic performance than the centralized scenarios, due to its high internal rate of return (31 %) and significant net present value (29.21 M USD). Meanwhile, the mobile pyrolysis facility achieved a GWP of -1.298 kgCO2-eq/kg, reducing emissions by 70.79 % and 38.82 % compared to the two centralized scenarios. In conclusion, mobile pyrolysis technology provides a promising solution for PMF residue recycling because of its economically competitive approach with a lower carbon footprint.

A negative-carbon footprint process with mixed biomass feedstock maximizes conversion efficiency, product value and CO2 mitigation.

The great variety of biomass species offers unique features for synergistic optimization of process outcomes. In this work, spent mushroom substrate and bagasse with optimize ratio were processed to produce value-added products of activated carbon and biofuel yet achieve negative CO2 emission. By integrating experimental characterization, this work uses process simulation, techno-economic analysis and life-cycle assessment to evaluate the techno-economic viability and CO2 footprint of processes with single or dual-/mixed-biomass feedstocks. The combination of biomass species provides unique match of the production of flue gas and primary carbon that is critical for the optimization of mass and energy flow. Such combination has been demonstrated effective to improve product yield and energy efficiency. Results show that mixed biomass feedstock offers favourable figures such as high carbon efficiency of 66.74%, short payback period of 3.16 years, considerable net present value of 80.48 million dollars, and low GWP of -2.37 kg CO2-eq.

Advanced Material-Oriented Biomass Precise Reconstruction: A Review on Porous Carbon with Inherited Natural Structure and Created Artificial Structure by Post-Treatment.

Manufacturing of porous carbon with biomass resources is intensively investigated in recent decades. The diversity of biomass species and great variety of processing methods enable the structural richness of porous carbon as well as their wide applications. This review specifically focuses on the structure of biomass-derived porous carbon either inherited from natural biomass or created by post-treatment. The intrinsic structure of plant biomass is briefly introduced and the utilization of the unique structures at different length-scales is discussed. In term of post-treatment, the structural features of activated carbon by traditional physical and chemical activation are summarized and compared in a wide spectrum of biomass species, statistical analysis is performed to evaluate the effectiveness of different activation methods in creating specific pore structures. The similar pore structure of biomass-derived carbon and coal-derived carbon suggests a promising replacement with more sustainable biomass resources in producing porous carbon. In summary, using biomass as porous carbon precursor endows the flexibility of using its naturally patterned microstructure and the tunability of controlled pore-creation by post-treatment.

Techno-economic analysis of biomass processing with dual outputs of energy and activated carbon.

Biomass utilization is facing great challenge mainly due to the low profit margin of biomass products. Bio-energy plants using gasification and liquefaction technologies are barely surviving, while biomass to activated carbon (AC) route has been demonstrated economically successful. In this work, spent mushroom substrate was used to produce AC and fuel gas with two different processes using internal flue gas and external air as activation agents, respectively. Experimental work was conducted to produce input data for Aspen Plus simulation including processing temperature, flue gas composition, AC yield, etc. Techno-economic analysis was performed, which reveals a great economic potential of integrating AC production in biomass processing. Air activation has obvious advantage in economic benefits, while the risk of precise temperature control and operation stability needs to be carefully evaluated in large-scale production. Flue gas activation is more reliable and it also generates less CO2 that is beneficial for the long-term operation.

Polyelectrolyte cellulose gel with PEG/water: Toward fully green lubricating grease.

Developing a fully green lubricant is an urgent need due to the growing consciousness of environmental protection and dwindling resources. In this work, fully green gel lubricants were developed out of cellulose derivatives as gelator and mixture of water and poly(ethylene glycol) 200 (PEG 200) as the base fluid. The non-ionic hydroxyethyl cellulose (HEC) and anionic sodium carboxymethyl cellulose (NaCMC) were chosen to understand the effect of ionic and non-ionic gelators on the thermal, rheological and the tribological properties of the gel lubricant. HEC or NaCMC is demonstrated as effective additive to reduce wear, stabilize friction coefficient and enhance the thermal stability of developed lubricants. It is shown that anionic gelator will result in producing lower friction and wear in comparison to non-ionic gelator, which may be attributed to the possible tribo-film formation due to the negative charge in the NaCMC molecules and its larger molecular weight.

Fat mimicking compounds as grease thickeners in Poly(ethylene glycol)/water: Adopting the solution from history.

Water-based lubricants are thought to be the next generation green lubricants, however, there are very few developments of aqueous grease lubricants. Here, water-based grease lubricants were developed using the food fat replacers. The concept of using fat replacers was inspired by the historical usage of fat as a lubricant. Dextrins were chosen as the fat replacers and mixture of water and PEG as the base fluid. Dextrins with different molecular weights were selected to study its effect on the rheological, tribological and thermal behavior of the gels. It was found that only higher molecular weight dextrins will form the colloidal gels, whereas low molecular weight dextrins will form the colloidal solution. The SEM images of the dried samples showed the agglomerated micro-spherical network with the void to hold the base fluid. It was found that, at an optimum concentration, the fat replacers showed 35-58% lower friction and 29-41% lower wear than the pure PEG200/water solution regardless of their molecular weight. The spherical shaped colloidal particles will form the film over the metal surface by nano-filling and these particles will act as nano-bearings which will reduce the wear and friction. These gel lubricants can be used where the highly biodegradable and bio-compatible green lubricant is needed.

Holistically Engineered Polymer-Polymer and Polymer-Ion Interactions in Biocompatible Polyvinyl Alcohol Blends for High-Performance Triboelectric Devices in Self-Powered Wearable Cardiovascular Monitorings.

The capability of sensor systems to efficiently scavenge their operational power from stray, weak environmental energies through sustainable pathways could enable viable schemes for self-powered health diagnostics and therapeutics. Triboelectric nanogenerators (TENG) can effectively transform the otherwise wasted environmental, mechanical energy into electrical power. Recent advances in TENGs have resulted in a significant boost in output performance. However, obstacles hindering the development of efficient triboelectric devices based on biocompatible materials continue to prevail. Being one of the most widely used polymers for biomedical applications, polyvinyl alcohol (PVA) presents exciting opportunities for biocompatible, wearable TENGs. Here, the holistic engineering and systematic characterization of the impact of molecular and ionic fillers on PVA blends' triboelectric performance is presented for the first time. Triboelectric devices built with optimized PVA-gelatin composite films exhibit stable and robust triboelectricity outputs. Such wearable devices can detect the imperceptible skin deformation induced by the human pulse and capture the cardiovascular information encoded in the pulse signals with high fidelity. The gained fundamental understanding and demonstrated capabilities enable the rational design and holistic engineering of novel materials for more capable biocompatible triboelectric devices that can continuously monitor vital physiological signals for self-powered health diagnostics and therapeutics.

Two important factors of selecting lignin as efficient lubricating additives in poly (ethylene glycol): Hydrogen bond and molecular weight.

Lignin, one of the most abundant natural polymers, has been successfully used as an effective lubricant additive with high value. The chemical structure of lignin is very diverse and strongly affected by both the source of lignin (i.e. plant species) and the lignin extraction process. In this work, a series of lignin from different biomass sources (hard or soft wood) and extraction process (organosolv with or without acid catalyst) has been successfully incorporated into poly(ethylene glycol) (PEG) and fortified lubricating properties were achieved. The effects of different lignin on the rheological, thermal and tribological properties of the lignin/EG lubricants were systematically investigated by different characterization techniques. Lignin in PEG significantly improves the lubricating property, where a wear reduction of 93.8% was observed. The thermal and lubrication properties of the PEG lubricants filled with different kinds of lignin are tightly related to the synergistic state of hydrogen bonding and molecular weight distribution. Lignin with broader molecular weight distribution and higher hydroxyl content shows better adhesion on metal surfaces and strengthened lubricating film, which could be used as the efficient lubricating additives. This work provides a criterion for selecting appropriate lignin as the efficient lubricant additive and accelerates the application of lignin.

The stiffness-thermal conduction relationship at the composite interface: the effect of particle alignment on the long-range confinement of polymer chains monitored by scanning thermal microscopy.

The polymer/filler interface is usually considered as a thermal barrier in composites due to the mismatch of the phonon frequency across the interface. How the interface plays its role in thermal conduction has not yet been fully understood. In this work, scanning thermal microscopy is used to map the probe current across the composite interface and force-displacement curves are obtained to assess the polymer stiffness. The microscale stiffness-thermal conduction relationship is investigated at the composite interface in three representative cases: a single aggregated particle domain, two neighboring particle domains and two parallelly aligned particle chains. In the studied poly(vinyl alcohol) (PVA)/Fe3O4 composites, it is revealed that the interface property dominates the thermal conduction behavior rather than particle percolation. The long range order of polymer chains surrounding the particle domains is responsible for the enhanced crystallinity and thermal conductivity of the composites. With magnetic alignment of Fe3O4 particles, PVA crystallinity and thermal conductivity can be further enhanced. The macroscopic thermal conductivity measurement is highly consistent with the microscale observation. Specifically, with only 2.3 vol% loading of Fe3O4 in PVA, the thermal conductivity can be increased by 56% to 0.42 W m-1 K-1. By the magnetic alignment of the particles at the same loading, 133% enhancement of thermal conductivity (∼0.63 W m-1 K-1) can be achieved. This work presents an experimental study on the exploration of the interface property-thermal conductivity relationship in differently structured micro-domains and reveals the positive role of the composite interface in thermal conduction.

Expedited Phonon Transfer in Interfacially Constrained Polymer Chain along Self-Organized Amino Acid Crystals.

In this work, poly(vinyl alcohol) (PVA)/amino acid (AA) composites were prepared by a self-organized crystallization process. Five different AAs (cysteine, aspartic acid, glutamic acid, ornithine, and lysine) were selected based on their similar functional groups but different molecular structures. The different PVA-AA interactions in the five PVA/AA composites lead to two crystal patterns, i.e., continuous network (cysteine and lysine) and discrete particles (glutamic acid, ornithine, and aspartic acid). Scanning thermal microscopy is then applied to map the distribution of thermal conduction in these composites. It is found that the interface surrounding the crystals plays a dominating role in phonon transport where the polymer chains are greatly restrained by the interfacial confinement effect. Continuous crystal network builds up a continuous interface that facilitates phonon transfer while phonon scattering occurs in discrete crystalline structures. Significantly improved thermal conductivity of ∼0.7 W/m·K is observed in PVA/cysteine composite with AA loading of 8.4 wt %, which corresponds to a 170% enhancement as compared to pure PVA. The strong PVA-AA molecular interaction and self-organized crystal structure are considered the major reasons for the unique interface property and superior thermal conductivity.

Engineering Hydrogen Bonding Interaction and Charge Separation in Bio-Polymers for Green Lubrication.

Synthetic additives are widely used in lubricants nowadays to upgrade lubrication properties. The potential of integrating sustainable components in modern lubricants has rarely been studied yet. In this work, two sustainable resources lignin and gelatin have been synergistically incorporated into ethylene glycol (EG), and their tribological properties were systematically investigated. The abundant hydrogen bonding sites in lignin and gelatin as well as their interchain interaction via hydrogen bonding play the dominating roles in tuning the physicochemical properties of the mixture and improving lubricating properties. Moreover, the synergistic combination of lignin and gelatin induces charge separation of gelatin that enables its preferable adsorption on the friction surface through electrostatic force and forms a robust lubrication layer. This layer will be strengthened by lignin through the interpolymer chain hydrogen bonding. At an optimized lignin:gelatin mass ratio of 1:1 and 19 wt % loading of each in EG, the friction coefficient can be greatly stabilized and the wear loss was reduced by 89% compared to pure EG. This work presents a unique synergistic phenomenon between gelatin and lignin, where hydrogen bonding and change separation are revealed as the key factor that bridges the individual components and improves overall lubricating properties.

Grafting heteroelement-rich groups on graphene oxide: Tuning polarity and molecular interaction with bio-ionic liquid for enhanced lubrication.

Two different heteroelement-rich molecules have been successfully grafted on graphene oxide (GO) sheets which were then used as lubricant additives in bio-ionic liquid. The grafting was processed with reactions between GO sheets and synthesized heteroelement-rich molecules (Imidazol-1-yl phosphonic dichloride and 1H-1,2,4-triazol-1-yl phosphonic dichloride, respectively). The modified GO (m-GO) was added into [Choline][Proline] ([CH][P]) bio-ionic liquid, and has been demonstrated effective additive in promoting lubrication. Different characterization techniques have been utilized to study the reaction between GO and the two modifiers. The effect of molecular structure of the modifiers on the rheological and tribological properties of m-GO/[CH][P] lubricants was systematically investigated. Both theoretical calculation and experimental results demonstrated that the introduced heteroelement-rich groups are beneficial to increase the robustness of lubrication film by intensified hydrogen bonding and enhance the lubricant/friction surface adhesion by increased polarity of the m-GO. As a result, the interfacial lubrication could be significantly improved by these newly developed m-GO/[CH][P] lubricants.

Paving the Thermal Highway with Self-Organized Nanocrystals in Transparent Polymer Composites.

Phonon transfer is greatly scattered in traditional polymer composites due to the unpaired phonon frequency at the polymer/filler interface. A key innovation of this work is to build continuous crystal network by self-organization and utilize it as "thermal highway" that circumvents the long-existing interfacial thermal barrier issue in traditional composites. By tuning the molecular diffusion rate of dicarboxylic acids (oxalic acid, malonic acid, and succinic acid), different crystal structures including skeletal, dendrite, diffusion-limited aggregates, and spherulite were synthesized in PVA film. These continuous crystal structures benefit the efficient phonon transfer in the composites with minimized interfacial scattering and lead to a significant thermal conductivity enhancement of up to 180% compared to that of pure polymer. Moreover, the transparent feature of these composite films provides additional benefits in display applications. The post heat treatment effect on the thermal conductivity of the composite films shows a time-dependent behavior. These uniquely structured polymer/crystal composites are expected to generate significant impacts in thermal management applications.

Ionic Grease Lubricants: Protic [Triethanolamine][Oleic Acid] and Aprotic [Choline][Oleic Acid].

Ionic liquid lubricants or lubricant additives have been studied intensively over past decades. However, ionic grease serving as lubricant has rarely been investigated so far. In this work, novel protic [triethanolamine][oleic acid] and aprotic [choline][oleic acid] ionic greases are successfully synthesized. These ionic greases can be directly used as lubricants without adding thickeners or other additives. Their distinct thermal and rheological properties are investigated and are well-correlated to their tribological properties. It is revealed that aprotic ionic grease shows superior temperature- and pressure-tolerant lubrication properties over those of protic ionic grease. The lubrication mechanism is studied, and it reveals that strong physical adsorption of ionic grease onto friction surface plays a dominating role for promoted lubrication instead of tribo-chemical film formation.