In Situ Characterization Techniques for Electrochemical Nitrogen Reduction Reaction.

The electrochemical reduction of nitrogen to produce ammonia is pivotal in modern society due to its environmental friendliness and the substantial influence that ammonia has on food, chemicals, and energy. However, the current electrochemical nitrogen reduction reaction (NRR) mechanism is still imperfect, which seriously impedes the development of NRR. In situ characterization techniques offer insight into the alterations taking place at the electrode/electrolyte interface throughout the NRR process, thereby helping us to explore the NRR mechanism in-depth and ultimately promote the development of efficient catalytic systems for NRR. Herein, we introduce the popular theories and mechanisms of the electrochemical NRR and provide an extensive overview on the application of various in situ characterization approaches for on-site detection of reaction intermediates and catalyst transformations during electrocatalytic NRR processes, including different optical techniques, X-ray-based techniques, electron microscopy, and scanning probe microscopy. Finally, some major challenges and future directions of these in situ techniques are proposed.

3D Printing Elastocaloric TiNiCu Thermoelectric Shape Memory Alloys.

The development of new thermoelectric conversion and cooling materials is an important means of addressing global climate and heat emissions in the future. While heavy and toxic elements like tellurium and lead are traditionally used to make thermoelectric materials with poor mechanical properties, recent decades have seen a gradual push towards greener and more sustainable alternatives. One such potential alternative material for thermoelectric and thermal management applications would be the Nitinol (TiNi) shape memory alloy, due to their superior mechanical properties. In this study, we have investigated the use of 3D melt printing techniques that can be used to achieve thermoelectric performance and efficiency of elastic memory alloys below 500 °C.　The electrical and thermal properties of TiNiCu materials and their relation to morphology were investigated. All the alloys show similar effect sizes, their fatigue behavior is however different. By adjusting the composition of Ti and Ni elements and we have obtained memory alloys with high thermoelectric properties, with a 50% increase in power factor and a 100% increase in ZT values.

Innovative biomaterials for food packaging: Unlocking the potential of polyhydroxyalkanoate (PHA) biopolymers.

Polyhydroxyalkanoate (PHA) biopolyesters show a good balance between sustainability and performance, making them a competitive alternative to conventional plastics for ecofriendly food packaging. With an emphasis on developments over the last decade (2014-2024), this review examines the revolutionary potential of PHAs as a sustainable food packaging material option. It also delves into the current state of commercial development, competitiveness, and the carbon footprint associated with PHA-based products. First, a critical examination of the challenges experienced by PHAs in terms of food packaging requirements is undertaken, followed by an assessment of contemporary strategies addressing permeability, mechanical properties, and processing considerations. The various PHA packaging end-of-life options, including a comprehensive overview of the environmental impact and potential solutions will also be discussed. Finally, conclusions and future perspectives are elucidated with a view of prospecting PHAs as future green materials, with a blend of performance and sustainability of food packaging solutions.

Low vaporization enthalpy of modified chitosan hydrogel for high performance solar evaporator.

The high vaporization enthalpy of water attributed to the strong hydrogen bonds between water molecules is limiting the performance of solar evaporators. This work demonstrates a deliberate attempt to significantly reduce the vaporization enthalpy of water through the introduction of weak water-amine hydrogen bond interactions in hydrogel evaporators. In this article, bio-based chitosan-agarose/multiwalled carbon nanotube hydrogel film evaporators (CAMFEs) exhibit larger vaporization enthalpy reduction with the presence of primary amine groups in chitosan. An interplay between vaporization enthalpy reduction and water diffusivity leads to an optimal ratio of chitosan to agarose = 7:1 (CAMFE7) showing an impressive evaporation rate of 4.13 kg m-2 h-1 under 1 sun irradiation. CAMFE7 also exhibits excellent salt resistance, with a stable water evaporation rate, using brine water of up to 10 % salinity under continuous 1 sun irradiation. The high mechanical robustness together with its scalability makes CAMFE7 a highly promising material for practical drinking water production.

Reprogrammable, Sustainable, and 3D-Printable Cellulose Hydroplastic.

Modern human societies are highly dependent on plastic materials, however, the bulk of them are non-renewable commodity plastics that cause pollution problems and consume large amounts of energy for their thermal processing activities. In this article, a sustainable cellulose hydroplastic material and its composites, that can be shaped repeatedly into various 2D/3D geometries using just water are introduced. In the wet state, their high flexibility and ductility make it conducive for the shaping to take place. In the ambient environment, the wet hydroplastic transits spontaneously into rigid materials with its intended shape in a short time of <30 min despite a thickness of hundreds of microns. They also possess humidity resistance and are structurally stable in highly humid environments. Given their excellent mechanical properties, geometry reprogrammability, bio-based, and biodegradable nature, cellulose hydroplastic poses as a sustainable alternative to traditional plastic materials and even "green" thermoplastics. This article also demonstrates the possibility of 3D-printing these hydroplastics and the potential of employing them in electronics applications. The demonstrated hydroshapable structural electronic components show capability in performing electronic functions, load-bearing ability and geometry versatility, which are attractive features for lightweight, customizable and geometry-unique electronic devices.

Bio-Polyethylene and Polyethylene Biocomposites: An Alternative toward a Sustainable Future.

Polyethylene (PE), a highly prevalent non-biodegradable polymer in the field of plastics, presents a waste management issue. To alleviate this issue, bio-based PE (bio-PE), derived from renewable resources like corn and sugarcane, offers an environmentally friendly alternative. This review discusses various production methods of bio-PE, including fermentation, gasification, and catalytic conversion of biomass. Interestingly, the bio-PE production volumes and market are expanding due to the growing environmental concerns and regulatory pressures. Additionally, the production of PE and bio-PE biocomposites using agricultural waste as filler materials, highlights the growing demand for sustainable alternatives to conventional plastics. According to previous studies, addition of ≈50% defibrillated corn and abaca fibers into bio-PE matrix and a compatibilizer, results in the highest Young's modulus of 4.61 and 5.81 GPa, respectively. These biocomposites have potential applications in automotive, building construction, and furniture industries. Moreover, the advancement made in abiotic and biotic degradation of PE and PE biocomposites is elucidated to address their environmental impacts. Finally, the paper concludes with insights into the opportunities, challenges, and future perspectives in the sustainable production and utilization of PE and bio-PE biocomposites. In summary, production of PE and bio-PE biocomposites can contribute to a cleaner and sustainable future.

Advances in Cellulose-Based Composites for Energy Applications.

The various forms of cellulose-based materials possess high mechanical and thermal stabilities, as well as three-dimensional open network structures with high aspect ratios capable of incorporating other materials to produce composites for a wide range of applications. Being the most prevalent natural biopolymer on the Earth, cellulose has been used as a renewable replacement for many plastic and metal substrates, in order to diminish pollutant residues in the environment. As a result, the design and development of green technological applications of cellulose and its derivatives has become a key principle of ecological sustainability. Recently, cellulose-based mesoporous structures, flexible thin films, fibers, and three-dimensional networks have been developed for use as substrates in which conductive materials can be loaded for a wide range of energy conversion and energy conservation applications. The present article provides an overview of the recent advancements in the preparation of cellulose-based composites synthesized by combining metal/semiconductor nanoparticles, organic polymers, and metal-organic frameworks with cellulose. To begin, a brief review of cellulosic materials is given, with emphasis on their properties and processing methods. Further sections focus on the integration of cellulose-based flexible substrates or three-dimensional structures into energy conversion devices, such as photovoltaic solar cells, triboelectric generators, piezoelectric generators, thermoelectric generators, as well as sensors. The review also highlights the uses of cellulose-based composites in the separators, electrolytes, binders, and electrodes of energy conservation devices such as lithium-ion batteries. Moreover, the use of cellulose-based electrodes in water splitting for hydrogen generation is discussed. In the final section, we propose the underlying challenges and outlook for the field of cellulose-based composite materials.

Bio-Polypropylene and Polypropylene-based Biocomposites: Solutions for a Sustainable Future.

Polypropylene (PP) is among the most widely used commodity plastics in our everyday life due to its low cost, lightweight, easy processability, and exceptional chemical, thermo-mechanical characteristics. The growing awareness on energy and environmental crisis has driven global efforts for creating a circular economy via developing sustainable and eco-friendly alternatives to traditional plastics produced from fossil fuels for a variety of end-use applications. This review paper presents a brief outline of the emerging bio-based PP derived from renewable natural resources, covering its production routes, market analysis and potential utilizations. This contribution also provides a comprehensive review of the PP-based biocomposites produced with diverse green fillers generated from agro-industrial wastes, with particular emphasis on the structural modification, processing techniques, mechanical properties, and practical applications. Furthermore, given that the majority of PP products are currently destined for landfills, research progress on enhancing the degradation of PP and its biocomposites is also presented in light of the environmental concerns. Finally, a brief conclusion with discussions on challenges and future perspectives are provided.

Thermoelectric Silver-Based Chalcogenides.

Heat is abundantly available from various sources including solar irradiation, geothermal energy, industrial processes, automobile exhausts, and from the human body and other living beings. However, these heat sources are often overlooked despite their abundance, and their potential applications remain underdeveloped. In recent years, important progress has been made in the development of high-performance thermoelectric materials, which have been extensively studied at medium and high temperatures, but less so at near room temperature. Silver-based chalcogenides have gained much attention as near room temperature thermoelectric materials, and they are anticipated to catalyze tremendous growth in energy harvesting for advancing internet of things appliances, self-powered wearable medical systems, and self-powered wearable intelligent devices. This review encompasses the recent advancements of thermoelectric silver-based chalcogenides including binary and multinary compounds, as well as their hybrids and composites. Emphasis is placed on strategic approaches which improve the value of the figure of merit for better thermoelectric performance at near room temperature via engineering material size, shape, composition, bandgap, etc. This review also describes the potential of thermoelectric materials for applications including self-powering wearable devices created by different approaches. Lastly, the underlying challenges and perspectives on the future development of thermoelectric materials are discussed.

Concepts and Emerging Trends for Structural Battery Electrolytes.

The structural battery is a multifunctional energy storage device that aims to address the weight and volume efficiency issues that conventional batteries face, especially in electric transportation. By combining the functions of mechanical load bearing and energy storage, structural batteries can reduce the reliance on, or even eventually replace the main power source in an electric vehicle or a drone. However, one of the key challenges to be addressed before achieving multifunctionality in structural batteries would be the design of a suitable multifunctional structural battery electrolyte. The structural battery electrolyte is the constituent that provides mechanical integrity under flexural loads or impact and hence determines the electrochemical and much of the mechanical performance of a structural battery device. This concept paper aims to cover the key considerations and challenges facing the design of structural battery electrolytes. In addition, the main approaches to surmount these challenges are highlighted, keeping design aspects like sustainability and recyclability in view.

Toughened Hydrogels for 3D Printing of Soft Auxetic Structures.

Materials with negative Poisson's ratio have attracted considerable attention and offered high potential applications as biomedical devices due to their ability to expand in every direction when stretched. Although negative Poisson's ratio has been obtained in various base materials such as metals and polymers, there are very limited works on hydrogels due to their intrinsic brittleness. Herein, we report the use of methacrylated cellulose nanocrystals (CNCMAs) as a macro-cross-linking agent in poly(2-hydroxyethyl methacrylate) (pHEMA) hydrogels for 3D printing of auxetic structures. Our developed CNCMA-pHEMA hydrogels exhibit significant improvements in mechanical properties, which is attributed to the coexistence of multiple chemical and physical interactions between the pHEMA and CNCMAs. Structures printed by using CNCMA-pHEMA hydrogels show auxetic behavior with greatly enhanced toughness and stretchability compared to the hydrogel with a traditional cross-linking agent. Such strong and tough auxetic hydrogels would contribute toward establishing advanced flexible implantable devices such as biodegradable oesophageal self-expandable stents.

Recent Advances in Host-Guest Supramolecular Hydrogels for Biomedical Applications.

The recognition-directed host-guest interaction is recognized as a valuable tool for creating supramolecular polymers. Functional hydrogels constructed through the dynamic and reversible host-guest complexation are endowed with a great many appealing features, such as superior self-healing, injectability, flexibility, stimuli-responsiveness and biocompatibility, which are crucial for biological and medicinal applications. With numerous topological structures and host-guest combinations established previously, recent breakthroughs in this area mostly focus on further improvement and fine-tuning of various properties for practical utilizations. The current contribution provides a comprehensive overview of the latest developments in host-guest supramolecular hydrogels, with a particular emphasis on the innovative molecular-level design strategies and hydrogel formation methodologies targeting at a wide range of active biomedical domains, including drug delivery, 3D printing, wound healing, tissue engineering, artificial actuators, biosensors, etc. Furthermore, a brief conclusion and discussion on the steps forward to bring these smart hydrogels to clinical practice is also presented.

Recent advances in the development of biodegradable PHB-based toughening materials: Approaches, advantages and applications.

Polyhydroxybutyrate (PHB) is a natural biodegradable polymer that is produced by many types of bacteria as an intracellular energy storage material. Due to its numerous advantages such as biodegradability, biocompatibility, availability and with physical properties comparable to petroleum-based thermoplastics, PHB is a potential substitute in biomedical and packaging fields. However, several physical drawbacks, such as high production cost, thermal instability, and poor mechanical properties, due to secondary crystallization and slow nucleation rate, limit its competition with traditional plastics in industrial and biomedical applications. Thereby, many attempts have been employed to improve the material performance of toughened PHB so as to achieve greater competitiveness and sustainability. In this review, the most recent developments of PHB-based toughening materials are discussed with respect to their approaches and strategies, which includes: drawing and thermal treatment, blending with materials from natural sources and synthetic polymers, as well as forming reinforced composites with natural fibers and inorganic fillers. The alternation of PHB chemical structure to form various types of functional copolymers with enhanced materials performance is also summarized. The expanded utilization of these newly developed sophisticated PHB materials as engineering materials and the biomedical significance in different domains are also addressed.