Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications.

Transition metal dichalcogenides (TMDs) are a promising class of layered materials in the post-graphene era, with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior. Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties, providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs. The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable (opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts (0-100%). Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase, band alignment/structure, carrier density, and surface reactive activity, enabling novel and promising applications. This review comprehensively elaborates on atomically substitutional engineering in TMD layers, including theoretical foundations, synthetic strategies, tailored properties, and superior applications. The emerging type of ternary TMDs, Janus TMDs, is presented specifically to highlight their typical compounds, fabrication methods, and potential applications. Finally, opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

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.

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.

Aqueous Synthesis, Doping, and Processing of n-Type Ag2Se for High Thermoelectric Performance at Near-Room-Temperature.

Herein, we have successfully synthesized binary Ag2Se, composite Ag0:Ag2Se, and ternary Cu+:Ag2Se through an ambient aqueous-solution-based approach in a one-pot reaction at room temperature and atmospheric pressure without involving high-temperature heating, multiple-processes treatment, and organic solvents/surfactants. Effective controllability over phases and compositions/components are demonstrated with feasibility for large-scale production through an exquisite alteration in reaction parameters especially pH for enhancing and understanding thermoelectric properties. Thermoelectric ZT reaches 0.8-1.1 at near-room-temperature for n-type Ag2Se and Cu+ doping further improves to 0.9-1.2 over a temperature range of 300-393 K, which is the largest compared to that reported by wet chemistry methods. This improvement is related to the enhanced electrical conductivity and the suppressed thermal conductivity due to the incorporation of Cu+ into the lattice of Ag2Se at very low concentrations (x%Cu+:Ag2Se, x = 1.0, 1.5, and 2.0).

Advances in photothermal nanomaterials for biomedical, environmental and energy applications.

Materials that exhibit photothermal effect have attracted enormous research interests due to their ability to strongly absorb light and effectively transform it into heat for a wide range of applications in biomedical, environmental and energy related fields. The past decade has witnessed significant advances in the preparation of a variety of photothermal materials, mainly due to the emergence of many nano-enabled new materials, such as plasmonic metals, stoichiometric/non-stoichiometric semiconductors, and the newly emerging MXenes. These photothermal nanomaterials can be hybridized with other constituents to form functional hybrids or composites for achieving enhanced photothermal performance. In this review, we present the fundamental insight of inorganic photothermal materials, including their photothermal conversion mechanisms/properties as well as their potential applications in various fields. Emphasis is placed on strategic approaches for improving their light harvesting and photothermal conversion capabilities through engineering their nanostructured size, shape, composition, bandgap and so on. Lastly, the underlying challenges and perspectives for future development of photothermal nanomaterials are proposed.

Tunable Nitrogen-Doping of Sulfur Host Nanostructures for Stable and Shuttle-Free Room-Temperature Sodium-Sulfur Batteries.

Room-temperature sodium-sulfur batteries have potential in stationary applications, but challenges such as loss of active sulfur and low electrical conductivity must be solved. Nitrogen-doped nanocarbon host cathodes have been employed in metal-sulfur batteries: polar interactions mitigate the loss of sulfur, while the conductive nanostructure addresses the low conductivity. Nevertheless, these two properties run contrary to each other as greater nitrogen-doping of nanocarbon hosts is associated with lower conductivity. Herein, we investigate the polarity-conductivity dilemma to determine which of these properties have the stronger influence on cycling performance. Lower carbonization temperatures produce more pyridinic nitrogen and pyrrolic nitrogen, which from density functional theory calculations preferentially bind discharge products (Na2S and short-chain polysulfides). Despite its lower conductivity, the highly doped composite showed better Coulombic efficiency and stability, retaining a high capacity of 980 mAh g(S)-1 after 800 cycles. Our findings represent a paradigm shift where nitrogen-doping should be prioritized in designing shuttle-free, long-life sodium-sulfur batteries.

Synthesis and optical and electronic properties of one-dimensional sulfoxonium-based hybrid metal halide (CH3)3SOPbI3.

We report the synthesis and optical and electronic properties of a one-dimensional sulfoxonium-based hybrid metal halide in an orthorhombic crystal system with a Pnma space group. To provide direct insights, a method is developed to calculate tolerance factors with the ionic radii of non-spherical cations from X-ray crystallographic data.

Facile solvothermal approach to pristine tetrahedrite nanostructures with unique multiply-voided morphology.

Tetrahedrite (Cu12Sb4S13) is a highly promising environmentally friendly material for energy conversion applications but its synthesis generally requires several days of heating at high temperature conditions. To fabricate tetrahedrite in a more rapid way and under milder conditions, solvothermal synthesis has been recently explored. However, a common problem faced when using this technique is the formation of significant amounts of other ternary Cu-Sb-S phases along with the desired tetrahedrite phase. Here, we present an optimized solvothermal procedure for synthesizing high-purity samples of tetrahedrite at moderate temperatures and reasonable heating times. The as-prepared samples are single-crystalline nanometer-sized structures having multiple voids or pores. By modifying certain experimental parameters such as the reaction temperature and heating time, we have shown that we can alter the nanocrystal architecture. The formation mechanism was investigated and it was found that these porous tetrahedrite nanostructures are a product of the non-classical oriented aggregation growth process. Porosity in nanomaterials is known to improve material properties and is desirable in many important applications so the construction of void-containing tetrahedrite nanostructures will potentially extend the utility of tetrahedrite to a wider range of applications. In this work, we explore its possible use as a photothermal-responsive drug delivery vehicle.

Electrostatic-Driven Exfoliation and Hybridization of 2D Nanomaterials.

Here, direct and effective electrostatic-driven exfoliation of tungsten trioxide (WO3 ) powder into atomically thin WO3 nanosheets is demonstrated for the first time. Experimental evidence together with theoretical simulations clearly reveal that the strong binding of bovine serum albumin (BSA) on the surface of WO3 via the protonation of NH2 groups in acidic conditions leads to the effective exfoliation of WO3 nanosheets under sonication. The exfoliated WO3 nanosheets have a greatly improved dispersity and stability due to surface-protective function of BSA, and exhibit a better performance and unique advantages in applications such as visible-light-driven photocatalysis, high-capacity adsorption, and fast electrochromics. Further, simultaneous exfoliation and hybridization of WO3 and MoS2 nanosheets are demonstrated to form hybrid WO3 /MoS2 nanosheets through respective electrostatic and hydrophobic interaction processes. In addition, this electrostatic-driven exfoliation strategy is applied to exfoliate ultrathin black-phosphorus nanosheets from its bulk to exhibit a greatly improved stability due to the surface protection by BSA. Overall, the work presented not only presents a facile and effective route to fabricate 2D materials but also brings more opportunities to exploit unusual exotic and synergistic properties in resulting hybrid 2D materials for novel applications.

Recent Progress in Energy-Driven Water Splitting.

Hydrogen is readily obtained from renewable and non-renewable resources via water splitting by using thermal, electrical, photonic and biochemical energy. The major hydrogen production is generated from thermal energy through steam reforming/gasification of fossil fuel. As the commonly used non-renewable resources will be depleted in the long run, there is great demand to utilize renewable energy resources for hydrogen production. Most of the renewable resources may be used to produce electricity for driving water splitting while challenges remain to improve cost-effectiveness. As the most abundant energy resource, the direct conversion of solar energy to hydrogen is considered the most sustainable energy production method without causing pollutions to the environment. In overall, this review briefly summarizes thermolytic, electrolytic, photolytic and biolytic water splitting. It highlights photonic and electrical driven water splitting together with photovoltaic-integrated solar-driven water electrolysis.

Metal nanostructures for non-enzymatic glucose sensing.

This review covers the recent development of metal nanostructures in electrochemical non-enzymatic glucose sensing. It highlights a variety of nanostructured materials including noble metals, other transition metals, bimetallic systems, and their hybrid with carbon-based nanomaterials. Particularly, attention is devoted to numerous approaches that have been implemented for improving the sensors performance by tailoring size, shape, composition, effective surface area, adsorption capability and electron-transfer properties. The correlation of the metal nanostructures to the glucose sensing performance is addressed with respect to the linear concentration range, sensitivity and detection limit. In overall, this review provides important clues from the recent scientific achievements of glucose sensor nanomaterials which will be essentially useful in designing better and more effective electrocatalysts for future electrochemical sensing industry.

Preparation, Functionality, and Application of Metal Oxide-coated Noble Metal Nanoparticles.

With their remarkable properties and wide-ranging applications, nanostructures of noble metals and metal oxides have been receiving significantly increased attention in recent years. The desire to combine the properties of these two functional materials for specific applications has naturally prompted research in the design and synthesis of novel nanocomposites, consisting of both noble metal and metal-oxide components. In this review, particular attention is given to core-shell type metal oxide-coated noble metal nanostructures (i.e., metal@oxide), which display potential utility in applications, including photothermal therapy, catalytic conversions, photocatalysis, molecular sensing, and photovoltaics. Emerging research directions and areas are envisioned at the end to solicit more attention and work in this regard.

Amorphous ruthenium nanoparticles for enhanced electrochemical water splitting.

This paper demonstrates an optimized fabrication of amorphous Ru nanoparticles through annealing at various temperatures ranging from 150 to 700 °C, which are used as water oxidation catalyst for effective electrochemical water splitting under a low overpotential of less than 300 mV. The amorphous Ru nanoparticles with short-range ordered structure exhibit an optimal and stable electrocatalytic activity after annealing at 250 °C. Interestingly, a small quantity of such Ru nanoparticles in a thin film on fluorine-doped tin oxide glass is also effectively driven by a conventional crystalline silicon solar cell that has excellent capability for harvesting visible light. Remarkably, it achieves an overall solar-to-hydrogen efficiency of 11.3% in acidic electrolyte.

Fabrication of bimetallic Cu/Au nanotubes and their sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

Herein, we report a facile two-step approach to produce gold-incorporated copper (Cu/Au) nanostructures through controlled disproportionation of the Cu(+)-oleylamine complex at 220 °C to form copper nanowires and the subsequent reaction with Au(3+) at different temperatures of 140, 220 and 300 °C. In comparison with copper nanowires, these bimetallic Cu/Au nanostructures exhibit their synergistic effect to greatly enhance glucose oxidation. Among them, the shape-controlled Cu/Au nanotubes prepared at 140 °C show the highest electrocatalytic activity for non-enzymatic glucose sensing in alkaline solution. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to the initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

Preparation of porosity-controlled calcium carbonate by thermal decomposition of volume content-variable calcium carboxylate derivatives.

We demonstrate a novel approach for synthesizing porosity-controlled calcium carbonate by one-step thermal decomposition of various calcium carboxylate derivatives as well as their mixtures with different molar ratios. By varying the volume content of calcium in the calcium compounds or mixtures, the resulting porous calcium carbonate exhibits distinct porosity and structures that are very promising for various applications.

Temperature and chemical bonding-directed self-assembly of cobalt phosphide nanowires in reaction solutions into vertical and horizontal alignments.

The preparation of vertically or horizontally aligned self-assemblies of CoP nanowires is demonstrated for the first time by aging them in the reaction solution for a sufficient time at 20 or 0 °C. This strategy opens up a way for exploring the controlled self-assembly of various highly anisotropic nanostructures into long-range ordered structures with collective properties.

Chiral palladium template promoted asymmetric hydrophosphination reaction between diphenylphosphine and vinylphosphines.

An organopalladium complex containing ortho-metalated (S)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric hydrophosphination reactions between diphenylphosphine and (E)- or (Z)-diphenyl-1-propenylphosphine in high regio- and stereoselectivities under mild conditions. Hydrophosphination of (Z)-diphenyl-1-propenylphosphine with diphenylphosphine gave (S)-(-)-prophos as the major product. Using the same chiral metal template, the corresponding hydrophosphination reaction with (E)-diphenyl-1-propenylphosphine gave (R)-(+)-prophos predominantly. The hydrophosphination reactions generated the asymmetric diphosphines as bidentate chelates on the chiral naphthylamine palladium templates. The template products obtained undergo cis-trans isomerization in solution to form an equilibrium mixture of regioisomers. X-ray analysis of the major template products obtained from the hydrophosphination of (Z)-diphenyl-1-propenylphosphine reveals that the two regioisomers are cocrystallized in a 1:1 ratio. The naphthylamine auxiliary could be removed chemoselectively from the template products by treatment with concentrated hydrochloric acid to form the corresponding optically pure neutral complexes [(R)- or (S)-(prophos)PdCl(2)]. Subsequently, the (R)- and (S)-dichloro complexes undergo ligand displacement with aqueous cyanide to generate the corresponding optically pure diphosphine ligands in high yields. Mechanistic pathways explaining the stereoselectivity of the chiral organopalladium template promoted hydrophosphination reactions are also proposed.