Recent Progress in Metal Phosphorous Chalcogenides: Potential High-Performance Electrocatalysts.

Since the discovery of graphene, research on the family of 2D materials has been a thriving field. Metal phosphorous chalcogenides (MPX3 ) have attracted renewed attention due to their distinctive physical and chemical properties. The advantages of MPX3 , such as tunable layered structures, unique electronic properties, thermodynamically appropriate band alignments and abundant catalytic active sites on the surface, make MPX3 material great potential in electrocatalysis. In this review, the applications of MPX3 electrocatalysts in recent years, including hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction, are summarized. Structural regulation, chemical doping and multi-material composite that are often effective and practical research methods to further optimize the catalytic properties of these materials, are introduced. Finally, the challenges and opportunities for electrocatalytic applications of MPX3 materials are discussed. This report aims to advance future efforts to develop MPX3 and related materials for electrocatalysis.

Co Nanoparticles Confined in Mesoporous Mo/N Co-Doped Polyhedral Carbon Frameworks towards High-Efficiency Oxygen Reduction.

Exploiting effective non-noble metal electrocatalysts for oxygen reduction reaction (ORR) is crucial for fuel cells and metal-air batteries. Herein, we designed and fabricated Co nanoparticles confined in Mo/N co-doped polyhedral carbon frameworks (Co-NP/MNCF) derived from polyoxometalate-encapsuled metal-organic framework, which showed comparable ORR performance with commercial Pt/C and a larger diffusion-limited current density. Moreover, the Co-NP/MNCF also exhibited excellent ORR stability and methanol tolerance. These appealing performances can be attributed to the porosity regulation and heteroatom doping of metal-organic framework derived polyhedral carbon frameworks, which could be beneficial for the exposure of more active sites, the optimization of electronic structure and the mass transfer of electrolyte/electron/ion.

Dynamical approach to the atomic and electronic structures of the ductile semiconductor Ag2S.

Silver sulfide in monoclinic phase (α-Ag2S) has attracted significant attention owing to its metal-like ductility and promising thermoelectric properties near room temperature. However, first-principles studies on this material by density functional theory calculations have been challenging as both the symmetry and atomic structure of α-Ag2S predicted from such calculations are inconsistent with experimental findings. Here, we propose that a dynamical approach is imperative for correctly describing the structure of α-Ag2S. The approach is based on a combination of ab initio molecular dynamics simulation and deliberately chosen density functional considering both proper treatment of the van der Waals interaction and on-site Coulomb interaction. The obtained lattice parameters and atomic site occupations of α-Ag2S are in good agreement with experimental data. A stable phonon spectrum at room temperature can be obtained from this structure, which also yields a bandgap in accord with experimental measurements. The dynamical approach thus paves the way for studying this important ductile semiconductor in not only thermoelectric but also optoelectronic applications.

Distinct Impact of Alkali-Ion Doping on Electrical Transport Properties of Thermoelectric p-Type Polycrystalline SnSe.

Recent findings about ultrahigh thermoelectric performance in SnSe single crystals have stimulated related research on this simple binary compound, which is focused mostly on its polycrystalline counterparts, and particularly on electrical property enhancement by effective doping. This work systematically investigated the thermoelectric properties of polycrystalline SnSe doped with three alkali metals (Li, Na, and K). It is found that Na has the best doping efficiency, leading to an increase in hole concentration from 3.2 × 10(17) to 4.4 × 10(19) cm(-3) at room temperature, accompanied by a drop in Seebeck coefficient from 480 to 142 µV/K. An equivalent single parabolic band model was found adequate to capture the variation tendency of Seebeck coefficient with doping levels within a wide range. A mixed scattering of carriers by acoustic phonons and grain boundaries is suitable for numerically understanding the temperature-dependence of carrier mobility. A maximum ZT of ∼0.8 was achieved in 1% Na- or K-doped SnSe at 800 K. Possible strategies to improve the mobility and ZT of polycrystals were also proposed.

Electrical and thermal transport properties of Pb(1-x)Sn(x)Se solid solution thermoelectric materials.

Both lead selenide (PbSe) and tin selenide (SnSe) are promising thermoelectric compounds consisting of earth-abundant elements, between which solid solutions can be formed over a wide composition range. This study investigated the electrical and thermal transport properties of n-type Pb1-xSnxSe (x = 0, 0.01, 0.05, 0.1 and 0.15) solid solutions with emphasis on the effect of Sn substitution. Small amounts of Sn substitution (x ≤ 0.1) increased electrical conductivity but showed less influence on the Seebeck coefficient, leading to improved power factors, which were revealed to be associated with the generation of native Se vacancies. The electrical conductivity tended to decrease when x > 0.1 due to the alloying effect, consequently the thermoelectric figure of merit was not further increased, even though the thermal conductivity can be reduced by increasing Sn content. A maximum dimensionless figure of merit ZT of up to 1.0 was obtained at moderate temperature (773 K) for the composition of Pb0.9Sn0.1Se.

Thermoelectric transport properties of pristine and Na-doped SnSe(1-x)Te(x) polycrystals.

SnSe, a "simple" and "old" binary compound composed of earth-abundant elements, has been reported to exhibit a high thermoelectric performance in single crystals, which stimulated recent interest in its polycrystalline counterparts. This work investigated the electrical and thermal transport properties of pristine and Na-doped SnSe1-xTex polycrystals prepared by mechanical alloying and spark plasma sintering. It is revealed that SnSe1-xTex solid solutions are formed when x ranges from 0 to 0.2. An energy barrier scattering mechanism is suitable for understanding the electrical conducting behaviour observed in the present SnSe polycrystalline materials, which may be associated with abundant defects at grain boundaries. The thermal conductivity was greatly reduced upon Te substitution due to alloy scattering of phonons as well explained by the Debye model. Due to the increased carrier concentration by Na-doping, thermoelectric figure of merit (ZT) was enhanced in the whole temperature range with a maximum value of 0.72 obtained at a relatively low temperature (773 K) for Sn0.99Na0.01Se0.84Te0.16.

Ductile P-Type AgCu(Se,S,Te) Thermoelectric Materials.

Ductile inorganic thermoelectric (TE) materials open a new approach to develop high-performance flexible TE devices. N-type Ag2(S,Se,Te) and p-type AgCu(Se,S,Te) pseudoternary solid solutions are two typical categories of ductile inorganic TE materials reported so far. Comparing with the Ag2(S,Se,Te) pseudoternary solid solutions, the phase composition, crystal structure, and physical properties of AgCu(Se,S,Te) pseudoternary solid solutions are more complex, but their relationships are still ambiguous now. In this work, via systematically investigating the phase composition, crystal structure, mechanical, and TE properties of about 60 AgCu(Se,S,Te) pseudoternary solid solutions, the comprehensive composition-structure-property phase diagrams of the AgCuSe-AgCuS-AgCuTe pseudoternary system is constructed. By mapping the complex phases, the "ductile-brittle" and "n-p" transition boundaries are determined and the composition ranges with high TE performance and inherent ductility are illustrated. On this basis, high performance p-type ductile TE materials are obtained, with a maximum zT of 0.81 at 340 K. Finally, flexible in-plane TE devices are prepared by using the AgCu(Se,S,Te)-based ductile TE materials, showing high output performance that is superior to those of organic and inorganic-organic hybrid flexible devices.

FeCu bimetallic clusters for efficient urea production via coupling reduction of carbon dioxide and nitrate.

Urea electrosynthesis has appeared to meet the nitrogen cycle and carbon neutrality with energy-saving features. Copper can co-electrocatalyze among CO2 and nitrogen species to generate urea, however developing effective electrocatalysts is still an obstacle. Here, we developed a nitrogen-doped porous carbon loaded with FeCu clusters that convert CO2 and NO3- into urea, with the highest Faradaic efficiency of 39.8 % and yield rate of 1024.6 µg h-1 mgcat.-1, under optimized ambient conditions, exceeding that at the Fe or Cu homogeneous sites. Furthermore, a favorable CN coupling pathway originates from *NHCO and *NHCONO two intermediates with lower free energy barriers on FeCu dual active sites are verified through in-situ Fourier transform infrared spectroscopy and theoretical calculations. This research might provide deep insights into coupling mechanisms and investigation of efficient catalysts for green urea production.

High-Throughput Strategies in the Discovery of Thermoelectric Materials.

Searching for new high-performance thermoelectric (TE) materials that are economical and environmentally friendly is an urgent task for TE society, but the advancements are greatly limited by the time-consuming and high cost of the traditional trial-and-error method. The significant progress achieved in the computing hardware, efficient computing methods, advance artificial intelligence algorithms, and rapidly growing material data have brought a paradigm shift in the investigation of TE materials. Many electrical and thermal performance descriptors are proposed and efficient high-throughput (HTP) calculation methods are developed with the purpose to quickly screen new potential TE materials from the material databases. Some HTP experiment methods are also developed which can increase the density of information obtained in a single experiment with less time and lower cost. In addition, machine learning (ML) methods are also introduced in thermoelectrics. In this review, the HTP strategies in the discovery of TE materials are systematically summarized. The applications of performance descriptor, HTP calculation, HTP experiment, and ML in the discovery of new TE materials are reviewed. In addition, the challenges and possible directions in future research are also discussed.

Easily constructed porous silver films for efficient catalytic CO2 reduction and Zn-CO2 batteries.

For the electroreduction of carbon dioxide into high value-added chemicals, highly active and selective catalysts are crucial, and metallic silver is one of the most intriguing candidate materials available at a reasonable cost. Herein, through a novel two-step operation of Ag paste/SBA-15 coating and HF etching, porous silver films on a commercial carbon paper with a waterproofer (p-Ag/CP) could be easily fabricated on a large scale as highly efficient carbon dioxide reduction reaction (CO2RR) electrocatalysts with a CO Faraday efficiency (FECO) as high as 96.7% at -1.0 V vs. the reversible hydrogen electrode (RHE), and it still reaches up to 90% FECO over applied potentials ranging from -0.8 to -1.1 V vs. the RHE. Meanwhile, the membrane electrode assembly (MEA) utilizing the p-Ag/CP catalyst has achieved a current density, FECO, and stability of ∼60 mA cm-2, >91%, and 11 h, respectively. Furthermore, the assembled aqueous Zn-CO2 battery using p-Ag/CP cathode yielded a peak power density of 0.34 mW cm-2, 75 charge-discharge cycles for 25 h, and 64% FECO at 2.5 mA cm-2. Compared with flat Ag/CP, the significant enhancement in the CO2RR activity of p-Ag/CP was mainly attributed to the distinctive porous structure and an improved three-phase boundary, which is capable of inducing the stabilization of *COOH intermediates, increased active specific surface areas, fast electron transfer kinetic and mass transportation. Further, theoretical calculations revealed that p-Ag/CP possessed an optimized energy barrier for *COOH intermediates.

High Thermoelectric Power Factors in Plastic/Ductile Bulk SnSe2 -Based Crystals.

The recently discovered plastic/ductile inorganic thermoelectric (TE) materials open a new avenue for the fabrication of high-efficiently flexible TE devices, which can utilize the small temperature difference between human body and environment to generate electricity. However, the maximum power factor (PF) of current plastic/ductile TE materials is usually around or less than 10 µW cm-1 K-2 , much lower than the classic brittle TE materials. In this work, a record-high PF of 18.0 µW cm-1 K-2 at 375 K in plastic/ductile bulk SnSe2 -based crystals is reported, superior to all the plastic inorganic TE materials and flexible organic TE materials reported before. The origin of such high PF is from the modulation of material's stacking forms and polymorph crystal structures via simultaneously doping Cl/Br at Se-site and intercalating Cu inside the van der Waals gap, leading to the significantly enhanced carrier concentrations and mobilities. An in-plane fully flexible TE device made of the plastic/ductile SnSe2 -based crystals is successfully developed to show a record-high normalized maximum power density to 0.18 W m-1 under a temperature difference of 30 K. This work indicates that the plastic/ductile material can realize high TE power factor to achieve large output electric power density in flexible TE technology.

Copper Phosphide Nanowires as High-Performance Catalysts for Urea-Assisted Hydrogen Evolution in Alkaline Medium.

Water electrolysis represented a promising avenue for the large-scale production of high-purity hydrogen. However, the high overpotential and sluggish reaction rates associated with the anodic oxygen evolution reaction (OER) posed significant obstacles to efficient water splitting. To tackle these challenges, the urea oxidation reaction (UOR) emerged as a more favorable thermodynamic alternative to OER, offering both the energy-efficient hydrogen evolution reaction (HER) and the potential for the treating of urea-rich wastewater. In this work, a two-step methodology comprising nanowire growth and phosphating treatment was employed to fabricate Cu3P nanowires on Cu foam (Cu3P-NW/CF) catalysts. These novel catalytic architectures exhibited notable efficiencies in facilitating both the UOR and HER in alkaline solutions. Specifically, within urea-containing electrolytes, the UOR manifested desirable operational potentials of 1.43 V and 1.65 V versus the reversible hydrogen electrode (vs. RHE) to reach the current densities of 10 and 100 mA cm-2, respectively. Concurrently, the catalyst displayed a meager overpotential of 60 mV for the HER at a current density of 10 mA cm-2. Remarkably, the two-electrode urea electrolysis system, exploiting the designed catalyst as both the cathode and anode, demonstrated an outstanding performance, attaining a low cell voltage of 1.79 V to achieve a current density of 100 mA cm-2. Importantly, this voltage is preferable to the conventional water electrolysis threshold in the absence of urea molecules. Moreover, our study shed light on the potential of innovative Cu-based materials for the scalable fabrication of electrocatalysts, energy-efficient hydrogen generation, and the treatment of urea-rich wastewater.

A dual-functional Bi-doped Co3O4 nanosheet array towards high efficiency 5-hydroxymethylfurfural oxidation and hydrogen production.

Here, we report that a Bi-doped Co3O4 nanosheet array grown on Ni foam can selectively catalyze HMF-to-FDCA oxidation at ambient conditions. The catalyst shows a faradaic efficiency of 97.7%, a yield rate of 362.5 µmol h-1, and a conversion of nearly 100%, surpassing those of pristine Co3O4. Furthermore, when the catalyst was adopted as both the anode and cathode in a two-electrode system, H2 and FDCA can be produced simultaneously.

Heterogeneous Ni-MoN nanosheet-assembled microspheres for urea-assisted hydrogen production.

Electrocatalytic water splitting is a promising technology for sustainable hydrogen (H2) production; however, it is restricted by the kinetically sluggish anodic oxygen evolution reaction (OER). Replacing OER with urea oxidation reaction (UOR) with low thermodynamic potential can simultaneously improve the energy efficiency of H2 production and purify urea-containing wastewater. Here we report a facile assembly-calcination two-step method to synthesize heterogeneous Ni-MoN nanosheet-assembled microspheres (Ni-MoN NAMs). The nanosheet-assembled structure and the synergistic metallic Ni-MoN heterogeneous interface endow the Ni-MoN NAMs with good OER (1.52 V@10 mA cm-2), UOR (1.28 V@10 mA cm-2), and hydrogen evolution reaction (HER, 0.16 V@10 mA cm-2) activity. The two-electrode urea electrolysis cell with Ni-MoN NAMs as both the cathode and anode requires an extremely low cell voltage of 1.41 V to afford 20 mA cm-2, which is 0.3 V lower than that of the water electrolyzer, paving the way for energy-saving H2 production.

Ag2 Q-Based (Q = S, Se, Te) Silver Chalcogenide Thermoelectric Materials.

Thermoelectric technology provides a promising solution to sustainable energy utilization and scalable power supply. Recently, Ag2 Q-based (Q = S, Se, Te) silver chalcogenides have come forth as potential thermoelectric materials that are endowed with complex crystal structures, high carrier mobility coupled with low lattice thermal conductivity, and even exceptional plasticity. This review presents the latest advances in this material family, from binary compounds to ternary and quaternary alloys, covering the understanding of multi-scale structures and peculiar properties, the optimization of thermoelectric performance, and the rational design of new materials. The "composition-phase structure-thermoelectric/mechanical properties" correlation is emphasized. Flexible and hetero-shaped thermoelectric prototypes based on Ag2 Q materials are also demonstrated. Several key problems and challenges are put forward concerning further understanding and optimization of Ag2 Q-based thermoelectric chalcogenides.

Single atomic cerium sites anchored on nitrogen-doped hollow carbon spheres for highly selective electroreduction of nitric oxide to ammonia.

Electrocatalytic nitric oxide reduction reaction (NORR) at ambient environments not only offers a promising strategy to yield ammonia (NH3) but also degrades the NO contaminant; however, its application depends on searching for high-performance catalysts. Herein, we present single atomic Ce sites anchored on nitrogen-doped hollow carbon spheres that are capable of electro-catalyzing NO reduction to NH3 in an acidic solution, achieving a maximal Faradaic efficiency of 91 % and a yield rate of 1023 µg h-1 mgcat.-1 at -0.7 V vs RHE for NH3 formation, both of which outperform these on Ce nanoclusters and approach the best-reported results. Meanwhile, the single atomic Ce catalyst shows good structural and electrochemical stability during the 30-h NO electrolysis. Furthermore, when the single atomic Ce catalyst was used as cathodic material in a proof-of-concept of Zn-NO battery, it delivers a maximal power density of 3.4 mW cm-2 and a high NH3 yield rate of 309 µg h-1 mgcat.-1. Theoretical simulations suggest that the Ce-N4 active moiety can not only activate NO molecules via a strong electronic interaction but also reduce the free energy barrier of *NO transition to *NOH intermediate as the limiting step, and therefore boosting the NORR kinetics and suppressing the competitive hydrogen evolution.

Amorphous Fe-Co oxide as an active and durable bifunctional catalyst for the urea-assisted H2 evolution reaction in seawater.

In this study, we prepared amorphous iron-cobalt oxide through the dealloying of trimetallic FeCoAl, showing excellent performance in both urea oxidation and hydrogen evolution reactions (UOR and HER) in alkaline seawater. The catalyst demonstrated stable UOR and HER activity during long-term operations due to the abundant active sites and oxygen vacancies. The catalyst required applied potentials of 1.52 and -0.185 V to yield 100 mA cm-2 for the UOR and HER, respectively. Moreover, when used as both the cathode and anode, the electrolyzer required a working voltage of 1.68 V to yield 100 mA cm-2 for urea-assisted hydrogen production.

Co doping promotes the alkaline overall seawater electrolysis performance over MnPSe3 nanosheets.

Herein, two-dimensional cobalt-doped MnPSe3 nanosheets (CMPS) were constructed, which served as an outstanding bifunctional catalyst for alkaline seawater splitting, i.e., offering the current density of 10 mA cm-2 with applied overpotentials of 59 and 300 mV for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. The assembled two-electrode system of CMPS//CMPS also demonstrated excellent catalytic activity (10 mA cm-2, 1.59 V) and can remain stable for more than 100 h. Moreover, the theoretical calculations showed that CMPS features a suitable H* adsorption beneficial for the HER, as well as a lower free energy barrier favorable for the OER.

Bifunctional bimetallic oxide nanowires for high-efficiency electrosynthesis of 2,5-furandicarboxylic acid and ammonia.

It is an appealing avenue for electrosyntheis of high-valued chemicals at both anode and cathode by coupling 5-hydroxymethylfurfural (HMF) oxidation and nitrate reduction reactions simultaneously, while the development such bifunctional electrocatalysts is still in its infancy with dissatisfied selectivity and low yield rate. Here, we first report that Zn-doped Co3O4 nanowires array can be served as an efficient and robust dual-functional catalyst for HMF oxidation and nitrate reduction at ambient conditions. Specifically, the catalyst shows a faradaic efficiency of 91 % and a yield rate of 241.2 µmol h-1 cm-2 for 2,5-furandicarboxylic acid formation together with a high conversion of nearly 100 % at a potential of 1.40 V. It also displays good cycling stability. Besides, the catalyst is capable of catalyzing the reduction of nitrate to NH3, giving a maximal faradaic efficiency of 92 % and a peak NH3 yield rate of 4.65 mg h-1 cm-2 at a potential of -0.70 V. These results surpass those obtained using pristine Co3O4 and are comparable to those of state-of-the-art electrocatalysts. Moreover, the catalyst is further employed as the cathode catalyst to assemble a Zn-nitrate battery, giving a peak power density of 5.24 mW cm-2 and a high yield rate of 0.72 mg h-1 cm-2. Theoretical simulations further reveal that Zn-doping favors the adsorption and dissociation of nitrate and HMF species and reduces the energy barrier as well. Our work demonstrates the potential interest of Co3O4-based materials for the highly selective production of valuable feedstocks via ambient electrolysis.

Covalently Assembled Black Phosphorus/Conductive C3N4 Hybrid Material for Flexible Supercapacitors Exhibiting a Superlong 30,000 Cycle Durability.

Black phosphorus (BP) has been demonstrated as a promising electrode material for supercapacitors. Currently, the main limitation of its practical application is the low electrical conductivity and poor structure stability. Hence, BP-based supercapacitors usually severely suffer from low capacitance and poor cycling stability. Herein, a chemically bridged BP/conductive g-C3N4 (BP/c-C3N4) hybrid is developed via a facile ball-milling method. Covalent P-C bonds are generated through the ball-milling process, effectively preventing the structural distortion of BP induced by ion transport and diffusion. In addition, the overall electrical conductivity is significantly enhanced owing to the sufficient coupling between BP and highly conductive c-C3N4. Moreover, the imbalanced charge distribution around the C atom can induce the generation of a local electric field, facilitating the charge transfer behavior of the electrode material. As a result, the BP/c-C3N4-20:1 flexible supercapacitor (FSC) exhibits an outstanding volumetric capacitance of 42.1 F/cm3 at 0.005 V/s, a high energy density of 5.85 mW h/cm3, and a maximum power density of 15.4 W/cm3. More importantly, the device delivers excellent cycling stability with no capacitive loss after 30,000 cycles.