Co0 -Coδ+ Interface Double-Site-Mediated C-C Coupling for the Photothermal Conversion of CO2 into Light Olefins.

Solar-driven CO2 hydrogenation into multi-carbon products is a highly desirable, but challenging reaction. The bottleneck of this reaction lies in the C-C coupling of C1 intermediates. Herein, we construct the C-C coupling centre for C1 intermediates via the in situ formation of Co0 -Coδ+ interface double sites on MgAl2 O4 (Co-CoOx /MAO). Our experimental and theoretical prediction results confirmed the effective adsorption and activation of CO2 by the Co0 site to produce C1 intermediates, while the introduction of the electron-deficient state of Coδ+ can effectively reduce the energy barrier of the key CHCH* intermediates. Consequently, Co-CoOx /MAO exhibited a high C2-4 hydrocarbons production rate of 1303 µmol g-1 h-1 ; the total organic carbon selectivity of C2-4 hydrocarbons is 62.5 % under light irradiation with a high ratio (≈11) of olefin to paraffin. This study provides a new approach toward the design of photocatalysts used for CO2 conversion into C2+ products.

Nanostructured Materials for Photothermal Carbon Dioxide Hydrogenation: Regulating Solar Utilization and Catalytic Performance.

Converting carbon dioxide (CO2) into value-added fuels or chemicals through photothermal catalytic CO2 hydrogenation is a promising approach to alleviate the energy shortage and global warming. Understanding the nanostructured material strategies in the photothermal catalytic CO2 hydrogenation process is vital for designing photothermal devices and catalysts and maximizing the photothermal CO2 hydrogenation performance. In this Perspective, we first describe several essential nanomaterial design concepts to enhance sunlight absorption and utilization in photothermal CO2 hydrogenation. Subsequently, we review the latest progress in photothermal CO2 hydrogenation into C1 (e.g., CO, CH4, and CH3OH) and multicarbon hydrocarbon (C2+) products. Finally, the relevant challenges and opportunities in this exciting research realm are discussed. This perspective provides a comprehensive understanding for the light-heat synergy over nanomaterials and instruction for rational photothermal catalyst design for CO2 utilization.

Novel One-Dimensional Nanofiber MnSe/CMK-3 High-Performance Cathode Material for Aluminum Batteries.

Transition metal selenides have shown outstanding performance as cathode materials for aluminum-ion batteries and have thus become a popular choice for cathode materials. Herein, Mn-based carbon fibers (Mn/CNFs) were first synthesized by electrospinning as a precursor, and then MnSe composites were prepared by a melt-diffusion method. However, due to polyselenides and selenides being generated during electrochemical reactions, the cycling stability of MnSe cathode materials is poor. After 200 cycles, the discharge specific capacity is only 176 mA h/g. To suppress the shuttle effect of selenides and polyselenides, a CMK-3-modified separator was used instead of a glass fiber separator. Compared with MnSe-800, the replaced MnSe-800/CMK-3 has a great capacity improvement; the initial discharge specific capacity is 1029.85 mA h/g, which after 3000 cycles, still remains at 297.84 mA h/g. The soft pack battery can still light up the LED normally under different degrees of folding, which proves the application of this material in wearable devices. This work provides a new way to improve the performance of transition metal selenides.

Unveiling the advantages of an ultrathin N-doped carbon shell on self-supported tungsten phosphide nanowire arrays for the hydrogen evolution reaction experimentally and theoretically.

Packaging electrocatalysts with carbon shells offers an opportunity to develop stable and effective hydrogen evolution reaction (HER) materials. Here, an ultrathin N-doped carbon-coated self-supported WP nanowire array (WP@NC NA) hybrid has been synthesized. Owing to the encapsulation of the ultrathin N-doped carbon shell on the WP surface, the as-prepared WP@NC NA hybrid exhibits enhanced physicochemical stability, more active sites, and superior conductivity compared with WP NA without carbon coating. Besides, density functional theory calculations demonstrate that the carbon shell can optimize the hydrogen adsorption step in the acidic HER, and simultaneously facilitate water physical adsorption, water dissociation, and hydroxyl group desorption steps during the alkaline HER. These findings demonstrate the intrinsic mechanism of how a carbon shell promotes the acidic and alkaline HER kinetics, and provide scientific guidance for the packaging design of promising carbon-encapsulating self-supported electrocatalysts.

Rational design of FeOx-MoP@MWCNT composite electrocatalysts toward efficient overall water splitting.

Herein, a series of FeOx-MoP@MWCNT composite electrocatalysts was designed and prepared to investigate the influence of the content of FeOx on the water splitting performance. The optimized FeOx-MoP@MWCNTs-2 exhibits excellent hydrogen and oxygen evolution reaction activity while a cell voltage of 1.51 V with outstanding stability is attained, attributed to the synergistic effect of each component, as evidenced by the experimental and density functional theory results. The observed electrocatalytic activity outperforms current state-of-the-art non-precious metal electrocatalysts.

Open-ended W18O49-filled tungsten dichalcogenide nanotubes grown on a W substrate to efficiently catalyze hydrogen evolution.

A scalable infrared-heating CVD method was developed to grow few-walled WSe2 or WS2 nanotube arrays in situ filled with highly conductive single-crystal W18O49, and a simple pressure control led to their universally uncapped top-ends. Open-ended WS2 nanotubes grown on the W substrate performed excellently as an electrocatalyst to facilitate the HER in acid, contributing to high-density active edge sites and good electronic coupling between the substrate and nanotubes.

Strategies for Semiconductor/Electrocatalyst Coupling toward Solar-Driven Water Splitting.

Hydrogen (H2) has a significant potential to enable the global energy transition from the current fossil-dominant system to a clean, sustainable, and low-carbon energy system. While presently global H2 production is predominated by fossil-fuel feedstocks, for future widespread utilization it is of paramount importance to produce H2 in a decarbonized manner. To this end, photoelectrochemical (PEC) water splitting has been proposed to be a highly desirable approach with minimal negative impact on the environment. Both semiconductor light-absorbers and hydrogen/oxygen evolution reaction (HER/OER) catalysts are essential components of an efficient PEC cell. It is well documented that loading electrocatalysts on semiconductor photoelectrodes plays significant roles in accelerating the HER/OER kinetics, suppressing surface recombination, reducing overpotentials needed to accomplish HER/OER, and extending the operational lifetime of semiconductors. Herein, how electrocatalyst coupling influences the PEC performance of semiconductor photoelectrodes is outlined. The focus is then placed on the major strategies developed so far for semiconductor/electrocatalyst coupling, including a variety of dry processes and wet chemical approaches. This Review provides a comprehensive account of advanced methodologies adopted for semiconductor/electrocatalyst coupling and can serve as a guideline for the design of efficient and stable semiconductor photoelectrodes for use in water splitting.

Nickel-Based (Photo)Electrocatalysts for Hydrogen Production.

Hydrogen is considered a promising energy carrier for replacing traditional fossil fuels. Electrochemical or solar-driven water splitting is a green and sustainable method of producing hydrogen. To lower the overpotential and minimize energy costs, numerous reports have focused on developing noble-metal-free catalysts for hydrogen production, with special attention paid to nickel-based materials. Herein, the current state of research on the use of Ni-based materials as electrocatalysts, cocatalysts, and photoactive materials in hydrogen production is reviewed. Recent research efforts toward the development of various Ni-based (photo)electrocatalysts, their applications in hydrogen production, and the corresponding mechanisms are covered. The approaches used to improve or optimize these materials are summarized, and the key remaining challenges are discussed.

Polyaniline decorated Bi2MoO6 nanosheets with effective interfacial charge transfer as photocatalysts and optical limiters.

Polyaniline (PANI)-decorated Bi2MoO6 nanosheets (BMO/PANI) were prepared by a facile solvothermal method. Different characterization techniques, including X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, diffuse reflectance ultraviolet-visible spectroscopy, photoluminescence spectroscopy, electrochemical impedance spectroscopy, photocurrent spectroscopy, and nanosecond time-resolved emission studies, have been employed to investigate the structure, optical and electrical properties of the BMO/PANI composites. The wide absorption of the samples in the visible light region makes them suitable for nonlinear transmission and photocatalytic activity studies. The associated photocatalytic activity and optical nonlinearities for the BMO/PANI composites are shown to be dependent on the PANI loadings. The rational mechanisms responsible for deteriorating pollutants and improving optical nonlinearities were also proposed, which could be mainly attributed to the efficient interfacial charge transfer and the interfacial electronic interactions between PANI and Bi2MoO6. The photoluminescence spectroscopy, electrochemical impedance spectroscopy, and photocurrent spectroscopy studies confirmed that the interface charge separation efficiency was greatly improved by coupling Bi2MoO6 with PANI. The tuning of photocatalysis and nonlinear optical behaviors with variation in the content of PANI provides an easy way to attain tunable properties, which are exceedingly required in optoelectronics applications.

Graphene Porous Foam Loaded with Molybdenum Carbide Nanoparticulate Electrocatalyst for Effective Hydrogen Generation.

A facile method is developed for the synthesis of graphene porous foam (Gr PF) loaded with dispersed molybdenum carbide (Mo2 C) nanoparticles; the material exhibits effective catalytic activity in the hydrogen evolution reaction (HER). Mo2 C/Gr PF is synthesized by the carbonization of glucose and the carbothermal reduction of hexaammonium molybdate in a confined space defined by the intervals between sodium chloride nanoparticles. The synthesis in the confined space results in thin Gr PF (≈8 nm) loaded with aggregation-free small Mo2 C nanoparticles [(13±2) nm]. The overpotential required for a current density of 20 mA cm(-2) in the electrochemical hydrogen generation is as small as 199 mV in acidic solution and 380 mV in basic solution. The performance is superior to that of a Mo2 C/C composite and compares favorably to those reported for Mo2 C nanostructures. The Mo2 C/Gr PF affords stable water electrolysis in both acidic and basic solution and exhibits nearly 100 % faradaic efficiency. The prominent performance, long-term stability, and high faradic efficiency make Mo2 C/Gr PF a promising HER catalyst for practical hydrogen generation from water electrolysis.

Ni12P5 nanoparticles as an efficient catalyst for hydrogen generation via electrolysis and photoelectrolysis.

The exploitation of a low-cost catalyst is desirable for hydrogen generation from electrolysis or photoelectrolysis. In this study we have demonstrated that nickel phosphide (Ni12P5) nanoparticles have efficient and stable catalytic activity for the hydrogen evolution reaction. The catalytic performance of Ni12P5 nanoparticles is favorably comparable to those of recently reported efficient nonprecious catalysts. The optimal overpotential required for 20 mA/cm(2) current density is 143 ± 3 mV in acidic solution (H2SO4, 0.5 M). The catalytic activity of Ni12P5 is likely to be correlated with the charged natures of Ni and P. Ni12P5 nanoparticles were introduced to silicon nanowires, and the power conversion efficiency of the resulting composite is larger than that of silicon nanowires decorated with platinum particles. This result demonstrates the promising application potential of metal phosphide in photoelectrochemical hydrogen generation.

Tungsten sulfide enhancing solar-driven hydrogen production from silicon nanowires.

Tungsten sulfides, including WS2 (crystalline) and WS3 (amorphous), were introduced to silicon nanowires, and both can promote the photoelectrochemical hydrogen production of silicon nanowires. In addition, more enhancement of energy conversion efficiency can be achieved by the loading of WS3, in comparison with loading of WS2. Polarization curves of WS3 and WS2 suggest that WS3 has higher catalytic activity in the hydrogen evolution reaction than WS2, affording higher energy conversion efficiency in silicon nanowires decorated with WS3. The higher electrocatalytic activity of WS3 correlates with the amorphous structure of WS3 and larger surface area of WS3, which result in more active sites in comparison with crystalline WS2.