Lun Pan

Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH-Value Electrochemical and Photocatalytic Hydrogen Evolution

The development of highly active, universal, and stable inexpensive electrocatalysts/cocatalysts for hydrogen evolution reaction (HER) by morphology and structure modulations remains a great challenge. Herein, a simple self-template strategy was developed to synthesize hollow Co-based bimetallic sulfide (MxCo3-xS4, M = Zn, Ni, and Cu) polyhedra with superior HER activity and stability. Homogenous bimetallic metal-organic frameworks are transformed to hollow bimetallic sulfides by solvothermal sulfidation and thermal annealing. Electrochemical measurements and density functional theory computations show that the combination of hollow structure and homoincorporation of a second metal significantly enhances the HER activity of Co3S4. Specifically, the homogeneous doping in Co3S4 lattice optimizes the Gibbs free energy for H* adsorption and improves the electrical conductivity. Impressively, hollow Zn0.30Co2.70S4 exhibits electrocatalytic HER activity better than most of the reported nobel-metal-free electrocatalysts over a wide pH range, with overpotentials of 80, 90, and 85 mV at 10 mA cm(-2) and 129, 144, and 136 mV at 100 mA cm(-2) in 0.5 M H2SO4, 0.1 M phosphate buffer, and 1 M KOH, respectively. It also exhibits photocatalytic HER activity comparable to that of Pt cocatalyst when working with organic photosensitizer (Eosin Y) or semiconductors (TiO2 and C3N4). Furthermore, this catalyst shows excellent stability in the electrochemical and photocatalytic reactions. The strategy developed here, i.e., homogeneous doping and self-templated hollow structure, provides a way to synthesize transition metal sulfides for catalysis and energy conversion.

Water-Mediated Promotion of Dye Sensitization of TiO2 under Visible Light

Preadsorbed water along with surrounding bulk water significantly modulates the surface electronic structure of TiO(2), switches the adsorption mode of dyes, and promotes dye sensitization of TiO(2) under visible-light irradiation. This opens a door toward facile improvement in the efficiency of photodegradation of dyes and dye-sensitized solar cells under visible-light irradiation without any complicated and expensive surface modulation.

Titanium-Defected Undoped Anatase TiO2 with p-Type Conductivity, Room-Temperature Ferromagnetism, and Remarkable Photocatalytic Performance

Defects are critically important for metal oxides in chemical and physical applications. Compared with the often studied oxygen vacancies, engineering metal vacancies in n-type undoped metal oxides is still a great challenge, and the effect of metal vacancies on the physiochemical properties is seldom reported. Here, using anatase TiO2, the most important and widely studied semiconductor, we demonstrate that metal vacancies (VTi) can be introduced in undoped oxides easily, and the presence of VTi results in many novel physiochemical properties. Anatase Ti0.905O2 was synthesized using solvothermal treatment of tetrabutyl titanate in an ethanol-glycerol mixture and then thermal calcination. Experimental measurements and DFT calculations on cell lattice parameters show the unstoichiometry is caused by the presence of VTi rather than oxygen interstitials. The presence of VTi changes the charge density and valence band edge of TiO2, and an unreported strong EPR signal at g = 1.998 presents under room temperature. Contrary to normal n-type and nonferromagnetic TiO2, Ti-defected TiO2 shows inherent p-type conductivity with high charge mobility, and room-temperature ferromagnetism stronger than Co-doped TiO2 nanocrystalline. Moreover, Ti-defected TiO2 shows much better photocatalytic performance than normal TiO2 in H2 generation (4.4-fold) and organics degradation (7.0-fold for phenol), owing to the more efficient charge separation and transfer in bulk and at semiconductor/electrolyte interface. Metal-defected undoped oxides represent a unique material; this work demonstrates the possibility to fabricate such material in easy and reliable way and thus provides new opportunities for multifunctional materials in chemical and physical devices.

Tungsten Oxides for Photocatalysis, Electrochemistry, and Phototherapy.

The conversion, storage, and utilization of renewable energy have all become more important than ever before as a response to ever-growing energy and environment concerns. The performance of energy-related technologies strongly relies on the structure and property of the material used. The earth-abundant family of tungsten oxides (WOx ≤3 ) receives considerable attention in photocatalysis, electrochemistry, and phototherapy due to their highly tunable structures and unique physicochemical properties. Great breakthroughs have been made in enhancing the optical absorption, charge separation, redox capability, and electrical conductivity of WOx ≤3 through control of the composition, crystal structure, morphology, and construction of composite structures with other materials, which significantly promotes the efficiency of processes and devices based on this material. Herein, the properties and synthesis of WOx ≤3 family are reviewed, and then their energy-related applications are highlighted, including solar-light-driven water splitting, CO2 reduction, and pollutant removal, electrochromism, supercapacitors, lithium batteries, solar and fuel cells, non-volatile memory devices, gas sensors, and cancer therapy, from the aspect of function-oriented structure design and control.

Morphology Evolution of TiO2 Facets and Vital Influences on Photocatalytic Activity

Modulation of anatase toward highly active facets has been attracting much attention, but the mechanism and photoactivity are still ambiguous. Here we demonstrate the inherent mechanisms for facets nucleation and morphology evolution, and clarify some vital influences of facets and surface nature on the photoactivity. Simply tuning the Ti/F ratio in the synthetic mixture leads to single anatase crystal exposed with different facets like {001}, {010}, or {110}. And complex sphere structure exposed with {001} facets can be formed by secondary nucleation and growth. Prolonging the hydrothermal treatment time causes selective etching on {001} facets, whereas defluorination via thermal calcination produces many pores on the surface. The photodegradation of positively and negatively charged, and zwitterionic dyes indicates that the type of reactant, adsorption mode and surface area play significant roles in photocatalysis. This work makes a step toward understanding the formation of facet-mediated structure and designing highly active materials for environmental remediation, hydrogen production, and dye-sensitized solar cells.

Highly selective self-condensation of cyclic ketones using MOF-encapsulating phosphotungstic acid for renewable high-density fuel

Transferring biomass-derived cyclic ketones such as cyclopentanone and cyclohexanone to a mono-condensed product through aldol self-condensation has great potential for the synthesis of a renewable high-density fuel. However, the selectivity is low for numerous catalysts due to the rapid formation of di-condensed by products. Herein, MIL-101-encapsulating phosphotungstic acid is synthesized to catalyze the self-condensation with selectivity of more than 95%. PTA clusters are uniformly dispersed in MOF cages and decrease the empty space (pore size), which provides both acidic sites and shape-selective capability. The optimal PTA amount decreases corresponding to the increase of reactant size. The shape-selectivity is also realized by changing the pore size of MOF such as from MIL-101 to MIL-100. Moreover, the catalyst is resistant to PTA leaching and performs stably after 5 runs. After hydrodeoxygenation of the mono-condensed product, high-density biofuels with densities of 0.867 g ml−1 and 0.887 g ml−1 were obtained from cyclopentanone and cyclohexanone, respectively. This study not only provides a promising route for the production of high-density biofuel but also suggests the advantage of MOF-based catalysts for shape-selective catalysis involving large molecular size.

Efficient water oxidation through strongly coupled graphitic C3N4 coated cobalt hydroxide nanowires

The development of low cost and durable electrocatalysts for the oxygen evolution reaction (OER) for water splitting remains a great challenge. Here, we developed strongly coupled hybrid nanowires (NWs) of anion (Cl− and CO−) doped cobalt hydroxide coated with nanosheets of graphitic carbon nitride (Co(OH)2@g-C3N4) through an in situ hydrothermal method. With 5% g-C3N4 added in the synthesis, we obtained perfectly coated Co(OH)2 by g-C3N4 nanosheets with an overall diameter of ∼110 nm and a coating layer of ∼10 nm. The structural and compositional analyses confirm the strong interaction between g-C3N4 and Co(OH)2 that makes the hybrid highly effective for the OER. As a result Co(OH)2@g-C3N4 NWs exhibit an excellent over-potential of 0.32 V at 10 mA cm−2 as well as extraordinary stability, which are better than those of the state-of-the-art noble metals (IrO2 and RuO2) and most reported Co- and C3N4-based electrocatalysts although both Co(OH)2 and g-C3N4 separately display very fair performance. Furthermore, a combination of Co(OH)2@g-C3N4 and Pt/C delivers a current density of 80 mA cm−2 at 1.9 V for overall water splitting.

Fabrication of zero to three dimensional nanostructured molybdenum sulfides and their electrochemical and photocatalytic applications

Transition metal dichalcogenides (TMDs) are emerging as promising materials, particularly for electrochemical and photochemical catalytic applications, and among them molybdenum sulfides have received tremendous attention due to their novel electronic and optoelectronic characteristics. Several review articles have summarized the recent progress on TMDs but no critical and systematic summary exists about the nanoscale fabrication of MoS2 with different dimensional morphologies. In this review article, first we will summarize the recent progress on the morphological tuning and structural evolution of MoS2 from zero-dimension (0D) to 3D. Then the different engineering methods and the effect of synthesis conditions on structure and morphology of MoS2 will be discussed. Moreover, the corresponding change in the electronic and physicochemical properties of MoS2 induced by structure tuning will also be presented. Further, the applications of MoS2 in various electrochemical systems e.g. hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and supercapacitors as well as photocatalytic hydrogen evolution will be highlighted. The review article will also critically focus on challenges faced by researchers to tune the MoS2 nanostructures and the resulting electrochemical mechanism to enhance their performances. At the end, concluding remarks and future prospects for the development of better MoS2 based nanostructured materials for the aforementioned applications will be presented.

Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions

Abstract Hydrogen evolution reaction (HER) in alkaline medium is currently a point of focus for sustainable development of hydrogen as an alternative clean fuel for various energy systems, but suffers from sluggish reaction kinetics due to additional water dissociation step. So, the state‐of‐the‐art catalysts performing well in acidic media lose considerable catalytic performance in alkaline media. This review summarizes the recent developments to overcome the kinetics issues of alkaline HER, synthesis of materials with modified morphologies, and electronic structures to tune the active sites and their applications as efficient catalysts for HER. It first explains the fundamentals and electrochemistry of HER and then outlines the requirements for an efficient and stable catalyst in alkaline medium. The challenges with alkaline HER and limitation with the electrocatalysts along with prospective solutions are then highlighted. It further describes the synthesis methods of advanced nanostructures based on carbon, noble, and inexpensive metals and their heterogeneous structures. These heterogeneous structures provide some ideal systems for analyzing the role of structure and synergy on alkaline HER catalysis. At the end, it provides the concluding remarks and future perspectives that can be helpful for tuning the catalysts active‐sites with improved electrochemical efficiencies in future.

C-doped ZnO ball-in-ball hollow microspheres for efficient photocatalytic and photoelectrochemical applications

ZnO is an important semiconductor and has been widely used in the field of photocatalysis, solar cell and environmental remediation. Herein, we fabricated C-doped ZnO ball-in-ball hollow microspheres (BHMs) by a facile solvothermal treatment of zinc acetate in ethylene glycol-ethanol mixture. The presence of ethylene glycol (EG) leads to the formation of initial single-layered hollow spheres and then a time-dependent evolution transforms them into uniform BHMs with tunable shell thickness and void space. XPS characterizations reveal that C-dopants are introduced into the lattice of ZnO BHMs, with its concentration increasing with solvothermal time and then becoming saturated in 12h. ZEG-12 (ZnO BHMs with 12-h solvothermal treatment), with an optimal hollow structure and C-doping concentration, performs the best optical absorption capability, efficiency of charge separation and transfer, and mass transfer in reaction media, as proved by SEM, TEM, PL, BET and EIS characterizations. When applied as photocatalyst for organic-pollutant degradation and as photoanode material for PEC water splitting, ZEG-12 exhibits respectively ca. 8.9-fold and 10.5-fold higher activity than pristine ZnO nanoparticles.