Hematite Hollow-Sphere-Array Photoanodes for Efficient Photoelectrochemical Water Splitting.

Constructing 3D nanophotonic structures is regarded as an effective method to realize efficient solar-to-hydrogen conversion. These photonic structures can enhance the absorbance of photoelectrodes by the light trapping effect, promote the charge separation by designable charge transport pathway and provide a high specific surface area for catalytic reaction. However, most 3D structures reported so far mainly focused on the influence of light absorption and lacked a systematic investigation of the overall water splitting process. Herein, hematite hollow-sphere-array photoanodes are fabricated through a facile hydrothermal method with polystyrene templates. Validating by simulations and experiments, the hollow sphere array is proved to enhance the efficiency of light harvesting, charge separation and surface reaction at the same time. With an additional annealing treatment in oxygen, a photocurrent density of 2.26 mA cm-2 at 1.23 V versus reversible hydrogen electrode can be obtained, which is 3.70 times larger than that with a planar structure in otherwise the same system. This work gains an insight into the photoelectrochemical water splitting process, which is valuable for the further design of advancing solar driven water splitting devices.

Surface Facets Reconstruction in Copper-Based Materials for Enhanced Electrochemical CO2 Reduction.

The unavoidable and unpredictable surface reconstruction of metallic copper (Cu) during the electrocatalytic carbon dioxide (CO2) reduction process is a double-edged sword affecting the production of high-value-added hydrocarbon products. It is crucial to control the surface facet reconstruction and regulate the targeted facets/facet interfaces, and further understand the mechanism between activity/selectivity and the reconstructed structure of Cu for CO2 reduction. Based on the current catalyst design methods, a facile strategy combining chemical reduction and electro-reduction is proposed to achieve specified Cu(111) facets and the Cu(110)/(111) interfaces in reconstructed Cu derived from cuprous oxide (Cu2O). The surface facet reconstruction significantly boosted the electrocatalytic conversion of CO2 into multi-carbon (C2+) products comparing to the unmodified catalyst. Theoretical and experimental analyses show that the Cu(110)/(111)s interface between Cu(110) and a small amount of Cu(111) can tailor the reaction routes and lower the reaction energy barrier of C-C coupling to ethylene (C2H4). The work will guide the surface facets reconstruction strategy for Cu-based CO2 electrocatalysts, providing a promising paradigm to understand the structural variation in catalysts.

Monolithic Microparticles Facilitated Flower-Like TiO2 Nanowires for High Areal Capacity Flexible Li-Ion Batteries.

Flexible lithium-ion batteries (FLIBs) are intensively studied using free-standing transition metal oxides (TMOs)-based anode materials. However, achieving high areal capacity TMO-based anode materials is yet to be effectively elucidated owing to the poor adhesion of the active materials to the flexible substrate resulting in low active mass loading, and hence low areal capacity is realized. Herein, a novel monolithic rutile TiO2 microparticles on carbon cloth (ATO/CC) that facilitate the flower-like arrangement of TiO2 nanowires (denoted ATO/CC/OTO) is demonstrated as high areal capacity anode for FLIBs. The optimized ATO/CC/OTO anode exhibits high areal capacity (5.02 mAh cm-2@0.4 mA cm-2) excellent rate capability (1.17 mAh cm-2@5.0 mA cm-2) and remarkable cyclic stability (over 500 cycles). A series of morphological, kinetic, electrochemical, in situ Raman, and theoretical analyses reveal that the rational phase boundaries between the microparticles and nanowires contribute to promoting the Li storage activity. Furthermore, a 16.0 cm2 all-FLIB pouch cell assembled based on the ATO/CC/OTO anode and LiNiCoMnO2 cathode coated on ATO/CC (ATO/CC/LNCM) exhibits impressive flexibility under different folding conditions, creating opportunity for the development of high areal capacity anodes in future flexible energy storage devices.

Emerging porous materials in confined spaces: from chromatographic applications to flow chemistry.

Searching for porous materials that can be employed as solid stationary phases for chromatographic separations, porous membrane matrixes and solid supports for catalysis has become an active research area. Strategies for embedding emerging porous materials in columnar systems and their subsequent applications (separation and catalysis) have been developed, which benefit from the remarkable progress in the discovery and development of porous materials based on metal-organic coordination or dynamic covalent bonding such as metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), porous organic cages, and porous organic polymers. In this review, porous materials that have been confined within capillary columns as packed, monolithic and open tubular columns are discussed. Progress in chromatographic separation and continuous flow catalytic synthesis is reviewed according to three major strategies. Applications of porous materials in membrane-separation fibre membrane systems and microfluidic devices with various functions are also highlighted.

Nitrogen and Phosphorus Codoped Vertical Graphene/Carbon Cloth as a Binder-Free Anode for Flexible Advanced Potassium Ion Full Batteries.

With the fast development in flexible electronic technology, power supply devices with high performance, low-cost, and flexibility are becoming more and more important. Potassium ion batteries (KIBs) have a brilliant prospect for applications benefiting from high voltage, lost cost, as well as similar electrochemistry to lithium ion batteries (LIBs). Although carbon materials have been studied as KIBs anodes, their rate capability and cycling stability are still unsatisfactory due to the large-size potassium ions. Herein, a nitrogen (N) and phosphorus (P) dual-doped vertical graphene (N, P-VG) uniformly grown on carbon cloth (N, P-VG@CC) is reported as a binder-free anode for flexible KIBs. With the combined advantages of rich active sites, highly accessible surface, highly conductive network, larger interlayer spacing as well as robust structural stability, this binder-free N, P-VG@CC anode exhibits high capacity (344.3 mAh g-1 ), excellent rate capability (2000 mA g-1 ; 46.5% capacity retention), and prominent long-term cycling stability (1000 cycles; 82% capacity retention), outperforming most of the recently reported carbonaceous anodes. Moreover, a potassium ion full cell is successfully assembled on the basis of potassium Prussian blue (KPB)//N, P-VG@CC, exhibiting a large energy density of 232.5 Wh kg-1 and outstanding cycle stability.

Flexible Zn-Ion Batteries: Recent Progresses and Challenges.

To keep pace with the increasing pursuit of portable and wearable electronics, it is urgent to develop advanced flexible power supplies. In this context, Zn-ion batteries (ZIBs) have garnered increasing attention as favorable energy storage devices for flexible electronics, owing to the high capacity, low cost, abundant resources, high safety, and eco-friendliness. Extensive efforts have been devoted to developing flexible ZIBs in the last few years. This work summarizes the recent achievements in the design, fabrication, and characterization of flexible ZIBs. Representative structures, such as sandwich and cable type, are particularly highlighted. Special emphasis is put on the novel design of electrolyte and electrode, which aims to endow reliable flexibility to the fabricated ZIBs. Moreover, current challenges and future opportunities for the development of high-performance flexible ZIBs are also outlined.

3D Hierarchical Nanorod@Nanobowl Array Photoanode with a Tunable Light-Trapping Cutoff and Bottom-Selective Field Enhancement for Efficient Solar Water Splitting.

Constructing 3D nanophotonic structures is regarded as an effective means to realize both efficient light absorption and efficient charge separation. However, most of the 3D structures reported so far enhance light trapping beyond the absorption onset wavelength, and thus greatly attentuate or even completely block the long-wavelength light, which could otherwise be efficiently absorbed by narrow-bandgap materials in a Z-scheme or tandem device. In addition, constructing a 3D conductive substrate often involves complex processes causing increased cost and upscaling problems. To overcome these shortcomings, a novel 3D hematite nanorod@nanobowl array nanophotonic structure is designed and fabricated by a low-cost method. This unique structure can enhance light absorption with tunable cutoffs and rationally concentrate photons right above the bowl bottom, enabling efficient charge separation. By loading NiFeOx as a cocatalyst, a high photocurrent density of 3.41 ± 0.2 mA cm-2 at 1.23 V versus reversible hydrogen electrode (RHE) can be obtained, which is 2.35 times that with a planar structure in otherwise the same system.

Co3 O4 @Cu-Based Conductive Metal-Organic Framework Core-Shell Nanowire Electrocatalysts Enable Efficient Low-Overall-Potential Water Splitting.

In the work reported herein, the electrocatalytic properties of Co3 O4 in hydrogen and oxygen evolution reactions have been significantly enhanced by coating a shell layer of a copper-based metal-organic framework on Co3 O4 porous nanowire arrays and using the products as high-performance bifunctional electrocatalysts for overall water splitting. The coating of the copper-based metal-organic framework resulted in the hybridization of the copper-embedded protective carbon shell layer with Co3 O4 to create a strong Cu-O-Co bonding interaction for efficient hydrogen adsorption. The hybridization also led to electronically induced oxygen defects and nitrogen doping to effectively enhance the electrical conductivity of Co3 O4 . The optimal as-prepared core-shell hybrid material displayed excellent overall-water-splitting catalytic activity that required overall voltages of 1.45 and 1.57 V to reach onset and a current density of 10 mA cm-2 , respectively. This is the first report to highlight the relevance of hybridizing MOF-based co-catalysts to boost the electrocatalytic performance of nonprecious transition-metal oxides.

Freeing the Polarons to Facilitate Charge Transport in BiVO4 from Oxygen Vacancies with an Oxidative 2D Precursor.

The BiVO4 photoelectrochemical (PEC) electrode in tandem with a photovoltaic (PV) cell has shown great potential to become a compact and cost-efficient device for solar hydrogen generation. However, the PEC part is still facing problems such as the poor charge transport efficiency owing to the drag of oxygen vacancy bound polarons. In the present work, to effectively suppress oxygen vacancy formation, a new route has been developed to synthesize BiVO4 photoanodes by using a highly oxidative two-dimensional (2D) precursor, bismuth oxyiodate (BiOIO3 ), as an internal oxidant. With the reduced defects, namely the oxygen vacancies, the bound polarons were released, enabling a fast charge transport inside BiVO4 and doubling the performance in tandem devices based on the oxygen vacancy eliminated BiVO4 . This work is a new avenue for elaborately designing the precursor and breaking the limitation of charge transport for highly efficient PEC-PV solar fuel devices.

Efficient Hydrogen Evolution on Cu Nanodots-Decorated Ni3S2 Nanotubes by Optimizing Atomic Hydrogen Adsorption and Desorption.

Low-cost transition-metal dichalcogenides (MS2) have attracted great interest as alternative catalysts for hydrogen evolution. However, a significant challenge is the formation of sulfur-hydrogen bonds on MS2 (S-Hads), which will severely suppress hydrogen evolution reaction (HER). Here we report Cu nanodots (NDs)-decorated Ni3S2 nanotubes (NTs) supported on carbon fibers (CFs) (Cu NDs/Ni3S2 NTs-CFs) as efficient electrocatalysts for HER in alkaline media. The electronic interactions between Cu and Ni3S2 result in Cu NDs that are positively charged and can promote water adsorption and activation. Meanwhile, Ni3S2 NTs are negatively charged and can weaken S-Hads bonds formed on catalyst surfaces. Therefore, the Cu/Ni3S2 hybrids can optimize H adsorption and desorption on electrocatalysts and can promote both Volmer and Heyrovsky steps of HER. The strong interactions between Cu and Ni3S2 cause the Cu NDs/Ni3S2 NTs-CFs electrocatalysts to exhibit the outstanding HER catalytic performance with low onset potential, high catalytic activity, and excellent stability.

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H+ and hamper the ability of H+ to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H+ from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

Designing Carbon Based Supercapacitors with High Energy Density: A Summary of Recent Progress.

Carbon based supercapacitors (CSCs), with high output power and long lifespan, are considered as promising power sources for modern electronic devices. The rush to find new approaches for optimizing their electrochemical behaviors is still vibrant, and particularly, widespread enthusiasm was focused on improving the energy density of CSCs through improving the specific capacitance and expanding the operating voltage. In this regard, this article provides a brief review about recent progress and new understanding about the assembly of CSCs with high energy density. Novel applied strategies were highlighted and discussed from the aspects of electrolyte, electrodes, and device modulation. Dynamic and mechanism factors associated with the energy storage process of CSCs are particularly emphasized. Finally, the opportunities and challenges are elaborated in the hope of guiding the promising direction for the design of high-energy CSCs.

Multiscale Pore Network Boosts Capacitance of Carbon Electrodes for Ultrafast Charging.

Increasing charge storage capability during fast charging (at ultrahigh current densities) has been a long-standing challenge for supercapacitors. In this work, a novel porous carbon foam electrode with multiscale pore network is reported that achieves a remarkable gravimetric capacitance of 374.7 ± 7.7 F g-1 at a current density of 1 A g-1. More importantly, it retains 235.9 ± 7.5 F g-1 (60% of its capacitance at 1 A g-1) at an ultrahigh current density of 500 A g-1. Electron microscopy studies reveal that this carbon structure contains multiscale pores assembled in a hierarchical pattern. The outstanding capacitive performance benefits from its extremely large surface area of 2905 m2 g-1, as around 88% of the electric charges are stored via electrical double layer. Significantly, electrochemical analyses show that the hierarchical porous structure containing macro-, meso-, and micropores allows efficient ion diffusion and charge transfer, resulting in the excellent rate capability. The findings pave the way for improving rate capability of supercapacitors and enhancing their capacitances at ultrahigh current densities.

Morphology and Doping Engineering of Sn-Doped Hematite Nanowire Photoanodes.

High-temperature activation has been commonly used to boost the photoelectrochemical (PEC) performance of hematite nanowires for water oxidation, by inducing Sn diffusion from fluorine-doped tin oxide (FTO) substrate into hematite. Yet, hematite nanowires thermally annealed at high temperature suffer from two major drawbacks that negatively affect their performance. First, the structural deformation reduces light absorption capability of nanowire. Second, this "passive" doping method leads to nonuniform distribution of Sn dopant in nanowire and limits the Sn doping concentration. Both factors impair the electrochemical properties of hematite nanowire. Here we demonstrate a silica encapsulation method that is able to simultaneously retain the hematite nanowire morphology even after high-temperature calcination at 800 °C and improve the concentration and uniformity of dopant distribution along the nanowire growth axis. The capability of retaining nanowire morphology allows tuning the nanowire length for optimal light absorption. Uniform distribution of Sn doping enhances the donor density and charge transport of hematite nanowire. The morphology and doping engineered hematite nanowire photoanode decorated with a cobalt oxide-based oxygen evolution reaction (OER) catalyst achieves an outstanding photocurrent density of 2.2 mA cm-2 at 0.23 V vs Ag/AgCl. This work provides important insights on how the morphology and doping uniformity of hematite photoanodes affect their PEC performance.

Activating CoOOH Porous Nanosheet Arrays by Partial Iron Substitution for Efficient Oxygen Evolution Reaction.

Iron-substituted CoOOH porous nanosheet arrays grown on carbon fiber cloth (denoted as Fex Co1-x OOH PNSAs/CFC, 0≤x≤0.33) with 3D hierarchical structures are synthesized by in situ anodic oxidation of α-Co(OH)2 NSAs/CFC in solution of 0.01 m (NH4 )2 Fe(SO4 )2 . X-ray absorption fine spectra (XAFS) demonstrate that CoO6 octahedral structure in CoOOH can be partially substituted by FeO6 octahedrons during the transformation from α-Co(OH)2 to Fex Co1-x OOH, and this is confirmed for the first time in this study. The content of Fe in Fex Co1-x OOH, no more than 1/3 of Co, can be controlled by adjusting the in situ anodic oxidation time. Fe0.33 Co0.67 OOH PNSAs/CFC shows superior OER electrocatalytic performance, with a low overpotential of 266 mV at 10 mA cm-2 , small Tafel slope of 30 mV dec-1 , and high durability.

Encapsulated Vanadium-Based Hybrids in Amorphous N-Doped Carbon Matrix as Anode Materials for Lithium-Ion Batteries.

Recently, researchers have made significant advancement in employing transition metal compound hybrids as anode material for lithium-ion batteries and developing simple preparation of these hybrids. To this end, this study reports a facile and scalable method for fabricating a vanadium oxide-nitride composite encapsulated in amorphous carbon matrix by simply mixing ammonium metavanadate and melamine as anode materials for lithium-ion batteries. By tuning the annealing temperature of the mixture, different hybrids of vanadium oxide-nitride compounds are synthesized. The electrode material prepared at 700 °C, i.e., VM-700, exhibits excellent cyclic stability retaining 92% of its reversible capacity after 200 cycles at a current density of 0.5 A g-1 and attractive rate performance (220 mAh g-1 ) under the current density of up to 2 A g-1 . The outstanding electrochemical properties can be attributed to the synergistic effect from heterojunction form by the vanadium compound hybrids, the improved ability of the excellent conductive carbon for electron transfer, and restraining the expansion and aggregation of vanadium oxide-nitride in cycling. These interesting findings will provide a reference for the preparation of transition metal oxide and nitride composites as well.

Enhanced Photoelectrochemical Activity by Autologous Cd/CdO/CdS Heterojunction Photoanodes with High Conductivity and Separation Efficiency.

The development for hydrogen from solar energy has attracted great attention due to the global demand for clean, environmentally friendly energy. Herein, autologous Cd/CdO/CdS heterojunctions were prepared in a carefully controlled process with metallic Cd as the inner layer and CdO as the interlayer. Further research revealed that the transportation and separation of photogenerated pairs were enhanced due to low resistance of the Cd inner layer and the type II CdO/CdS heterojunction. As a result, the optimized Cd/CdO/CdS heterojunction photoanode showed outstanding and long-term photoelectrochemical activity for water splitting, with a current density of 3.52 mA cm-2 , or a benchmark specific hydrogen production rate of 1.65 µmol cm-2 min-1 at -0.3 V versus Ag/AgCl, by using the environmental pollutants of sulfide and sulfite as sacrificial agents.

Boosting the Energy Density of Carbon-Based Aqueous Supercapacitors by Optimizing the Surface Charge.

The voltage of carbon-based aqueous supercapacitors is limited by the water splitting reaction occurring in one electrode, generally resulting in the promising but unused potential range of the other electrode. Exploiting this unused potential range provides the possibility for further boosting their energy density. An efficient surface charge control strategy was developed to remarkably enhance the energy density of multiscale porous carbon (MSPC) based aqueous symmetric supercapacitors (SSCs) by controllably tuning the operating potential range of MSPC electrodes. The operating voltage of the SSCs with neutral electrolyte was significantly expanded from 1.4 V to 1.8 V after simple adjustment, enabling the energy density of the optimized SSCs reached twice as much as the original. Such a facile strategy was also demonstrated for the aqueous SSCs with acidic and alkaline electrolytes, and is believed to bring insight in the design of aqueous supercapacitors.

Efficient Hydrogen Evolution Electrocatalysis Using Cobalt Nanotubes Decorated with Titanium Dioxide Nanodots.

TiO2 Co nanotubes decorated with nanodots (TiO2 NDs/Co NSNTs-CFs) are reported as high-performance earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. TiO2 NDs/Co NSNTs can promote water adsorption and optimize the free energy of hydrogen adsorption. More importantly, the absorbed water can be easily activated in the presence of the TiO2 -Co hybrid structure. These advantages will significantly promote HER. TiO2 NDs/Co NSNTs-CFs as electrocatalysts show a high catalytic performance towards HER in alkaline solution. This study will open up a new avenue for designing and fabricating low-cost high-performance HER catalysts.

Silica-Polypyrrole Hybrids as High-Performance Metal-Free Electrocatalysts for the Hydrogen Evolution Reaction in Neutral Media.

Constructing inorganic-organic hybrids with superior properties in terms of water adsorption and activation will lead to catalysts with significantly enhanced electrocatalytic activity in the hydrogen evolution reaction (HER) in environmentally benign neutral media. Herein, we report SiO2 -polypyrrole (PPy) hybrid nanotubes supported on carbon fibers (CFs) (SiO2 /PPy NTs-CFs) as inexpensive and high-performance electrocatalysts for the HER in neutral media. Because of the strong electronic interactions between SiO2 and PPy, the SiO2 uniquely serves as the centers for water adsorption and activation, and accordingly promotes the HER. The metal-free SiO2 /PPy NTs-CFs displayed high catalytic activity in the HER in neutral media, such as a low onset potential and small Tafel slope, as well as excellent long-term durability.