A Simple and Scalable Route to Synthesize Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 Yolk-Shell Microspheres, A High-Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production.

Yolk-shell structured micro/nano-sized materials have broad and important applications in different areas due to their unique spatial configurations. In this study, yolk-shell structured Co3 O4 @Co3 O4 is prepared using a simple and scalable hydrothermal reaction, followed by a calcination process. Then, Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microspheres are synthesized via adsorption and calcination processes using the as-prepared Co3 O4 @Co3 O4 as the precursor. A possible formation mechanism of the yolk-shell structures is proposed based on the characterization results, which is different from those of yolk-shell structures in previous study. For the first time, the catalytic activity of yolk-shell structured catalysts in ammonia borane (AB) hydrolysis is studied. It is discovered that the yolk-shell structured Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microspheres exhibit high performance with a turnover frequency (TOF) of 81.8 molhydrogen min-1 molcat -1 . This is one of the highest TOF values reported for a noble-metal-free catalyst in the literature. Additionally, the yolk-shell structured Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microspheres are highly stable and reusable. These yolk-shell structured Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microsphere is a promising catalyst candidate in AB hydrolysis considering the excellent catalytic behavior and low cost.

Multifunctional TiO2-C/MnO2 core-double-shell nanowire arrays as high-performance 3D electrodes for lithium ion batteries.

The unique TiO2-C/MnO2 core-double-shell nanowires are synthesized for the first time using as anode materials for lithium ion batteries (LIBs). They combine both advantages from TiO2 such as excellent cycle stability and MnO2 with high capacity (1230 mA h g(-1)). The additional C interlayer intends to improve the electrical conductivity. The self-supported nanowire arrays grown directly on current-collecting substrates greatly simplify the fabrication processing of electrodes without applying binder and conductive additives. Each nanowire is anchored to the current collector, leading to fast charge transfer. The unique one-dimensional core-double-shell nanowires exhibit enhanced electrochemical performance with a higher discharge/charge capacity, superior rate capability, and longer cycling lifetime.

Visible light-assisted hydrogen generation from ammonia borane over Z-Scheme NiO-CuO heterostructures.

The design and fabrication of cheap and high-efficiency catalysts for ammonia borane (AB) hydrolysis for hydrogen production is crucial for its commercial applications. Improvement of the catalytic performance of the catalysts with the assistance of sunlight, a costless resource, is extremely attractive. Herein, we have constructed Z-scheme heterostructured VO-NiO-CuO catalysts with strong interfacial electronic interactions and abundant oxygen vacancies to enhance hydrogen production from NH3BH3 solution under visible light illumination. The as-prepared VO-NiO-CuO catalysts exhibit excellent catalytic activity with a high turnover frequency (TOF) of 35.3 molH2 molcat.-1 min-1 toward AB hydrolysis under visible light. It is demonstrated that excellent catalytic performance is highly related to the effective separation and migration of charge on the catalyst surface. As a result, dual active sites were created, making it easier for various reactants to be adsorbed and activated on the catalyst surface. Furthermore, the density functional theory (DFT) calculations indicate that the adsorption and activation of H2O occurred mainly at the Ni site of VO-NiO-CuO. When the VO-NiO-CuO is irradiated with visible light, the photogenerated electrons assembled on the conduction band were transferred to the O atom through the Ni-O bond, which made the bond length of H2O molecules longer and OH bonds more prone to breaking, thus facilitating AB hydrolysis under illumination. The findings in this work pave the way to design novel and efficient heterostructured catalysts for fast hydrogen release from NH3BH3 under visible light irradiation.

Hydrothermal fabrication of quasi-one-dimensional single-crystalline anatase TiO2 nanostructures on FTO glass and their applications in dye-sensitized solar cells.

One-dimensional and quasi-one-dimensional semiconductor nanostructures are desirable for dye-sensitized solar cells (DSSCs), since they can provide direct pathways for the rapid collection of photogenerated electrons, which could improve the photovoltaic performance of the device. Quasi-1D single-crystalline anatase TiO(2) nanostructures have been successfully prepared on transparent, conductive fluorine-doped tin oxide (FTO) glass with a growth direction of [101] through a facile hydrothermal approach. The influences of the initial titanium n-butoxide (TBT) concentration, hydrothermal reaction temperature, and time on the length of quasi-1D anatase TiO(2) nanostructures and on the photovoltaic performance of DSSCs have been investigated in detail. A power conversion efficiency of 5.81% has been obtained based on the prepared TiO(2) nanostructure photoelectrode 6.7 µm thick and commercial N719 dye, with a short-circuit current density of 13.3 mA cm(-2) , an open-circuit voltage of 810 mV, and a fill factor of 0.54.

Organic dye bearing asymmetric double donor-π-acceptor chains for dye-sensitized solar cells.

A novel efficient metal free sensitizer containing asymmetric double donor-π-acceptor chains (DC) was synthesized for dye-sensitized solar cells (DSSCs). Comparing to 3.80%, 4.40% and 4.64% for the DSSCs based on the dyes with single chain (SC1, SC2) and cosensitizers (SC1 + SC2), the overall conversion efficiency reaches 6.06% for DC-sensitized solar cells as a result of its longer electron lifetime and higher incident monochromatic photon-to-current conversion efficiency.

Balanced capture and catalytic ability toward polysulfides by designing MoO2-Co2Mo3O8 heterostructures for lithium-sulfur batteries.

Lithium-sulfur (Li-S) batteries, as the next generation of energy storage systems, are currently limited by insufficient capture ability and sluggish catalytic reaction kinetics, thus leading to serve the shuttle effect of lithium polysulfides (LiPSs). Realizing the accelerated conversion of polysulfides in the cathode host of Li-S batteries is an effective way to improve its coulombic efficiency. The essence of fast conversion relies on enhanced oxidation reaction kinetics by virtue of the metal catalyst, but the generation of various intermediates exacerbate the complexity of the system and perplex the perfect operation of batteries relying on only one catalyst. In this work, the xMoO2:yCo2Mo3O8 heterostructures were designed, in which controlling the content of cobalt could balance the capture capability towards LiPSs by MoO2 and catalytic ability of liquid-solid conversion by Co2Mo3O8 catalytic sites. Therefore, utilizing synergy effect of MoO2-Co2Mo3O8 heterostructure enhances capture and catalytic ability toward polysulfides in Li-S batteries. As a result, the 9MoO2:2Co2Mo3O8-based cathode delivers excellent reversibility of 880 mA h g-1 after 100 cycles at 0.2C and 509 mA h g-1 after 1000 cycles at 1C with 0.056% capacity decay each cycle. This work provides a new method for synthesizing heterostructures by doping metals. Moreover, it promotes the understanding of balancing and promoting the capture capacity and catalytic conversion ability toward LiPSs.

Dual-Core Supercapacitor Yarns: An Enhanced Performance Consistency and Linear Power Density.

Pliable energy-storage devices have attracted great attention recently due to their important roles in rapid-growing wearable/implantable electronic systems among which yarn-shaped supercapacitors (YSCs) are promising candidates since they exhibit great design versatility with tunable sizes and shapes. However, existing challenges of YSCs include an inferior power output and poor performance consistency as compared to their planar counterparts, mainly due to their unique linear geometry and curved interfaces. Here, a YSC comprising wet-spun fibers of reduced graphene oxide and MXene sheets is demonstrated, which exhibits prominent decreases in the equivalent series resistance and thus increases in the power output upon increasing the length, which is contradictory to the common expectations of a typical YSC, showing revolutionary promises for practical applications. A much higher power density (2502.6 µW cm-2) can be achieved at an average energy density of 27.1 µWh cm-2 (linearly, 510.9 µW cm-1 at 5.5 µWh cm-1) via our unique dual-core design. The YSCs also present good stability upon stretching and bending, compatible with further textile processing. This work provides new insights into the fabrication of textile-based energy-storage devices for real-world applications.

Nonstoichiometric Cu0.6Ni0.4Co2O4 Nanowires as an Anode Material for High Performance Lithium Storage.

Transition metal oxide is one of the most promising anode materials for lithium-ion batteries. Generally, the electrochemical property of transition metal oxides can be improved by optimizing their element components and controlling their nano-architecture. Herein, we designed nonstoichiometric Cu0.6Ni0.4Co2O4 nanowires for high performance lithium-ion storage. It is found that the specific capacity of Cu0.6Ni0.4Co2O4 nanowires remain 880 mAh g-1 after 50 cycles, exhibiting much better electrochemical performance than CuCo2O4 and NiCo2O4. After experiencing a large current charge and discharge state, the discharge capacity of Cu0.6Ni0.4Co2O4 nanowires recovers to 780 mAh g-1 at 50 mA g-1, which is ca. 88% of the initial capacity. The high electrochemical performance of Cu0.6Ni0.4Co2O4 nanowires is related to their better electronic conductivity and synergistic effect of metals. This work may provide a new strategy for the design of multicomponent transition metal oxides as anode materials for lithium-ion batteries.

Correction: Lu, D., et al. MoO3-Doped MnCo2O4 Microspheres Consisting of Nanosheets: An Inexpensive Nanostructured Catalyst to Hydrolyze Ammonia Borane for Hydrogen Generation. Nanomaterials 2019, 9, 21.

In the original version of our article [...].

Hexagonal CuCo2O4 Nanoplatelets, a Highly Active Catalyst for the Hydrolysis of Ammonia Borane for Hydrogen Production.

Catalytic hydrolysis of ammonia borane (AB) has been considered as an effective and safe method to generate hydrogen. Development of highly active and low-cost catalysts is one of the key tasks for this technology. In this work, hexagonal CuCo2O4 nanoplatelets with a thickness of approximately 55 nm were prepared. In AB hydrolysis, those nanoplatelets exhibited ultrahigh catalytic activity with turnover frequency (TOF) of 73.4 molhydrogen min-1 molcat-1. As far as we know, this is one of the highest TOF values ever reported for non-noble metal catalysts. In addition, the effects of viscosity and different alkalis on the hydrolysis were also investigated. It is revealed that high viscosity of the reaction medium will retard the hydrolysis reaction. The presence of NaOH, KOH, and Na2CO3 in the reaction solution is favorable for hydrolytic process. In contrast, NH3·H2O will slow down the hydrolysis rate of ammonia borane. This work can provide some novel insight into the design of catalysts with both high performance and low cost. Besides, some findings in the present study can also offer us some information about how to improve the hydrolysis rates by optimizing the hydrolysis condition.

MoO3-Doped MnCo2O4 Microspheres Consisting of Nanosheets: An Inexpensive Nanostructured Catalyst to Hydrolyze Ammonia Borane for Hydrogen Generation.

Production of hydrogen by catalytically hydrolyzing ammonia borane (AB) has attracted extensive attention in the field of catalysis and energy. However, it is still a challenge to develop a both inexpensive and active catalyst for AB hydrolysis. In this work, we designed a series of MoO3-doped MnCo2O4 (x) catalysts, which were fabricated by a hydrothermal process. The morphology, crystalline structure, and chemical components of the catalysts were systematically analyzed. The catalytic behavior of the catalyst in AB hydrolysis was investigated. Among these catalysts, MoO3-doped MnCo2O4 (0.10) microspheres composed of nanosheets exhibited the highest catalytic activity. The apparent activation energy is 34.24 kJ mol-1 and the corresponding turnover frequency is 26.4 molhydrogen min-1 molcat-1. Taking into consideration the low cost and high performance, the MoO3-doped MnCo2O4 (0.10) microspheres composed of nanosheets represent a promising catalyst to hydrolyze AB for hydrogen production.

Substantially enhanced rate capability of lithium storage in Na2Ti6O13 with self-doping and carbon-coating.

Na2Ti6O13 (NTO) has recently been reported for lithium ion storage and showed very promising results. In this work, we report substantially enhanced rate capability in NTO nanowires by Ti(iii) self-doping and carbon-coating. Ti(iii) doping and carbon coating were found to work in synergy to increase the electrochemical performances of the material. For 300 cycles at 1C (1C = 200 mA g-1) the charge capacity of the electrode is 206 mA h g-1, much higher than that (89 mA h g-1) of the pristine NTO electrode. For 500 cycles at 5C the electrode can still deliver a charge capacity of 180.5 mA h g-1 with a high coulombic efficiency of 99%. At 20C the capacity of the electrode is 2.6 times that of the pristine NTO. These results clearly demonstrate that the Ti(iii) self-doping and uniform carbon coating significantly enhanced the kinetic processes in the NTO nanowire crystal, making it possible for fast charge and discharge in Li-ion batteries.

Core/Double-Shell Type Gradient Ni-Rich LiNi0.76Co0.10Mn0.14O2 with High Capacity and Long Cycle Life for Lithium-Ion Batteries.

A concentration-gradient Ni-rich LiNi0.76Co0.1Mn0.14O2 layered oxide cathode has been developed by firing a core/double-shell [Ni0.9Co0.1]0.4[Ni0.7Co0.1Mn0.2]0.5[Ni0.5Co0.1Mn0.4]0.1(OH)2 hydroxide precursor with LiOH·H2O, where the Ni-rich interior (core) delivers high capacity and the Mn-rich exterior (shells) provides a protection layer to improve the cyclability and thermal stability for the Ni-rich oxide cathodes. The content of nickel and manganese, respectively, decreases and increases gradually from the center to the surface of each gradient sample particle, offering a high capacity with enhanced surface/structural stability and cyclability. The obtained concentration-gradient oxide cathode exhibits high-energy density with long cycle life in both half and full cells. With high-loading electrode half cells, the concentration-gradient sample delivers 3.3 mA h cm(-2) with 99% retention after 100 cycles. The material morphology, phase, and gradient structure are also maintained after cycling. The pouch-type full cells fabricated with a graphite anode delivers high capacity with 89% capacity retention after 500 cycles at C/3 rate.

Solid-state-reaction synthesis of cotton-like CoB alloy at room temperature as a catalyst for hydrogen generation.

A novel room-temperature solid-state reaction is developed to synthesize cotton-like CoB alloy (CoBSSR) catalysts with a large specific surface area of 222.4m(2)g(-1). In the hydrolysis of ammonia borane catalyzed by the CoBSSR, the rate of hydrogen generation can reach 68.7mLmin(-1) with a turnover frequency (TOF) value of ca. 6.9Lhydrogenmin(-1)gcatalyst(-1) at 25°C. The TOF value is about 2 times as large as that of CoB alloy prepared by a regular solid-state reaction, which is also much higher than those of the CoB catalysts recently reported in the literature. The activation energy of the hydrolysis of ammonia borane catalyzed by the CoBSSR is as low as 22.78kJmol(-1), hinting that the CoBSSR possesses high catalytic activity, which may be attributed to the large specific surface area and the abundant porous structure. The high catalytic performance, good recoverability and low cost of the CoBSSR enable it to be a promissing catalyst condidate in the hydrolysis of ammonia borane for hydrogen production in commercial application.

Template-free TiO2 hollow submicrospheres embedded with SnO2 nanobeans as a versatile scattering layer for dye-sensitized solar cells.

Nanobean SnO2-embedded TiO2 hollow submicrospheres are presented as a scattering layer for the first time in dye-sensitized solar cells. This designed mesoporous submicrostructure simultaneously promotes dye adsorption, light harvesting, and electron transport, leading to 28% improvement in the conversion efficiency compared to film-based SnO2.

Self-supported single crystalline H2Ti8O17 nanoarrays as integrated three-dimensional anodes for lithium-ion microbatteries.

Well-ordered, one-dimensional H2Ti2O5, H2Ti8O17, TiO2-B, and anatase TiO2/TiO2-B nanowire arrays were innovatively designed and directly grown on current collectors as high performance three dimensional (3D) anodes for binder and carbon free lithium ion batteries (LIBs). The prepared thin nanowires exhibited a single crystalline phase with highly uniform morphologies, diameters ranging from 70-80 nm, and lengths of around 15 µm. Specifically, reversible Li insertion and extraction reactions around 1.6-1.8 V with initial intercalation capacities of 326 and 271 mA h g(-1) at a cycling rate of 0.1 C (where 1 C = 335 mA g(-1)) were observed for H2Ti8O17 and TiO2-B nanowire arrays, respectively. Among the four compounds investigated, the H2Ti8O17 nanowire electrode demonstrated optimal cycling stability, delivering a high specific discharge capacity of 157.8 mA h g(-1) with a coulombic efficiency of 100%, even after the 500th cycle at a current rate of 1 C. Furthermore, the H2Ti8O17 nanowire electrode displayed superior rate performance with rechargeable discharge capacities of 127.2, 111.4, 87.2, and 73.5 mA h g(-1) at 5 C, 10 C, 20 C, and 30 C, respectively. These results present the potential opportunity for the development of high-performance LIBs based on nanostructured Ti-based anode materials in terms of high stability and high rate capability.

Magnetic-field-induced deposition to fabricate multifunctional nanostructured Co, Ni, and CoNi alloy films as catalysts, ferromagnetic and superhydrophobic materials.

A novel and facile magnetic-field-induced deposition process was put forward to fabricate nanostructured Co, Ni and CoNi alloy films supported on Cu foil, which are multifunctional nanomaterials with wide applications in different areas due to their ferromagnetic and superhydrophobic properties, as well as their excellent catalytic performance.

Highly catalytic carbon nanotube/Pt nanohybrid-based transparent counter electrode for efficient dye-sensitized solar cells.

Low-cost transparent counter electrodes (CEs) for efficient dye-sensitized solar cells (DSSCs) are prepared by using nanohybrids of carbon nanotube (CNT)-supported platinum nanoparticles as highly active catalysts. The nanohybrids, synthesized by an ionic-liquid-assisted sonochemical method, are directly deposited on either rigid glass or flexible plastic substrates by a facile electrospray method for operation as CEs. Their electrochemical performances are examined by cyclic voltammetry, current density-voltage characteristics, and electrochemical impedance spectroscopy (EIS) measurements. The CNT/Pt hybrid films exhibit high electrocatalytic activity for I(-)/I(3)(-) with a weak dependence on film thickness. A transparent CNT/Pt hybrid CE film about 100 nm thick with a transparency of about 70% (at 550 nm) can result in a high power conversion efficiency (η) of over 8.5%, which is comparable to that of pyrolysis platinum-based DSSCs, but lower cost. Furthermore, DSSC based on flexible CNT/Pt hybrid CE using indium-doped tin oxide-coated polyethylene terephthalate as the substrate also exhibits η=8.43% with J(sc)=16.85 mA cm(-2), V(oc)=780 mV, and FF=0.64, and this shows great potential in developing highly efficient flexible DSSCs.

Dynamic study of highly efficient CdS/CdSe quantum dot-sensitized solar cells fabricated by electrodeposition.

An in situ electrodeposition method is described to fabricate the CdS or/and CdSe quantum dot (QD) sensitized hierarchical TiO(2) sphere (HTS) electrodes for solar cell application. Intensity modulated photocurrent spectroscopy (IMPS), intensity modulated photovoltage spectroscopy (IMVS) and electrochemical impedance spectroscopy (EIS) measurements are performed to investigate the electron transport and recombination of quantum dot-sensitized solar cells (QDSSCs) based on HTS/CdS, HTS/CdSe, and HTS/CdS/CdSe photoelectrodes. This dynamic study reveals that the CdSe/CdS cosensitized solar cell performs ultrafast electron transport and high electron collection efficiency (98%). As a consequence, a power conversion efficiency as high as 4.81% (J(SC) = 18.23 mA cm(-2), V(OC) = 489 mV, FF = 0.54) for HTS/CdS/CdSe photoelectrode based QDSSC is observed under one sun AM 1.5 G illumination (100 mW cm(-2)).