Replacing Oxygen Evolution with Hydrazine Borane Oxidation for Energy-Saving Electrochemical Hydrogen Production.

Electrochemical water splitting is a green strategy for hydrogen (H2) production but is severely hindered by the sluggish anodic oxygen evolution reaction (OER). Therefore, replacing the sluggish anodic OER with more favorable oxidation reactions is an energy-saving approach for hydrogen production. Hydrazine borane (HB, N2H4BH3) is considered a potential hydrogen storage material due to its easy preparation, nontoxicity, and high chemical stability. Furthermore, the complete electrooxidation of HB has a unique characteristic of a much lower potential compared to that of OER. All these make it an ideal alternative for energy-saving electrochemical hydrogen production, however, which has never been reported so far. Herein, HB oxidation (HBOR)-assisted overall water splitting (OWS) is proposed for the first time for energy-saving electrochemical hydrogen production. The as-synthesized NiCoP@CoFeP nanoneedle array catalyst exhibited superefficient OER, hydrogen evolution reaction (HER), and HBOR performance. Impressively, NiCoP@CoFeP serves as both anodic and cathodic electrocatalysts for HB-assisted OWS, only requires a low cell voltage of only 0.078 V to achieve a current density of 10 mA cm-2, which was 1.4 V lower than that for HB-free OWS, indicating the highly energy-saving H2 production.

Engineering Electronic and Morphological Structure of Metal-Organic-Framework-Derived Iron-Doped Ni2P/NC Hollow Polyhedrons for Enhanced Oxygen Evolution.

The rational design of an oxygen electrocatalyst with low cost and high activity is greatly desired for realization of the practical water-splitting industry. Herein, we put forward a rational method to construct nonprecious-metal catalysts with high activity by designing the microstructure and modulating the electronic state. Iron (Fe)-doped Ni2P hollow polyhedrons decorated with nitrogen-doped carbon (Fe-Ni2P/NC HPs) are prepared by a sequential metal-organic-framework-templated strategy. Benefiting from the strong electronic coupling, rapid charge-transfer capability, and abundant catalytic active sites, the obtained Fe-Ni2P/NC HPs exhibit an impressive electrocatalytic performance toward the oxygen evolution reaction (OER) with an ultralow overpotential of 228 mV at a current density of 10 mA cm-2 and a small Tafel slope of 33.4 mV dec-1, superior to the commercial RuO2 and most reported electrocatalysts. Notably, this catalyst also shows long durability with an almost negligible activity decay over 210 h for the OER. Combining density functional theory calculations with experiments demonstrates that the doped Fe and the incorporated carbon effectively modulate the electronic structure, enhance the conductivity, and greatly reduce the energy barrier of the rate-determining step in the process of OER. Thus, fast OER kinetics is realized. Moreover, this synthetic strategy can be extended to the synthesis of Fe-NiS2/NC HPs and Fe-NiSe2/NC HPs with excellent OER performance and long-term durability. This work furnishes an instructive idea in pursuit of nonprecious-metal materials with robust electrocatalytic activity and long durability.

Consecutive Nucleation and Confinement Modulation towards Li Plating in Seeded Capsules for Durable Li-Metal Batteries.

A dual modulation strategy of consecutive nucleation and confined growth of Li metal is proposed by using the metal-organic framework (MOF) derivative hollow capsule with inbuilt lithiophilic Au or Co-O nanoparticle (NP) seeds as heterogeneous host. The seeding-induced nucleation enables the negligible overpotential and promotes the inward injection of Li mass into the abundant cavities in host, followed by the conformal plating of Li on the outer surface of host during discharging. This modulation alleviates the dendrite growth and volume expansion of Li plating. The interconnected porous host network enables enhancement of cycling and rate performances of Li metal (a lifespan over 1200 h for Au-seeding symmetric cells, and an endurance of 220 cycles under an ultrahigh current density of 10 mA cm-2 for corresponding asymmetric cells). The hollow capsules integrated with lithiophilic seeds solve the deformation problem of Li metal for durable and long-life Li-metal batteries.

Robustness-Heterogeneity-Induced Ultrathin 2D Structure in Li Plating for Highly Reversible Li-Metal Batteries.

Anode interface modification is crucial for the stabilization of Li-metal batteries (LMBs), which have been considered as the most promising system for the electric vehicle market owing to their high energy density (500 W h kg-1). However, the biggest challenge for LMBs lies in the preservation of anode reversibility, including plated Li morphology control and dendritic Li inhibition during cycling. Here, we propose a nanostructure modulation strategy of Li grains and plating to activate the anode kinetics of LMBs without the compromise of anode stability. This modulation is triggered by the rapid deposition of ultrathin polydopamine coating on the Cu foil (PDA@Cu), which results in an unusual interlaced growth of vertical or lie-down two-dimensional Li nanoflakes on PDA. The high binding energy (>3 eV) between Li atoms and rich imino/carbonyl groups enables a superior lithiophilicity of PDA to homogenize the Li-ion flowing and Li-mass electroplating with negligible nucleation overpotential. The high Coulombic efficiency (98%) and low voltage hysteresis (∼20 mV) are stabilized for at least 300 cycles in the Li-PDA@Cu cell architecture. This PDA@Cu electrode can even tolerate much higher current densities of 5 and 10 mA cm-2 for 170 and 100 cycles, respectively. The interlaced network of Li nanosheets reinforces the electric contact and therefore charge transfer at the anode-electrolyte interface characterized by small interfacial resistance (<3 Ω cm2) and activation energy (0.28 eV). A viewpoint of robustness loss or mechanical heterogeneity in Li plating is discussed to disclose the evolution from column-like Li grains to porous Li sponges and then to compactly stacked Li nanoflakes with porosity shrinkage.

Population dynamics of Spodoptera litura (Lepidoptera: Noctuidae) on Bt cotton in the Yangtze River Valley of China.

Genetically modified cotton that produces a crystalline protein from Bacillus thuringiensis subsp. kurstaki (Berliner) (Bt) has been widely deployed to manage lepidopteran insect pests in cotton growing areas worldwide. However, susceptibility of different insect species to Bt protein varies, which may affect lepidopteran pest populations in the field. Studies on effects of two transgenic cotton lines (BG1560 and GK19) carrying a Cry1A gene on common cutworm Spodoptera litura F. (Lepidoptera: Noctuidae), were conducted during 2002-2005 in the cotton planting region of the Yangtze River valley of China. Results showed that common cutworm larvae had low susceptibility to Bt cotton. There was no significant difference in larval population densities in conventional and Bt cotton fields. However, the larval populations of the insect on conventional plants treated with chemical insecticides for control of target pest of Bt cotton were significantly lower than that in Bt cotton fields. These results indicated that the common cutworm was the potential to become a major and alarming pest in Bt cotton fields, and therefore efforts to develop an effective alternative management strategy are needed.

High-Capacity Mg-Organic Batteries Based on Nanostructured Rhodizonate Salts Activated by Mg-Li Dual-Salt Electrolyte.

A magnesium battery is a promising candidate for large-scale transportation and stationary energy storage due to the security, low cost, abundance, and high volumetric energy density of a Mg anode. But there are still some obstacles retarding the wide application of Mg batteries, including poor kinetics of Mg-ion transport in lattices and low theoretical capacity in inorganic frameworks. A Mg-Li dual-salt electrolyte enables kinetic activation by dominant intercalation of Li-ions instead of Mg-ions in cathode lattices without the compromise of a stable Mg anode process. Here we propose a Mg-organic battery based on a renewable rhodizonate salt ( e. g., Na2C6O6) activated by a Mg-Li dual-salt electrolyte. The nanostructured organic system can achieve a high reversible capacity of 350-400 mAh/g due to the existence of high-density carbonyl groups (C═O) as redox sites. Nanocrystalline Na2C6O6 wired by reduced graphene oxide enables a high-rate performance of 200 and 175 mAh/g at 2.5 (5 C) and 5 A/g (10 C), respectively, which also benefits from a high intrinsic diffusion coefficient (10-12-10-11 cm2/s) and pesudocapacitance contribution (>60%) of Na2C6O6 for Li-Mg co-intercalation. The suppressed exfoliation of C6O6 layers by a firmer non-Li pinning via Na-O-C or Mg-O-C and a dendrite-resistive Mg anode lead to a long-term cycling for at least 600 cycles. Such an extraordinary capacity/rate performance endows the Mg-Na2C6O6 system with high energy and power densities up to 525 Wh/kg and 4490 W/kg (based on active cathode material), respectively, exceeding the level of high-voltage insertion cathodes with typical inorganic structures.

Adult Exposure to Bt Toxin Cry1Ac Reduces Life Span and Reproduction of Resistant and Susceptible Pink Bollworm (Lepidoptera: Gelechiidae).

Insecticidal proteins from Bacillus thuringiensis (Bt) are used widely in sprays and transgenic plants to control insect pests. Although much research has elucidated the effects of Bt toxins on larvae, relatively little is known about their effects on adults. Here, we evaluated the effects of exposing adults to Bt toxin Cry1Ac on the life span and reproduction of two strains of pink bollworm ( Pectinophora gossypiella (Saunders)). In larval diet bioassays, the concentration of Cry1Ac killing 50% of larvae (LC 50 ) was 640 times higher for the laboratory-selected resistant strain (AZP-R) than the susceptible strain (APHIS-S). In experiments with adults, the highest concentrations of Cry1Ac tested (160 and 640 µg Cry1Ac per ml of 5% honey water) reduced life span for both strains. Treatments with 10, 40, and 160 µg Cry1Ac per ml reduced the duration of the oviposition period as well as the number of eggs laid by both strains, but did not affect the percentage of pairs producing eggs, the duration of the preoviposition period, or the percentage of eggs hatching for either strain. Adult life span did not differ between strains at low to moderate concentrations of Cry1Ac, but it was significantly greater for the resistant strain than the susceptible strain at the two highest concentrations of Cry1Ac tested. The reduced susceptibility to high concentrations of Cry1Ac in adults of the AZP-R strain relative to the APHIS-S strain provides the first evidence of expression of resistance to a Bt toxin in adult Lepidoptera.

Seasonal expression profiles of insecticidal protein and control efficacy against Helicoverpa armigera for Bt cotton in the Yangtze River valley of China.

Seasonal levels of Bacillus thuringiensis (Bt) insecticidal protein and its control efficacy against Helicoverpa armigera (Hübner) in Bt transgenic cotton GK19 (carrying a Cry1Ac/Cry1Ab fused gene) and BG1560 (carrying a Cry1Ac gene) were investigated in Tianmen County, Hubei Province, located in the Yangtze River valley of China, in 2001 and 2002. The results showed that the toxin content in Bt cotton changed significantly over time, and that the structure, growth stage, and variety were significant sources of variability. Generally, insecticidal protein levels were high during the early stages of cotton growth; they declined in mid-season, and rebounded in late season. On most dates sampled, the toxin contents in leaf, square, petal, and stamens (including nonovule pistil tissue) were much higher than those in ovule and boll. Compared with BG1560, the expression of Cry1Ac/Cry1Ab protein in GK19 was more variable during the whole growth period of cotton. The field evaluation on larval population dynamics of H. armigera in Bt and conventional cotton showed that the larval densities in BG1560 and GK19 fields decreased, respectively, 92.04 and 81.85% in 2001, and 96.84 and 91.80% in 2002.

Diminishing returns from increased percent Bt cotton: the case of pink bollworm.

Regional suppression of pests by transgenic crops producing insecticidal proteins from Bacillus thuringiensis (Bt) has been reported in several cropping systems, but little is known about the functional relationship between the ultimate pest population density and the pervasiveness of Bt crops. Here we address this issue by analyzing 16 years of field data on pink bollworm (Pectinophora gossypiella) population density and percentage of Bt cotton in the Yangtze River Valley of China. In this region, the percentage of cotton hectares planted with Bt cotton increased from 9% in 2000 to 94% in 2009 and 2010. We find that as the percent Bt cotton increased over the years, the cross-year growth rate of pink bollworm from the last generation of one year to the first generation of the next year decreased. However, as the percent Bt cotton increased, the within-year growth rate of pink bollworm from the first to last generation of the same year increased, with a slope approximately opposite to that of the cross-year rates. As a result, we did not find a statistically significant decline in the annual growth rate of pink bollworm as the percent Bt cotton increased over time. Consistent with the data, our modeling analyses predict that the regional average density of pink bollworm declines as the percent Bt cotton increases, but the higher the percent Bt cotton, the slower the decline in pest density. Specifically, we find that 95% Bt cotton is predicted to cause only 3% more reduction in larval density than 80% Bt cotton. The results here suggest that density dependence can act against the decline in pest density and diminish the net effects of Bt cotton on suppression of pink bollworm in the study region. The findings call for more studies of the interactions between pest density-dependence and Bt crops.

The halo effect: suppression of pink bollworm on non-Bt cotton by Bt cotton in China.

In some previously reported cases, transgenic crops producing insecticidal proteins from Bacillus thuringiensis (Bt) have suppressed insect pests not only in fields planted with such crops, but also regionally on host plants that do not produce Bt toxins. Here we used 16 years of field data to determine if Bt cotton caused this "halo effect" against pink bollworm (Pectinophora gossypiella) in six provinces of the Yangtze River Valley of China. In this region, the percentage of cotton hectares planted with Bt cotton increased from 9% in 2000 to 94% in 2009 and 2010. We found that Bt cotton significantly decreased the population density of pink bollworm on non-Bt cotton, with net decreases of 91% for eggs and 95% for larvae on non-Bt cotton after 11 years of Bt cotton use. Insecticide sprays targeting pink bollworm and cotton bollworm (Helicoverpa armigera) decreased by 69%. Previously reported evidence of the early stages of evolution of pink bollworm resistance to Bt cotton in China has raised concerns that if unchecked, such resistance could eventually diminish or eliminate the benefits of Bt cotton. The results reported here suggest that it might be possible to find a percentage of Bt cotton lower than the current level that causes sufficient regional pest suppression and reduces the risk of resistance.

Increased frequency of pink bollworm resistance to Bt toxin Cry1Ac in China.

Transgenic crops producing insecticidal proteins from Bacillus thuringiensis (Bt) kill some key insect pests, but evolution of resistance by pests can reduce their efficacy. The main approach for delaying pest adaptation to Bt crops uses non-Bt host plants as "refuges" to increase survival of susceptible pests. To delay evolution of pest resistance to transgenic cotton producing Bt toxin Cry1Ac, the United States and some other countries have required refuges of non-Bt cotton, while farmers in China have relied on "natural" refuges of non-Bt host plants other than cotton. The "natural" refuge strategy focuses on cotton bollworm (Helicoverpa armigera), the primary target of Bt cotton in China that attacks many crops, but it does not apply to another major pest, pink bollworm (Pectinophora gossypiella), which feeds almost entirely on cotton in China. Here we report data showing field-evolved resistance to Cry1Ac by pink bollworm in the Yangtze River Valley of China. Laboratory bioassay data from 51 field-derived strains show that the susceptibility to Cry1Ac was significantly lower during 2008 to 2010 than 2005 to 2007. The percentage of field populations yielding one or more survivors at a diagnostic concentration of Cry1Ac increased from 0% in 2005-2007 to 56% in 2008-2010. However, the median survival at the diagnostic concentration was only 1.6% from 2008 to 2010 and failure of Bt cotton to control pink bollworm has not been reported in China. The early detection of resistance reported here may promote proactive countermeasures, such as a switch to transgenic cotton producing toxins distinct from Cry1A toxins, increased planting of non-Bt cotton, and integration of other management tactics together with Bt cotton.