Molecular Wiring of Electrocatalytic Nitrate reduction to Ammonia and Water Oxidation by Iron-Coordinated Macroporous Conductive Networks.

Developing stable electrocatalysts with accessible isolated sites is desirable but highly challenging due to metal agglomeration and low surface stability of host materials. Here we report a general approach for synthesis of single-site Fe electrocatalysts by integrating a solvated Fe complex in conductive macroporous organic networks through redox-active coordination linkages. Electrochemical activation of the electrode exposes high-density coordinately unsaturated Fe sites for efficient adsorption and conversion of reaction substrates such as NO3 - and H2O. Using the electrode with isolated active Fe sites, electrocatalytic NO3 - reduction and H2O oxidation can be coupled in a single cell to produce NH3 and O2 at Faradaic efficiencies of 97 % and 100 %, respectively. The electrode exhibits excellent robustness in electrocatalysis for 200 hours with small decrease in catalytic efficiencies. Both the maximized Fe-site efficiency and the microscopic localization effect of the conductive organic matrix contribute to the high catalytic performances, which provides new understandings in tuning the efficiencies of metal catalysts for high-performance electrocatalytic cells.

Molecular Self-Assembly in Conductive Covalent Networks for Selective Nitrate Electroreduction to Ammonia.

Electrochemical nitrate (NO3-) reduction in aqueous media provides a useful approach for ammonia (NH3) synthesis. While efforts are focused on developing catalysts, the local microenvironment surrounding the catalyst centers is of great importance for controlling electrocatalytic performance. Here, we demonstrate that a self-assembled molecular iron catalyst integrated in a free-standing conductive hydrogel is capable of selective production of NH3 from NO3- at efficiencies approaching unity. With the electrocatalytic hydrogel, the NH3 selectivity is consistently high under a range of negative biases, which results from the hydrophobicity increase of the polycarbazole-based electrode substrate. In mildly acidic media, proton reduction is suppressed by electro-dewetting of the hydrogel electrode, enhancing the selectivity of NO3- reduction. The electrocatalytic hydrogel is capable of continuous production of NH3 for at least 100 h with NH3 selectivity of ∼89 to 98% at high current densities. Our results highlight the role of constructing an internal hydrophobic surface for electrocatalysts in controlling selectivity in aqueous media.

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia.

In the design of photoelectrocatalytic cells, a key element is effective photogeneration of electron-hole pairs to drive redox activation of catalysts. Despite recent progress in photoelectrocatalysis, experimental realization of a high-performance photocathode for multi-electron reduction of chemicals, such as nitrate reduction to ammonia, has remained a challenge due to difficulty in obtaining efficient electrode configurations for extraction of high-throughput electrons from absorbed photons. This work describes a new design for catalytic photoelectrodes using chromophore assembly-functionalized covalent networks for boosting eight-electron reduction of nitrate to ammonia. Upon sunlight irradiation, the photoelectrode stores a mass of reducing equivalents at the photoexcited chromophore assembly for multielectron reduction of a copper catalyst, enabling efficient nitrate reduction to ammonia. By introducing the new photoelectrode structure, it is demonstrated that the electronic interplay between charge photo-accumulating assembly and multi-electron redox catalysts can be optimized to achieve proper balance between electron transfer dynamics and thermodynamic output of photoelectrocatalytic systems.

Strong Tough Thermogalvanic Hydrogel Thermocell With Extraordinarily High Thermoelectric Performance.

Thermocells can continuously convert heat into electricity, and they are widely used to power wearable electronic devices. However, they have a risk of leakage and poor mechanical properties. Although quasi-solid ionic thermocells can overcome the issue of electrolyte leakage, the trade-off between their excellent mechanical properties and high thermopower remains a major challenge. In this study, stretching-induced crystallization and the thermoelectric effect are combined to propose a high-strength quasi-solid stretchable polyvinyl alcohol thermogalvanic thermocell (SPTC) with a large tensile strength of 19 MPa and high thermopower of 6.5 mV K-1 . The SPTC exhibits a high stretchability of 1300%, ultrahigh toughness of 163.4 MJ m-3 , and high specific output power density of 1969 µW m-2  K-2 . These comprehensive properties are superior to those of previously reported quasi-solid stretchable thermogalvanic thermocells. The use of SPTC-based systems in wearable devices for energy-autonomous strain sensors and health monitoring is demonstrated. This can facilitate the rapid implementation of sustainable wearable electronics in the Internet of Things era.

[Simulation of the responses of spring wheat yield to the rates and depths of nitrogen application in dryland based on APSIM model]. / 基于APSIM模型的旱地春小麦产量对施氮量和施氮深度的响应模拟.

Nitrogen limitation is an important factor for the improvement of crop water production potential in rain-fed areas of the Loess Plateau. The reasonable deep application of nitrogen fertilizer is a promising method to increase yield of rain-fed crop. Based on APSIM model, this study simulated spring wheat yield under different nitrogen application rates and depths, by using meteorological observation data from 1990 to 2020 in the semiarid areas of central Gansu Province, aiming to provide theoretical reference for optimizing wheat fertilization strategy. The results showed that the determination coefficient of simulated spring wheat yield, biomass and soil water content in 0-200 cm soil profile was greater than 0.80, the normalized root mean square error was less than 0.2, and the model validity index was greater than 0.5. These results indicated that the model had good fitting and adaptability in the test area. Across all the levels within the experimental design, increasing nitrogen application rates could significantly increase the yield of spring wheat in different precipitation years, and increasing nitrogen application depth could significantly increase spring wheat yield in wet and normal years, but had no effect in dry years. The rate and depth of nitrogen application had significant interaction effects on spring wheat yield in wet and normal years, but not in dry years. According to the binary quadratic regression fitting equation, when the potential maximum yield reached 2749 kg·hm-2 in wet year, nitrogen application depth was 22.7 cm, and nitrogen application rate was 245 kg·hm-2. When the maximum potential yield reached 2596 kg·hm-2 in normal year, nitrogen application depth was 20.6 cm, and nitrogen application rate was 235 kg·hm-2. Integrating the effects of nitrogen application rate and depth on yield, biomass and agronomic efficiency of nitrogen fertilizer, and farmer's fertilizer application habits, the recommended nitrogen application depth was 20-23 cm, and nitrogen application amount was 120-150 kg·hm-2, which could further improve water productivity and nitrogen use efficiency of spring wheat in arid areas of central Gansu Province.

[Effects of vertical rotary subsoiling with combined organic and inorganic fertilization on water use efficiency and yield of forage maize in a semi-arid area.] / åŠå¹²æ—±åŒºç«‹å¼æ·±æ—‹è€•å’Œæœ‰æœºæ— æœºè‚¥é æ–½å¯¹é¥²ç”¨çŽ‰ç±³æ°´åˆ†åˆ©ç”¨æ•ˆçŽ‡å’Œäº§é‡çš„å½±å“.

Both reasonable soil tillage and fertilization management play critical roles in improving the yield and water use efficiency (WUE) of forage maize in the semi-arid area of Loess Plateau. A field experiment was conducted at Dingxi experimental station of Gansu Academy of Agricultural Sciences between 2017 and 2019. We explored the effects of tillage method and fertilization type on yields and WUE of forage maize, as well as the economic benefits. There were four treatments in the experiment, including traditional rotary tillage + organic-inorganic fertilization (TOF), deep rotary tillage + organic-inorganic fertilization (DOF), and vertical rotary subsoiling + organic-inorganic fertilization (VROF), and the traditional rotary tillage + inorganic fertilization as the control (TF). Our results showed that, compared with DOF, TOF, TF, and VROF all decreased soil water storage in 0-300 cm soil layer at flowering stage, ranging from 16.9 mm to 79.9 mm, but they all increased soil water consumption by 9.7-22.4 mm during vegetative growing stages, 11.0-19.8 mm during reproductive stage in the dry years. Due to significant improvement in water absorption, VROF increased dry matter weight at maturity by 3.9%-13.4% compared to other treatments. Similarly, plant height, ear length, grain number per ear, 100-grain weight, and double ear rate under VROF were significantly increased, while bald head length was decreased significantly, when compared with other treatments. As a result, over the three experimental seasons, VROF increased the grain and biological yield by 4.3%-51.5% and 4.3%-25.7% compared to other treatments, respectively. Accordingly, WUE calculated by grain and biomass yields were increased by 2.7%-36.9% and 3.6%-13.5% under VROF, compared to other treatments. VROF increased the unit gross total output value and the net income by 5.1%-32.9% and 6.9%-80.5% respectively, compared to other treatments. These results demonstrated that VROF is a drought-resistant and yield-increasing farming technology for sustainable forage maize production in the semi-arid area of the Loess Plateau, Northwest China.

[Effects of optimal nitrogen fertilizer management on water and fertilizer utilization efficiency and yield under double-ridge-furrow sowing with the whole plastic film mulching in maize in a semi-arid area]. / åŠå¹²æ—±åŒºæ°®è‚¥è¿ç­¹å¯¹å ¨è†œåŒåž„æ²Ÿæ’­çŽ‰ç±³æ°´è‚¥åˆ©ç”¨å’Œäº§é‡çš„å½±å“.

Improper fertilization style is one of the main reasons for low water and fertilizer use efficiency of double-ridge-furrow sowing with the whole plastic film mulching in maize production in the semi-arid area. Understanding the effects of reduction, postponing, and organic fertilizer substitution of nitrogen fertilizer on water and fertilizer use efficiency and yield of maize can provide theore-tical basis for effective management of water and fertilizer in maize production. Based on a 4-year field experiment with three treatments: all fertilizers as base fertilizer under double-ridge-furrow sowing with the whole plastic film mulching (CK), nitrogen fertilizer reduced by 15% and topdres-sing in tasseling stage (RN), 30% of the chemical fertilizer replaced by organic fertilizer and topdressing in tasseling stage (RNM), we measured water consumption characteristics, growth and development, water and fertilizer utilization efficiency of maize. The results showed that fertilization pattern significantly affected water and fertilizer utilization efficiency and yield of maize, which was dependent on annual rainfall. In dry and normal rainfall year, water consumption in pre-flowering stage of RN was decreased by 16.1%-18.8% and that in post-flowering stage was increased by 18.0%-22.2%, while water consumption in pre-flowering and post-flowering stages of RNM did not differ from that in CK. In wet year, water consumption in pre-flowering stage of RN and RNM was decreased by 16.7% and 6.3%, while that in post-flowering stage was increased by 11.4% and 29.7%, respectively. Compared with CK, RN significantly increased the relative content of chlorophyll (SPAD) of maize leaves after topdressing, the biomass in post-flowering stage was increased by 15.6%-44.9%, the ear length, the number and weight of grains per spike and the 100-grain weight were increased significantly, yield was increased by 9.8%-17.0%, and water use efficiency (WUE) was increased by 6.3%-21.4%, with the partial productivities of fertilizer (PEPT), N (PEPTN), P (PEPTP) and K (PEPTK) were all increased significantly. In conclusion, RN could improve water consumption and the SPAD value in post-flowering stage of maize in different precipitation years, increase post-flowering biomass, and optimize the ear character, obviously improve yield, water and fertilizer use efficiency. It was a effective fertilizer management mode with high-efficiency utilization of water and fertilizer under double-ridge-furrow sowing with the whole plastic film mulching in maize in the semi-arid area.

[Effects of annual whole-film mulching on freezing-thawing characteristics, moisture, and temperature distribution of maize soil in semi-arid area]. / åŠå¹²æ—±åŒºå‘¨å¹´å ¨è†œè¦†ç›–å¯¹çŽ‰ç±³ç”°åœŸå£¤å†»èžç‰¹æ€§å’Œæ°´çƒ­åˆ†å¸ƒçš„å½±å“.

Based on a 3-year field experiment (2015-2017) with two treatments, annual whole-film mulching (PM) and uncovered (CK), we analyzed the relationship between soil temperature, moisture, and soil hydrothermal movement in semi-arid area. The results showed that freezing-thawing processes under both PM and CK were one-way freezing and two-way melting. Compared with CK, the freezing period in PM treatment was lagged, freezing rate was slowed down, freezing depth was 20 cm shallower, but melting rate was faster, and melting period was shortened by 6-7 days. In freezing period, soil temperature gradients of PM and CK were positive, with heat being transmitted toward top soil layer, and the conduction strength in PM treatment was greater than CK. During the melting period, soil temperature gradient of PM was also positive, with heat being transmitted toward upper soil layer, and that of CK was conversed. Soil water in PM treatment transported to upper soil layer during freezing-thawing period, but it appeared a "down-up-down" movement mode under CK in freezing period, "up-down" in thawing period. There was positively correlation between temperature and moisture gradient in the freezing period under both PM and CK treatments, with closer correlation in PM than CK. During melting period, soil temperature and moisture gradient was positively correlated in PM treatment with soil heat and moisture moved upward synchronously, while that in CK was negatively correlated with soil heat and moisture simultaneously moved to the lower layer soil. Driven by soil temperature and moisture gradient, soil temperature in 0-10 cm, 10-20 cm and 20-30 cm layers increased by 1.13-1.34 ℃, 0.96-1.24 ℃ and 0.89-1.32 ℃, while average soil water content increased by 3.4%-5.6%, 1.4%-2.2% and 6.7%-7.8%, respectively in PM treatment before sowing. Our results indicated that PM could provide water and heat protection for re-greening of winter crop and sowing, emergence and seedling of spring-sown crops in semi-arid areas.

[Effects of micro-ridge-furrow with plastic mulching and bunching seeding on soil hydrothermal environment and its response to photosynthesis and grain yield of spring wheat]. / å ¨è†œå¾®åž„æ²Ÿç©´æ’­å¯¹æ˜¥å°éº¦åœŸå£¤æ°´çƒ­çŽ¯å¢ƒçš„å½±å“åŠå ¶å ‰åˆå’Œäº§é‡æ•ˆåº”.

The relieving of drought and cold restriction on spring wheat development is one of the key factors increasing wheat yield in arid areas of central Gansu Province. A field experiment with spring wheat (Longchun No. 35) was carried out in central Gansu Province from 2016 to 2018. There were three treatments: 1) micro-ridge-furrow with whole field plastic mulching and bunching seeding (PRF), 2) whole field soil plastic mulching and bunching seeding (PMS), 3) bunching seeding without mulching (CK). We measured soil temperature in 0-25 cm profile, soil water content in 0-300 cm profile, leaf SPAD, photosynthetic rate, transpiration rate, aboveground biomass in different growth stages, and grain yield to understand the effect of PRF on soil hydrothermal environment, spring wheat yield and water use efficiency (WUE) from the aspect of soil hydrothermal, canopy development and grain yield. The results showed that mean soil temperature in 0-25 cm profile of PRF and PMS increased by 2.8 ℃ and 2.5 ℃ at the seedling stage, decreased by 1.4 ℃ and 0.9 ℃ from filling to maturity stage, respectively. Soil water storage in 0-300 cm profile of PRF and PMS increased by 59.7 mm and 41.8 mm from sowing to seedling stage. Water consumption of PRF and PMS increased by 46.1 mm and 39.8 mm from seedling to filling stage. PRF increased average soil temperature in 0-25 cm profile by 0.3 ℃ at seedling stage, but decreased by 0.5 ℃ from filling to maturity stage, and increased soil water storage in 0-300 cm profile by 18.0 mm from sowing to seedling stage. PMF increased water consumption by 13.0 mm from booting to maturing stage, as compared with PMS. Based on the optimizated soil hydrothermal conditions, leaf SPAD value, aboveground biomass, net photosynthetic rate, and transpiration rate of PRF increased, as compared with PMS and CK. The PRF increased grain yield by 9.1% and 36.5%, WUE by 5.9% and 30.8% compared to PMS and CK, respectively. Consequently, PRF increased soil temperature at wheat seedling stage, reduced it from filling to maturing stage, improved wheat water consumption from sowing to filling stage, increased leaf SPAD value and aboveground biomass, promoted photosynthetic function in leaf from seedling to filling stage, and consequently led to increased yield and water utilization. Such effects were more significant in dry year (2016 and 2017).

[Effects of organic fertilizer application on flag leaf C/N ratio, photosynthetic characteristics and yield of spring wheat with full plastic film mulching]. / å ¨è†œè¦†åœŸä¸‹æ–½æœ‰æœºè‚¥å¯¹æ˜¥å°éº¦æ——å¶ç¢³æ°®æ¯”ã€å ‰åˆç‰¹æ€§å’Œäº§é‡çš„å½±å“.

A field experiment was conducted in the rain-fed semi-arid region of central Gansu in 2016 and 2017, with the treatments 1) hill-drop flat planting with full plastic film mulching (PMS), 2) hill-drop flat planting with full plastic film mulching plus organic fertilizers (PMO), and 3) hill-drop flat planting without soil mulching (CK). We investigated the relations among soil moisture, photosynthetic rate (Pn), stomatal conductance (gs) and transpiration rate (Tr), C/N ratio, and total nitrogen of flag leaf from the heading stage to the seed-filling stage in different treatments to probe into their effects on the yield and yield components of spring wheat variety 'Longchun 27'. The results showed that organic fertilizer application could increase soil moisture at the middle and late growth stages of spring wheat. PMO increased soil water storage in 0-300 cm depth from the heading stage to the seed filling stage by 4.6% and 8.5%, decreased population canopy temperature by 0.1-1.3 ℃ and 1.4-4.9 ℃, increased net photosynthetic rate of flag leaf by 9.3% and 29.7%, stomatal conductance by 30.9% and 103.8%, transpiration rate by 5.1% and 55.0%, total nitrogen content by 6.6% and 18.9%, and decreased C/N ratio by 6.4% and 22.8%, respectively. Compared with PMS and CK, PMO significantly improved grain number per spike and 1000-grain weight, and increased grain yield by 9.1% and 53.7%, respectively. From the heading stage to filling stage, the Pn and gs of flag leaf had negative correlation with C/N, while C/N was negatively correlated with grain yield. Consequently, PMO could improve soil water storage and promote photosynthesis of flag leaf, reduce the intensity of physiological drought stress and the limitations of nitrogen absorption and assimilation in flag leaf from the heading stage to the seed-filling stage, and increase grain number and grain weight and consequently the yield of spring wheat in semi-arid region.